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Materials by design for energy applications

The discovery of new materials have always played a critical role in energy production, conversion and storage. Today, both the demand for new materials and the demands that these materials have to meet are greater than ever. Despite its importance, the discovery of new materials is often based on trial and error. The need for a more systematic approach to materials discovery combining modelling, experiment and big data approaches is urgent. High-throughput materials science shows great promise in this respect. These methodologies bring their own challenges such as: handling and generation of large datasets, Cross validation of experimental and theoretical high-throughput studies and the application of data-mining methods for discovering patterns in large data-sets.

With special focus on materials for energy applications, the symposium will cover state-of-the-art experimental and theoretical work aimed at meeting these challenges for designing new materials with specific properties.

The symposium will follow up on the successful 2014 symposium and will bring together design strategies from such diverse fields as battery materials, photo-voltaic materials, thermoelectric materials, fuel cell materials and power electronics. Furthermore, special focus will be put on interface dominated materials properties, for the understanding of realistic materials across the length scales.

Hot topics to be covered by the symposium:

  • Materials for energy harvesting and storage including
    - Battery materials
    - Photo-voltaic materials
    - Thermoelectric materials
    - Fuel cell materials
    - Power electronics
  • Interface dominated materials properties
  • Handling and generation of large datasets
  • Cross validation of experimental and theoretical high-throughput studies
  • Data-driven and knowledge based materials design
  • Kinetics and Materials by design

Invited speakers:

  • Anne de Baas (European Union, Bruxelles)
  • Gus Hart (Brigham Young University, USA)
  • Geoffroy Hautier (Université catholique de Louvain, Belgium)
  • Wolfram Jaegermann (TU Darmstadt, Germany)
  • Philippe Jund (Université Montpellier, France)
  • Normand Mousseau (Université de Montreal, Canada)
  • Vladan Stevanovic (NREL, USA)

Scientific committee:

  • Peter Blaha (TU Wien, Austria)
  • Stefano Curtarolo (Duke University, USA)
  • Isao Tanaka (Kyoto University, Japan)
  • Eric Toberer (Colorado School of Mines, USA)
  • Natalio Mingo (CEA Grenoble, France)
  • Ichiro Takeuchi (University of Maryland, USA)
  • Stefano Sanvito (Trinity College, Ireland)
  • Karl Sandeman (Imperial College, UK)
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Thermoelectrics : Gilles Dennler
Authors : P. Jund, K. Niedziolka, P. Hermet
Affiliations : ICGM - University of Montpellier

Resume : Adaptation of thermoelectric materials to industrial applications demands to design relatively complex materials. The search and optimization of these materials requires not only to have an in depth knowledge of their thermoelectric properties but also of other physical properties such as their mechanical and thermodynamical stability often linked to the presence of structural defects. Experimentally the study of these properties can often not be performed exhaustively and is sometimes difficult to tackle especially concerning the defects. This is where ab initio calculations can be of a precious help especially in permitting to select better materials in silico before going to the synthesis. In this presentation we will illustrate the input of first principles calculations on three aspects and on three different thermoelectric materials: - the influence of defects/dopants on the thermoelectric properties of ZnSb [1] - the phase stability of High Manganese Silicides (HMS) [2] - the mechanical and thermal properties of Ni-Ti-Sn half-Heusler and Heusler compounds [3] [1] P. Jund, R. Viennois, X. Tao, K. Niedziolka and J-C Tedenac, Physical Review B, 85, 224105 (2012) [2] A. Berche, J-C Tedenac and P Jund, Intermetallics, 47, 23-30 (2014) [3] P. Hermet, K. Niedziolka and P. Jund, RSC Advances, 3, 22176-22184 (2013); P. Hermet, R.-M. Ayral, E. Theron, P. G. Yot, F. Salles, M. Tillard and P. Jund , The Journal of Physical Chemistry C 118, 22405 (2014

Authors : Kristian Berland, Clas Persson
Affiliations : Centre for Materials Science and Nanotechnology (SMN), University of Oslo; Structure Physics, University of Oslo

Resume : An accurate theoretical description of transport and optical properties of energy materials generally require a very densely sampled Brillouin zone, such as in calculations based on the density functional theory (DFT). This demand limits the use of computationally-expensive state-of the arts methods such as hybrid functionals or GW approaches. To deal with this issue, we have developed an efficient and accurate interpolation scheme that builds on the extrapolative kp-method. Putting this new method to use, and considering a set of simple bulk thermoelectric materials, we find that a more accurate calculation with the hybrid functionals can significantly change the transport properties compared to the standard (semi-)local functional, beyond what is captured with a simple band gap widening. This new method can accelerate the use of more sophisticated methods in screening of energy materials.

Authors : Sandip Bhattacharya, Georg K.H. Madsen
Affiliations : ICAMS, Ruhr-Universitaet Bochum, Germany

Resume : Large scale utilization of thermoelectric materials is conceivable with the discovery of new highly efficient materials comprised of Earth abundant and non-toxic constituents. With the improvement of computational resources and simultaneously reliable ab-initio codes, high-throughput techniques can predict next-generation thermoelectrics. We will discuss our work on Half-Heuslers compounds . By combining defect thermochemistry and first-principles transport calculations, we can correctly predict the operating conditions which optimize the transport properties in thin-film TiNiSn [1]. We will then present a material design strategy based on Vegard's law to optimize the thermoelectric power factor (PF). This idea will be established in binary silicides/germanide-tin alloys [2]. We then identify the descriptors of a high PF and the underlying chemical bonding in Half-Heusler compounds and show how they can be automatically detected in high-throughput databases of electronic structure calculations. References: [1] M. Wambach, R. Stern, S. Bhattacharya, P. Ziolkowski, E. Mueller, G.K.H. Madsen and A. Ludwig, Adv. Electron. Mater., 1500208. doi:10.1002/aelm.201500208. [2] S. Bhattacharya and G.K.H. Madsen, Phys. Rev. B 92 (8), 085205 (2015).

Authors : Alexandra Zevalkink, Alim Ormeci, Matej Bobnar, Rodrigo Castillo, Ulrich Schwarz, Yuri Grin
Affiliations : Max Planck Institute for Chemical Physics of Solids, Dresden, Germany

Resume : Intermetallic Zintl phases, which form complex structures characterized bycovalently-bonded polyanions stabilized by surrounding cations, have emerged as promising thermoelectric materials. In particular, several compoundswith the layered CaAl2Si2 structure type show excellent p-type thermoelectric performance (zT> 1). Here we report on the reconstructive phase transformation ofSrAl2Si2from the CaAl2Si2 structure type into the ThCr2Si2 structure under high temperature and high pressure conditions. By cooling the materials under applied pressure in a walker type multi-anvil press, metastable samples are obtained, allowing direct comparison of the ambient and high pressure polymorphs using standard laboratory measurement techniques. By combining low temperature transport measurements anddensity functional calculations, this research provides a unique window into the relationship between the structure and properties of two ubiquitous and technologically important structure types.

Authors : Ronan Murphy, Eamonn Murray, Stephen Fahy, Ivana Savic
Affiliations : Tyndall National Institute, Cork, Ireland

Resume : Efficient thermoelectric energy conversion is highly desirable as 60% of the consumed energy is wasted as heat. Low lattice thermal conductivity is one of the key factors leading to high thermoelectric efficiency of a material [1]. The major obstacle in the design of materials with low lattice thermal conductivity is the difficulty in efficiently scattering phonons across the entire frequency spectrum [2]. Using first principles calculations, we show that driving PbTe materials to the brink of the ferroelectric phase transition to a rhombohedral structure could be a powerful strategy to solve this problem. We illustrate this concept by applying tensile [001] strain to PbTe and its alloys with another rock-salt IV-VI material, PbSe; and by alloying PbTe with a rhombohedral IV-VI material, GeTe. This induces extremely soft optical modes at the zone center, which increase acoustic-optical phonon coupling and decrease phonon lifetimes at all frequencies. We predict that PbTe, Pb(Se,Te) and (Pb,Ge)Te alloys driven close to the phase transition in the described manner will have considerably lower lattice thermal conductivity than that of PbTe (by a factor of 2-3). The proposed concept may open new opportunities for the development of more efficient thermoelectric materials. [1] G. J. Snyder and E. S. Toberer, Nature Mater. 7, 105 (2008). [2] K. Biswas et al. Nature 489, 414 (2012).

15:30 Coffee break    
Authors : Vladan Stevanovic
Affiliations : Colorado School of Mines, National Renewable Energy Laboratory, Golden, Colorado, United States

Resume : In the context of thermoelectric materials design the need to compute electron and phonon transport properties renders direct prediction of the thermoelectric figure of merit (zT) for large numbers of compounds untenable. In this talk I will discuss integrated theory-computations-experiment efforts in developing a robust set of materials descriptors that are computationally tractableto allow high-throughput materials searches. The starting point is the thermoelectric quality factor (β), a quantity that depends solely on intrinsic materials properties such as charge carrier mobility (μo), DOS effective mass (mDOS) and lattice thermal conductivity (κL). To overcome the limitations associated with direct calculations of μo and κL we develop semi-empirical models, motivated by the classic theories for electron-phonon and phonon-phonon scattering rates. This is done by combining only the quantities readily available from standard first-principles calculations with the large body of available experimental data. These models of transport properties are then combined into a semi-empirical descriptor termed βSE, which is demonstrated to correctly identify known thermoelectric materials. I will also discuss routes to predict the dopability of candidate materials, which will ultimately add to a more complete set of search criteria.

Authors : Kahyun Hur, Richard G. Hennig, Ulrich Wiesner
Affiliations : Center for Computational Science, Korea Institute of Science and Technology, Seoul, 136-791, Republic of Korea; Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611, US; Department of Materials Science and Engineering, Cornell University, Ithaca, NY, 14853, US

Resume : The control of thermal energy transport is highly important for efficient thermoelectrics and thermal insulation. Here we introduce a rational strategy to control thermal energy transport utilizing periodic nanostructures derived from bottom-up type self-assembly that allows facile and large-scale fabrication of three-dimensionally (3D) structured functional nanomaterials. We computationally identify 6 bicontinuous cubic network nanostructures with a phononic and investigate 3D nanostructure effects on thermal energy transport. The thermal conductivity is significantly reduced by phonon wave interferences in the nanostructures for low frequency phonons below 0.4 THz whose control by traditional techniques is usually ineffective. Further reduction can be achieved by the choice of 3D nanostructures with complete phononic bandgaps. Based on simulation results design rules to tailor network structures for improved thermoelectric properties are revealed. We expect that our strategy will stimulate experimental as well as further theoretical developments towards enhanced control of heat transmission in thermal devices.

Authors : Jiun-Yi Tseng1,2,*, Po-Wei Chi3, Cheng-Lung Chen2, Yuan-Tsung Chen4, Yung-Chi Lee2,Yu-Ze Chen1, Chih-Chung Lai1, Da-Hua Wei3, Yang-Yuan Chen2, Ming-Jye Wang2,5, Mau-Kuen Wu2,* and Yu-Lun Chueh1,*
Affiliations : 1Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, 30013, Taiwan; 2Institute of Physics, Academia Sinica, Taipei 11529, Taiwan; 3Institute of Manufacturing Technology and Department of Mechanical Engineering, National Taipei University of Technology (TAIPEI TECH), Taipei 10608, Taiwan; 4Graduate School of Materials Science, National Yunlin University of Science and Technology, 123 University Road,Section 3, Douliou, Yunlin 64002, Taiwan; 5Institute of Astronomy and Astrophysics, Academia Sinica, Taipei 106, Taiwan;

Resume : One main stream of thermoelectric (TE) material developments is that big efficiency is grained from small features in the nanostructured materials(ref 1). In this work, our novel strategy is that both of self-assembly Kirkendall nanovoids and metallic nanocrystals are developed within the TE thin films. This is the first time to report the porous (BiSb)2Te3 thin film with metallic Pt-based nanocrystals is successfully fabricated based on the Kirkendall effect by a designed and reliable combo approach of sputtering and heat treatment in vacuum. The created 0-D nanostructures are expected to affect the electronic carrier and thermal phonon transport effectively. The Seebeck coefficient of the sample with a thickness ratio (dBST/dpt) of ~34/3.6 has ~10% growth (S~196 μV/K at 300 K) compared with the BST single layer. According to the Pisarenko relation, the anomalous enhancement of the Seebeck coefficient in the nanocomposite BST thin film can be probably attributed to the carrier energy filtering in heterostructures. And TE power factor has a significant increase of ~40% (the maximum is about 1480 μW/K2-m at ~300 K) with the increase of the Seebeck coefficient and electrical conductivity. These results have demonstrated the feasibility of the porous TE materials based on the Kirkendall effect, as an effective energy-harvesting material, that is an important milestone to open a promising avenue for the advanced zero dimensional TE materials. Furthermore, this powerful approach will attempt to discover the next-generation TE materials with high-efficiency and low-cost.

Authors : Shashank MISHRA, Sylvie LE FLOCH, Guillaume BONNEFONT, Gilbert FANTOZZI, Stéphane PAILHES, Stéphane DANIELE
Affiliations : Université de Lyon, IRCELyon, CNRS, UMR 5256, F-69626 Villeurbanne, France Université de Lyon, ILM, CNRS, UMR 5306, F-69622 Villeurbanne, France INSA-LYON, MATEIS, CNRS, UMR 5510, F-69621 Villeurbanne, France

Resume : High-efficiency thermoelectric (TE) materials are important for power-generation devices that are designed to convert waste heat into electrical energy or to use in solid-state refrigeration. These applications require innovative materials which not only possess high conversion efficiency (related to high dimensionless number called figure of merit, "ZT" which is a combination of three material properties: Seebeck coefficient, electrical conductivity and thermal conductivity), but should also be no toxic and have high chemical stability in air, over a wide temperature range such as oxide materials. From last decade, a major breakthrough in the field of TE came by designing nanostructures that scatter phonons more effectively than electrons, so that the thermal conductivity is reduced more than the electrical conductivity. Herein we present a cheap and thermodynamically driven process to produce intra-granular nanostructures in bulk materials: the spinodal decomposition in the Nb5+-doped SnO2-TiO2 system via an original molecular approach. Such in-situ partitioning takes advantage to produce nanostructuration with coherent interfaces. While classical approach based on SnO2 (nano)powders mixing faces trouble to sinter dense ceramics, our innovative bottom-up approach, trough synthesis of mixed TixSn1-xO2 (x = 0.25; 0.5; 0.75) rutile nanoparticles, suppress pure SnO2 grains and allow full densification at low temperature by SPS process. Impact of the pressure, heating rate and soaking time of SPS process onto the densification, the nano-structuration and the dopant distribution will be addressed towards the thermoelectric properties.

Authors : Chungyeon Cho; Gregory Moriarty; Choongho Yu; Jaime C. Grunlan
Affiliations : Department of Mechanical Engineering, Texas A&M University, College Station, TX 77843-3123 (USA)

Resume : Low electrical conductivity (q) and thermopower (S) have long excluded polymers from thermoelectric applications. Carbon nanotube-filled polymers exhibit thermoelectric behavior (i.e., generate electricity via a thermal gradient), with electrical conductivity as high as 200,000 S/m and a reasonable S (35 – 70 uV/K). Power factors (PF = S2q) are as high as 500 uW m-1 K-2 for tcomposites containing carbon nanotubes stabilized by porphines and PEDOT:PSS, making them competitive with inorganic semiconductors (e.g., lead telluride) in terms of conversion efficiency. More recent work using layer-by-layer assembly will also be described. Sequential layering of PANi, graphene, and double walled carbon nanotubes produces films with increased carrier mobility. The resulting multilayer thin films exhibit a remarkable power factor (> 3000 uW m-1 K-2) that exceeds bulk bismuth telluride. This material can be applied like ink or paint, which could allow waste heat to be harnessed from exhaust manifolds or the body (from clothing).

Poster I : Ivano Castelli
Authors : Yonghe Li, Yujie Li, Yuefei Zhang, Zhenyu Wang, Haoyu Fu, Xiaona Zhang, Yanhui Chen, Hongzhou Zhang, Xiaodong Li
Affiliations : Institute of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing 100124, P. R. China School of Physics and Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2, Republic of Ireland Department of Mechanical and Aerospace Engineering, University of Virginia, Charlottesville, Virginia 22904, United States

Resume : For pseudocapacitors, the electrode material plays a vital role in the electrochemical properties. Among various electrode materials, spinel nickel cobaltite (NiCo2O4) has been widely investigated as an advanced electrode material owing to its better electronic conductivity (two orders of magnitude higher than conventional transition metal oxides), low cost, and high availability. With all the excitement about new electrode materials, less attention has been paid to their dynamic storage mechanism that commonly exhibit intriguing capacitive activation during charge/discharge cycling. Here, we report a simple and cost-effective approach to the synthesis of hierarchical mesporous Co3O4@NiCo2O4 nanoforests on Ni foam for supercapacitor (SC) electrode applications by a coupled one-step solution and annealing process. The synthesized electrode exhibits capacitive activation during charge-discharge cycling (from 0.73 F/cm2 of the pristine state to the peak value of 1.12 F/cm2 after 2000 cycles with only 1.8% loss compared to the peak capacitance after another 2000 cycles). Using ex situ TEM characterization and electrical test, We attribute such dynamic capacitive activation to (1) enlarged electroactive surface area through the formation of Co3O4@NiCo2O4 core-shell structure and (2) enhanced electrical conductivity by forming oxygen vacancies and hydroxyl groups during charge-discharge cycling. Our findings provide a scientific explanation for the capacitive activation in cobalt oxide-binary nickel cobaltite compounds, and a new design guideline for the development of capacitive activation enabled, high performance transitional oxide electrodes.

Authors : Bilal Ahmed, H. N. Alshareef
Affiliations : Materials Science and Engineering, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955–6900, Saudi Arabia

Resume : Recently, atomic layer deposition (ALD) has emerged as a promising and powerful technique to fabricate nanostructured electrodes and improve electrode/electrolyte interface in energy storage devices such as Li and Na ion batteries. In this project, we have deposited an electrochemically inert oxide material, hafnium oxide (HfO2), on different anode materials. We demonstrate that a nanoscale layer of HfO2 on zero dimensional (0D) SnO2 nanospheres, one dimensional (1D) MoO3 nanorods and two dimensional (2D) MoS2 nanosheets significantly improves the cyclic stability, when these materials were applied as anode in Li ion batteries. Moreover, HfO2 coated MoS2 nanosheets were tested as anode material in Na ion batteries and, after 50 charge/discharge cycles, HfO2 coated MoS2 electrodes retained 91% of the initial capacity and bare MoS2 electrodes retained only 63%. Most importantly, the mechanism of capacity retention was explained by ex situ high resolution transmission electron microscopy (HRTEM), electrical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and X-ray diffraction. We showed that capacity retention is directly related to the degree of crystallinity retention after charge/discharge process. For instance, in case of MoO3, ex-situ HRTEM analysis showed that after 50 charge/discharge cycles, the crystal structure of bare MoO3 electrodes degrades severely while HfO2 preserves the crystal structure during charge/discharge process. Furthermore, it was found that thickness and amorphous nature of HfO2 layer plays critical role because Li+ ions has to diffuse through this layer. In summary, a mechanistic insight into capacity retention after HfO2 coating has been provided by post – electrochemical ex-situ analysis.

Authors : Haidong Bian, Jie Zhang, Muk-Fung Yuen, Wenpei Kang, Yawen Zhan, Denis Y.W.Yu, Zhengtao Xu*, Yang Yang Li*
Affiliations : Center of Super-Diamond and Advanced Films (COSDAF), Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong, China; Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, China Centre for Advanced Structural Materials, City University of Hong Kong Shenzhen,Research Institute, 8 Yuexing 1st Road, Shenzhen Hi-Tech Industrial Park, Nanshan District, Shenzhen, China

Resume : We present a convenient, low-cost strategy to fabricate one-dimensional, vertically oriented nanoporous assembly of SnO2 upon a Cu substrate as a potentially promising anode system for Na-ion batteries application. The major novelty of the fabrication stage resides in anodizing a Sn/Cu bilayer film that is created by a facile cold-rolling procedure amenable to large-scale production. The open, nanoporous morphology of SnO2 facilitates the diffusion of electrolytes to access the SnO2 surface. The high porosity of the SnO2 phase also provides large void space to effectively accommodate the volume expansion/contraction during sodiation/desodiation. As a result, the 1-D nanoporous SnO2 thus assembled on the Cu substrate can be directly used as an effective electrode system for Na-ion storage--without the need for additives, dielivering a remarkable capacity of 326 mA h g-1 over 200 cycles at a current rate of 0.2 C.

Authors : Seokho Son, Young Jun Kwak, Hae Kyoung Kim, Seung Woo Lee
Affiliations : Seokho Son, Young Jun Kwak, Seung Woo Lee School of Chemical Engineering, Yeungnam University; Hae Kyoung Kim School of Materials Science and Engineering, Yeungnam University

Resume : Wholly aromatic sulfonated poly(arylene thioether sulfone) copolymers were synthesized usimg 3,3-disulfonate-4,4’-dichlorodiphenyl sulfone, 4,4’-dichlorodiphenylsulfone and 4,4’- thiobisbenzenethiol in the presence of potassium carbonate as a catalyst. Degree of sulfonation was controlled by feeding ratio of 3,3-disulfonate-4,4’-dichlorodiphenyl sulfone. The composition and incorporated sulfonic acid groups into the copolymers were confirmed by ¹H-NMR and Fourier transform infrared spectroscopy. To obtain the charateristics of the copolymers as polymer electrolyte membranes, the membranes were prepared from the solution casting of the synthesized polymers. In addition, ion exchange capacity (IEC), water uptake (WU) and ion conductivity were investigated by the composition of incorporated sulfonic acid groups. The WU value and IEC value of sulfonated copolymers is 8.12-38.0% and 0.4-1.95meq/g, respectively, depending on the composition of sulfonic acid groups. And the ion conductivity of the sulfonated copolymers is depending on the content of sulfonic acid groups.

Authors : 1.Jin-Jia Yang, 2.Chi-Young Lee, 3.Hsin-Tien Chiu
Affiliations : 1,3.Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan, R.O.C. ;2.Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan, R.O.C.

Resume : Li-O2 batteries have been attracting increasing attention in recent years owing to its extremely high specific energy density. The critical challenge of Li-O2 battery is the relatively low activity of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) which occur at the cathode. The low activity of ORR and OER may limit the electrochemical performance such as high charge and discharge overpotential, low round-trip efficiency, and a poor cycle life. To accelerate the OER and ORR, transition metal and metal oxide are employed in the cathode material of Li-O2 batteries as a bifunctional catalyst. In this work, a binder-free electrodes were fabricated through electrochemical deposition and post-annealing to grow NiCo2O4 on Ni foam. We avoid the use of binder because its carbon component would react with the discharge product Li2O2 to form Li2CO3, which results in bad electrochemical performance. On the other hand, the high abundance, low cost and high conductivity make NiCo2O4 a promising candidate for the cathode material of Li-O2 batteries. In this work, we tune the plating time to control the amount of NiCo2O4 deposited on the nickel foam. Their electrochemical performance are compared.

Authors : Yu-Xuan Wang1, Yi-Chun Chang1, Chi-Young Lee2, Hsin-Tien Chiu1
Affiliations : 1Department of Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan, R.O.C.; 2Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan, R.O.C.

Resume : High specific surface area TiO2 microspheres were synthesized through a simple solvothermal reaction. Due to the special biomolecular structures and outstanding self-assembling functions, we could use basic amino acid (arginine or monosodium glutamate) to assist the formation of TiO2 microspheres. Titanium tetrabutoxide Ti(OBu)4, used as the TiO2 precusor, together with absolute ethanol as the solvent were reacted in a heated Teflon stainless-steel autoclave. The as-synthesized TiO2 was further processed at 400 °C under air for 4h to obtain the anatase TiO2 microspheres. They were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and nitrogen adsorption-desorption analysis. SEM and TEM images showed the nanosheet spheres were prepared by arginine as the assisted molecule, and the formation of solid spheres were assisted by mixing arginine and monosodium glutamate. XRD spectra showed all the peaks of as-synthesized products were assigned to anatase TiO2. The nitrogen adsorption-desorption isotherms revealed specific surface areas were 108 m2/g for nanosheet spheres and 144 m2/g for solid spheres. The TiO2 microspheres were used as an anode for Na+ ion battery. The cells demonstrated a stable capacity reached 140.6 mAh/g after 100 discharge–charge cycles at a rate of 0.1 C. A good reversible performance and cycling stability were presented.

Authors : Do Van Lam, Kyungmin Jo, Chang-Hyun Kim, Sejeon Won, Hwangbo Yun, Jae-Hyun Kim, Hak-Joo Lee, Seung-Mo Lee
Affiliations : Do Van Lam, Nano Mechatronics, Korea University of Science and Technology (UST), 217 Gajeong-ro, Yuseong-gu, Daejeon 305-333, Korea; Kyungmin Jo, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Chang-Hyun Kim, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Sejeong Won, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Hwangbo Yun, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Jae-Hyun Kim, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Hak-Joo Lee, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea; Seung-Mo Lee, Korea Institute of Machinery & Materials (KIMM), 156 Gajungbukno, Yuseong-gu, Daejeon 305-343, Korea;

Resume : The ‘washability’ issue has still remained as a daunting goal in the field of current wearable electronics. It has been rarely dealt in literature although it is of prime importance, most likely due to great difficulty to resolve. Through this research, we would like to address that the calligraphy ink used as a writing and painting tool in East Asian cultural area for thousands years could provide a royal road for actualizing the wearable electrode with great washability. We prepared washable electrodes by simple dip coating of textiles with the calligraphy ink. It was observed that the electrical performance of the fabricated electrodes remains nearly unchanged even after several times of vigorous laundering using a regular washing machine. In addition, electrochemical capacitors made with those electrodes exhibited excellent cycling stability and high energy/power density. These results establish that the omnipresent calligraphic ink is simple yet powerful resources for fashioning normal textiles into washable and wearable electrodes for diverse electronic devices.

Authors : Hyun Ju, Myeongjin Kim, Kiho Kim, Jooheon Kim*
Affiliations : School of Chemical Engineering & Materials Science, Chung-Ang University, Republic of Korea

Resume : Bi2Te3 nanowire/graphene composites were fabricated with a wet chemical synthesis and sintering process, and their thermoelectric properties were investigated. The Bi2Te3 nanowires were evenly intercalated between the prepared graphene layers, forming the layered hybrid structure. These composites showed improved thermoelectric performances compared to the pristine graphene without Bi2Te3 nanowires. This was attributed to both the reduced lattice thermal conductivity, which is attributed to the exceptional phonon scattering at the interfaces between the nanowires and graphene layers, and the large Seebeck coefficient, which is intrinsic to the Bi2Te3 nanowires. The Bi2Te3 nanowire/graphene composite with a nanowire content of 20 wt.% produced a dramatically enhanced thermoelectric figure of merit (ZT) value of 0.2, which was ~27 times greater than that of the pristine graphene sample.

Authors : Chao-Wei Wu and Yuh-Renn Wu
Affiliations : Graduate Institute of Photonics and Optoelectronics, National Taiwan University

Resume : In this paper, the thermoelectric (TE) properties of the GaAs/AlAs super lattice with a ridge structure were studied. The ridge width is 25nm and the influence of smooth and rough surface at the sidewall of the ridge was investigated. Elastic continuum model was employed to calculate the phonon dispersion relation and the related phonon group velocity. The lattice thermal conductivity(kph), electrical conductivity, Seebeck coefficient, and electronic thermal conductivity are calculated by Boltzmann transport equations and relaxation time approximation. To verify our model, the results of thermal conductivity in the GaAs/AlAs SL structure are compared with published experimental results and a good agreement was obtained. Further optimization was applied by changing the SL structure with random arrangement and different surface roughness. The phonon surface roughness scattering shows strong influence on the TE properties. The optimal configuration of our proposed GaAs/AlAs SL structure is with 4 different layer thickness and the periodic length Lp is 11nm, surface roughness RMS=1.0nm, and auto-covariance length L=6.0nm. The lowest calculated kph is 0.23W/mK. At room temperature T=300K, ZT=0.84 is obtained at electron doping density ND=3.5x10^19 (cm^-3). Furthermore, ZT equal to 2.27 can be achieved at T=1000K with ND=3.06x10^19(cm^-3) for the ridge SL structure.

Authors : Jin Seo Park, Yoon Joon Park
Affiliations : Department of Advanced Materials Engineering, Kyonggi University

Resume : Li[Ni0.8Co0.15Al0.05]O2 is promising cathode material because of its high capacity. However, it has some weaknesses such as poor cyclic performance caused by thermal stability, low ionic and electronic conductivity for commercial usage. To overcome these problems, surface modification by coating is considered as effective approach. Surface coating using stable materials such as oxides and phosphates can suppress the unwanted side reactions between cathode and electrolyte. Herein, Li[Ni0.8Co0.15Al0.05]O2 was surface modified with stable solid electrolyte (oxide). The oxide with high ionic conductivity is expected to compensate for low ionic conductivity of the Li[Ni0.8Co0.15Al0.05]O2 cathode as well as stabilize the surface against the reactive electrolyte. So, the surface coating with solid electrolyte may result in enhanced electrochemical performance of Li[Ni0.8Co0.15Al0.05]O2 cathode such as improved cyclic performance, rate capability, and thermal stability.

Authors : Weidan An, Ling Liu, Yanfang Gao, Yang Liu, Jinrong Liu
Affiliations : College of Chemical Engineering, Inner Mongolia University of Technology

Resume : As a newly developing energy storage platform, supercapacitors have attracted much attention in recent decades because of their high electrochemical performance, high power density, long cycle lifetime, fast charge-discharge capability and low maintenance cost.[1,2] The use of electrode materials with high areal capacitance in supercapacitors shows advantages for power supply applications.[3] In this paper, a new electrode material consisting of Ni0.9Co1.92Se4 nanostructures grown on Ni foam has been synthesized via a simple and controlled two-step solvothermal method. This material is not only novel but also presents high electrochemical performance. The Ni0.9Co1.92Se4 nanostructures on Ni foam show a superior areal capacitance of 8.52 to 5.41 F·cm-2 under current densities from 3 to 50 mA·cm-2. Even after more than 1000 cycles at various high current densities, an areal capacitance of 5.17 F·cm-2 at 10 mA·cm-2 with 78.03% retention is achieved. Our results suggest that the new Ni0.9Co1.92Se4 nanostructured material may provide a good choice for supercapacitor applications. More importantly, the unique coral-like Ni0.9Co1.92Se4 nanostructures are composed of nanoparticles with sizes of a few tens of nanometres, which effectively increases the specific surface area, reduces the diffusion resistance of the electrolytes, and shortens the electron and ion transport pathways. Keywords: Ni0.9Co1.92Se4 nanostructures, double-transition-metals selenide, high areal capacitance, supercapacitors [1] Lou X W D, Archer L A, Yang Z. Advanced Materials, 2008, 20(21): 3987-4019. [2]Xinhui Xia, Jiangping Tu, Yongqi Zhang, Xiuli Wang, Changdong Gu, Xin-bing Zhao, Hong Jin Fan. ACS nano, 2012, 6(6): 5531-5538. [3] Jiang H, Lee P S, Li C. Energy & Environmental Science, 2013, 6(1): 41-53.

Authors : D. Flahaut1, J. Allouche1, A. Sotelo2, Sh. Rasekh2, M. A. Torres2, M. A. Madre2, J. C. Diez2
Affiliations : 1IPREM, Université de Pau, Hélioparc Pau Pyrénées, 2 av. Angot, 64053 Pau cedex 9, France 2Instituto de Ciencia de Materiales de Aragón, ICMA (CSIC-Universidad de Zaragoza), Mª de Luna, 3. 50018 Zaragoza, Spain

Resume : Misfit textured thermoelectric ceramics (TE) have been successfully grown from the melt, using the laser floating zone method. A high power factor value (0.30 mW/(K2.m) at 650 ºC) is obtained for the Bi2Ca2Co1.7Ox-4 wt.% Ag containing samples. To better understand the role of silver on the thermoelectric properties, we performed systematical investigations by combining SEM/XPS/AES techniques on cross-cut sections of Bi2Ca2Co1.7Ox-x wt.% Ag materials. All doped materials exhibit four phases assigned to the thermoelectric Bi2Ca2Co1.7Ox phase, the secondary (Bi3CaOy and CoO) phases and Ag domains. The microstructure has shown a reduction of the amount of secondary phases for Ag contents up to 4 wt.%. High resolution AES chemical analysis provided a Bi-Ca-Co-Ag overlay map where metallic Ag inclusions (B.E. Ag 3d5/2 = 367.8 eV) are clearly identifiable among all other Bi, Ca and Co rich domains. Moreover, a mixed valency of the cobalt has been observed for the 4 wt.% Ag sample. This microstructural evolution leads to a decrease of the electrical resistivity values until an Ag content of 4 wt.%, whereas Seebeck coefficient has been maintained unchanged. This is in agreement with the presence of metallic Ag in all samples, confirmed by X-ray photoelectron and Auger spectroscopy. In this communication, we demonstrate the efficiency of XPS/AES/SAM coupling techniques for the investigation of nanostructures TE materials.

Authors : Sung Hoon Ha, Chae Won Lee, Tae-Geun Kang, Chang Sun Lee, Ye Yeong Hwang and Yun Jung Lee
Affiliations : Department of Energy Engineering, Hanyang University, Korea

Resume : In the past, only the performance of electronic devices was important. In these days, however, electronic equipment is regarded as one of the fashion items to express individuals and required to satisfy the design needs as well as device’s original purpose. The biggest barrier to the design versatility of electronic equipment is the battery's limited shape. To overcome this limitation, there are many active researches on flexible batteries recently. However, these researches mostly focus on two-dimensional forms and have several weaknesses, such as limited physical flexibility, an incommodious wearing sensation and limited design flexibility. As a fully wearable battery with comfortable wearing sensation, fibrous battery that can be knitted or weaved into desired shape might be suitable. For this purpose, we introduce an all-in-one electrode thread concept with enhanced flexibility and mechanical stability. The strategies include improving flexibility of active materials, enhancing interface adhesion, and adopting lightweight and flexible core current collectors. The monolith electrode threads of the anode and the cathode were fabricated by coating the carbon fiber core with the active material shell and subsequently with a thin-film membrane. The cathode thread and the anode thread showed a linear capacity of 0.1 mAh cm-1 and 0.5 mAh cm-1, respectively. They also showed stable electrochemical characteristics in a bended state at a bending radius below 5 mm.

Authors : Tae-Geun Kang, Sung Hoon Ha, Chae Won Lee, Chang Sun Lee, Ye Yeong Hwang, and Yun Jung Lee
Affiliations : Department of Energy Engineering, Hanyang University, Korea

Resume : Although the high theoretical specific capacity of lithium oxygen (Li-O2) battery is extremely beneficial, low energy efficiency resulting from the large potential gap between discharge and charge makes this system impractical. Previously, numerous reports have explored catalysts such as noble metal (Ru, Ir, Pt, Pd) and their derivatives (RuO2, IrO2). However, noble metal based catalysts can hardly overcome their inherent weakness on the cost efficiency. Therefore, a low cost catalyst with acceptable performance is essential for the Li-O2 battery. In this research, we focused on iron cobalt bimetal decorated carbon nanotube (FeCo-CNT) composite as a catalytic air cathode material for Li-O2 batteries. Li-O2 battery using FeCo-CNT air electrodes showed higher efficiency (72.15 %) than that of pristine CNT (62.57 %) and higher capacity (3600 mAh g-1 vs 1276 mAh g-1) at the full discharge test until 2.4 V. Also FeCo-CNT presented better stability upon cycling compared to the pristine CNT. Since the clogging problems resulting from the incomplete decomposition of Li2O2 have been improved the voltage profile of the FeCo-CNT cathode were stable during 50 cycles. Spectroscopic and electron microscope analyses supported that the improved cell performance is attributed to the catalytic effect of FeCo.

Authors : R. I. Eglitis
Affiliations : Institute of Solid State Physics, University of Latvia, 8 Kengaraga Str., Riga LV1063, Latvia

Resume : Due to the rapid development of computers and forefront research methods, it is now possible to use a quantum mechanical electronic structure theory of solids to obtain, completely from first principles, the average battery voltage based on intercalation reaction energetics. The results of ab initio calculations by means of the full potential linearized augmented plane wave (FP-LAPW) method, using the computer code WIEN2k, for spin-polarized mixtures of Li2CoxMn4-xO8 (x=0, 1, 2, 3 and 4), treating exchange and correlation effects within the GGA approximation are presented. The calculated average battery voltage for Li2CoMn3O8 cathode material is around 5 Volts [1,2]. The ab initio calculation result for a 5 V average battery voltage perfectly describes recently experimentally-synthesized LiCo0.5Mn1.5O4 battery cathode material, which showed a discharge plateau starting at around 5 V. The calculated average battery voltages for other x values in the mixture Li2CoxMn4-xO8 (x=0, 2, 3 and 4) (3.95 V; 4.47 V; 4.19 V and 3.99 V) are considerably below 5 Volt. References: 1. R. I. Eglitis and G. Borstel, Phys. Stat. Sol. A 202, R13 (2005). 2. R. I. Eglitis, Physica Scripta 90, 094012 (2015).

Authors : Yang Liu, Yanfang Gao,*
Affiliations : College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot, 010051, P.R. China

Resume : Innovative energy storage technology lies at the heart of the advances that have already been made in energy conversion and storage devices, for example the introduction of supercapacitors. They can operate at high charge and discharge rates over an almost unlimited number of cycles and realize energy recovery, and therefore are gaining increasing popularity in high power energy storage applications.[1] To build high performing supercapacitor electrodes, one should know whether the increase in capacitance is due only to reduce the dimensions of electrode materials down to the nanoscale level, or if the spatial structure also plays a role.[2] Herein, nickel foam as an ideal electrode architecture, which consists of a 3D interconnected network of electronic transmission. More interesting, uniform nano carbon particles (~20 nm) will be generated and can be well distributed on the surface of nickel substrate in a candle flame.[3] The synthesized carbon particles consisted of a unique structure of 3D chain-like interconnected struts with highly wrinkled surfaces. Unlike other fabrication methods of supercapacitor electrodes, the processing described in this work is fast and straightforward, with no toxicity. Electrochemical measurements indicated that the flame-spray processing of supercapacitors obtained a high electric double layer capacitance (236.8 F g-1 at 0.3 A g-1) and excellent cycling stability (only 3% loss was observed after 10000 cycles at 5 A g-1), which are much higher than the electrodes fabricated by a traditional binder-bearing technique. References [1] K. Xie, B. Wei, Advanced Materials 2014, 26, 3592. [2] Q. Zhang, E. Uchaker, S. L. Candelaria, G. Cao, Chemical Society Reviews 2013, 42, 3127. [3] H. Liu, T. Ye, C. Mao, Angewandte Chemie International Edition 2007, 46, 6473.

Authors : Gi-Hun Nam, Cheol-Min Park*
Affiliations : School of Materials and Engineering, Kumoh National Institute of Technology

Resume : The antimony selenide (Sb2Se3) and its nanostructured composite (Sb2Se3/C) were prepared by a simple solid state synthetic route, and their potential as electrode materials for rechargeable Li-ion and Na-ion batteries was investigated. The electrochemical reaction mechanism was investigated using ex situ X-ray diffraction (XRD) and EXAFS analyses. Interesting recombination reactions between Sb2Se3 and Li/Na were demonstrated. Additionally, XRD and high resolution transmission electron microscopy confirmed that the amorphous Sb2Se3/C composites consisted of uniformly distributed amorphized Sb2Se3 within amorphous carbon metrics. The amorphous Sb2Se3/C composites electrode showed good electrochemical performances such as a high initial coulombic efficiency of ca. 81% and long cycle retention of 652 mA h g-1 after 100th cycle for Li-ion batteries. Additionally, the electrode was applied to Na-ion batteries, it also showed promising electrochemical performances with high discharge capacity of 406 mA h g-1 and a long capacity retention of ca. 88% after 80th cycle. "This research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under the C-ITRC(Convergence Information Technology Research Center) (IITP-2015-H8601-15-1011) supervised by the IITP(Institute for Information & communications Technology Promotion)"

Authors : Geon-Kyu Sung, Cheol-Min Park
Affiliations : Materials science and Engineering, Kumoh National Institute of Technology ;Materials science and Engineering, Kumoh National Institute of Technology

Resume : A new Li-Te battery system with a redox potential of ~1.7V (vs. Li /Li) adapted on a Li metal anode and an advanced Te/C nanocomposite, prepared by a simple solid state route was investigated. Mechanically reduced Te/C electrode using a simple concept of transforming TeO2 into nanocrystalline Te shows good electrochemical performances. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) reveal that the Te/C nano composite is composed of nano-sized Te and amorphous C. The electrochemical reaction mechanism of the Te/C nano composite electrode is identified by ex situ XRD analyses combined with a differential capacity plot. Reduced Te/C cathode for Li-Te secondary battery system has a high energy density (initial discharge/charge : 1088/740 mA h cm-3), excellent cyclability (ca. 705 mA h cm-3 over 100 cycles), and fast rate capability (ca. 550 mA h cm-3 at 5C rate). "This research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under the C-ITRC(Convergence Information Technology Research Center) (IITP-2015-H8601-15-1011) supervised by the IITP(Institute for Information & communications Technology Promotion)"

Authors : Dong-Hun Lee, Cheol-min Park*
Affiliations : Shcool of Advanced Materials&System Engineering, Kumoh National Institute of Technology

Resume : The SnSe-C nanocomposites, prepared by a simple mechanical solid-state synthesis technique and heat treatment with polyvinyl chloride, were investigated as high-capacity anode materials for rechargeable Li-ion batteries. The SnSe-C nanocomposites were confirmed by X-ray diffraction (XRD) and high-resolution transmission electron microscopy. The SnSe-C nanocomposite electrode showed excellent electrochemical performances, such as a high initial charge capacity of 885 mAh g-1, good initial Coulombic efficiency of ca. 81.8 %, and long capacity retention of 618 mAh g-1 after 200 cycles, fast rate capability (2C: 583 mAh g-1, 3C: 450 mAh g-1). Additionally, the electrochemical reaction mechanisms of SnSe and SnSe-C nanocomposites were thoroughly demonstrated by ex-situ XRD and extended X-ray absorption fine structure. "This research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under the C-ITRC(Convergence Information Technology Research Center) (IITP-2015-H8601-15-1011) supervised by the IITP(Institute for Information & communications Technology Promotion)"

Authors : Ah-Ram Park, Cheol-Min Park*
Affiliations : School of Materials Science and Engineering, Kumoh National Institute of Technology

Resume : SnTe and its nanocomposite (SnTe/C) were synthesized through a simple solid state synthesis method using Sn and Te powders. SnTe and SnTe/C nanocomposites were confirmed by X-ray diffraction (XRD), high-resolution transmission electron microscopy. Furthermore, the reaction mechanism of SnTe as anode material for Lithium-ion batteries was thoroughly investigated on the basis of ex-situ XRD and extended X-ray absorption fine structure analyses. SnTe/C nanocomposites electrode showed good electrochemical performances, such as a high initial dicharge and charge capacity of 873.8 and 622.83 mAh g-1, good initial Coulombic efficiency of ca. 76 %, and long capacity retention of 647.3 mAh g-1 after 100 cycles. "This research was supported by the MSIP(Ministry of Science, ICT and Future Planning), Korea, under the C-ITRC(Convergence Information Technology Research Center) (IITP-2015-H8601-15-1011) supervised by the IITP(Institute for Information & communications Technology Promotion)"

Authors : Seung-Su Lee, Cheol-Min Park*
Affiliations : School of Materials Science and Engineering, Kumoh National Institute of Technology

Resume : The amorphous SiO2-based composite, prepared by a simple solid-state synthetic technique, was investigated as high-capacity anode materials for rechargeable Li-ion batteries. The amorphous SiO2-based composite was confirmed by X-ray diffraction (XRD) and fourier-transform infrared reflection (FTIR). The amorphous SiO2-based composite electrode showed excellent electrochemical performances, such as a high initial charge capacity of 990 mAh g-1, good initial Coulombic efficiency of ca. 74 %, and long capacity retention of 717 mAh g-1 after 200 cycles. Additionally, its electrochemical reaction mechanism was thoroughly demonstrated using various analytical methods. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIP) (NRF- 2014R1A2A1A11053057).

Authors : Jeongmin Park, Jae hyun Cho, Byungwon Cho, Heonjin Choi
Affiliations : Department of Materials Science and Engineering Yonsei University, Center for Energy Convergence KIST

Resume : Lithium ion batteries (LIBs) are used as the power sources for many electronic systems from portable electronic devices to electric vehicles. Meanwhile, graphite has been used as the anode material for LIBs by virtue of its low working voltage and good cycle ability. However the theoretical capacity of carbon is limited to 372mA/g and therefore, alternative anode materials with the higher capacity have to be developed. Regarding this, silicon (Si) has been proposed to replace the graphite due to its high theoretical capacity of 4,200mA/g. Meanwhile, most of Si anode materials have been suffered a capacity fading with lithium intercalation due to volume expansion and amorphization. Regarding this, nanostructured materials have been studied because of the potential for relaxing mechanical stress during lithium insertion/ extraction process. In this study, we explored Si nanosheets as anodes materials for LIBs. The Si nano-sheets with thickness and diameter of < 2 nm and > 2 m, were grown on graphite foil by chemical vapor deposition process. A half-cells tests were carried out using Si nanosheet as anode. The half-cells test showed reversible crystalline-amorphous phase transition that can accommodate the stresses and high cycle ability over 350 cycles. The advantages of Si nanosheets as stress durable anode materials will be discussed in terms of their size and morphology.

Authors : Zeynel Ozturk, Samed Sertac Seyitoglu, Ali Kiliçarslan
Affiliations : Hitit University, Engineering Faculty, Department of Chemical Engineering, Corum, 19030, Turkey; Hitit University, Faculty of Engineering, Department of Mechanical Engineering, Corum, 19030, Turkey; Hitit University, Faculty of Engineering, Department of Mechanical Engineering, Corum, 19030, Turkey

Resume : Hydrogen as the main component of hydrogen energy system could be produced in different way and electrolysis is an attractive alternative for production. Thus, PEM electrolysers gets more attention by their high performance and tunable capacities in both mobile and stationary systems. Gas flow channels with different geometries, flow rates and gas compositions had excessively attention and research but another important component of PEM electrolyser, catalyst layer needed to have more attention. Thus, the use of platinium and nickel decorated zeolites investigated for PEM electrolyser. In the present work, CHA type silicon based zeolite decorated by different numbers of platinium and nickel atoms to produce novel PEM electrolyser catalyst, theoretically. Simulated annealing task used for platinium and nickel loading to the zeolite then the structures relaxed to the lowest energy configuration by using GGA functional with RPBE algorithm. By the way characteristic properties of the catalyst calculated and used for PEM electrolyser. At last, thermodynamic analysis of the electrolyser calculated in EES. It is found out that the novel catalyst had good potential for the use as catalyst in PEM electrolysers.

Authors : Christian Reitz, Ben Breitung, Horst Hahn and Torsten Brezesinski
Affiliations : Christian Reitz 1, Ben Breitung 1,2, Horst Hahn 1,3 and Torsten Brezesinski 1,2 1: Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany; 2: Institute of Nanotechnology, Battery and Electrochemistry Laboratory, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany. 3: Helmholtz Institute Ulm for Electrochemical Energy Storage, Helmholtzstr. 11, 89081 Ulm, Germany;

Resume : The development of high performance, and at the same time, intrinsically safe and durable lithium ion batteries (LIBs) is of significant importance (e.g., for EV applications). Recently, atomic layer deposition (ALD) has emerged as a promising technique for advanced composite design. ALD is a self-limiting deposition process and is well suited for generating novel LIB electrode materials. Here, we first describe the hard templating synthesis of highly conductive carbon (2-3 S/cm at 25 °C) with hierarchical porosity using a tricyanomethanide-based ionic liquid precursor and its use as a promising anode candidate for long life LIBs (~440 mA h g−1 at C/2 over >600 cycles). Then, we focus on ALD-derived TiO2 composite electrodes and demonstrate that the pores of the hierarchical N-doped carbon can be conformally coated with anatase TiO2. Long term cycling tests (>9000 cycles) indicate a capacity fading of only 0.004% per cycle at 5C. Lastly, we show that the carbon can also be used to trap lithium polysulfide species in Li-S batteries. The corresponding cathodes - with reasonably high sulfur loading of 2 mg/cm2 - display good cyclability with areal capacities of ~1.5 mAh/cm2 at C/5 and without obvious decay over several hundreds of cycles.

Authors : Omer Meroz, Dana Ben-Ayoun, Ofer Beeri and Yaniv Gelbstein
Affiliations : Ben Gurion University of the Negev

Resume : In an ever changing world the quest for new alternative energy resources enables new technological developments and brings society one step closer to a cleaner environment. The steady decline in the quantity of current resources and subsequently the climb in their price as well as the rising awareness of the global warming effect drive the search for improving current energy usage and finding new energy resources. In recent years there has been great technological progress in utilizing of novel alternative energy resources as well as more efficient ways have been found to improve the usage of current energy resources. Thermoelectric devices take thermal heat, either directly from solar energy or as a byproduct of fuel burn, and transform it to electricity. The efficiency of thermoelectric devices can be gauged by the dimensionless figure of merit ZT of the material, defined as ZT =α2σT/k, where α, σ, k and T are the Seebeck coefficient, the electrical conductivity, the thermal conductivity and the temperature in Kelvin, respectively. The inter-correlated σ, α and k make it difficult to improve the thermoelectric performance in a satisfactory way just by electronic doping approaches. Bismuth–telluride-based alloys are of great importance not only as the best thermoelectric materials with the maximum ZT values close to unity near room temperature, but also due to the potential for further performance improvement. Since these alloys are highly anisotropic, there is a direct relation between the orientation and the thermoelectric properties of the ingots. Hence, higher ZT values can be achieved by improving the orientation anisotropy of the ingots. In this study the Bi2Te2.4Se0.6 composition was optimized by CHI3 doping, preferred alignment of the crystallographic orientation, and lattice thermal conductivity minimization. The synthesis route included rocking furnace melting, energetic ball milling and hot pressing with optimal parameters for enhancement of the thermoelectric figure of merit, ZT, at temperatures higher than 200oC, commonly applied in low temperature power generation applications. The transport properties in the directions parallel and perpendicular to the pressing direction were examined. In the direction perpendicular to the pressing axis, a maximal ZT of ~0.9 was obtained at ~175oC, which is as far as we know among the highest ever reported for n-type Bi2TexSe3-x based alloys.

Authors : Bahadir Kucukgok, Frederico Severgnini, Yao Liu, Zhe Chuan Feng, Ian T. Ferguson, and Na Lu
Affiliations : Lyles School of Civil Engineering, Purdue University, West Lafayette, IN 47907, U.S.A; Lyles School of Civil Engineering, Purdue University, West Lafayette, IN 47907, U.S.A; Institute of Photonics and Optoelectronics, and Department of Electrical Engineering, National Taiwan University, Taipei 106-17, Taiwan; Institute of Photonics and Optoelectronics, and Department of Electrical Engineering, National Taiwan University, Taipei 106-17, Taiwan; College of Engineering and Computing, Missouri University of Science and Technology, 305 McNutt Hall, 1400 N. Bishop, Rolla, MO 65409, U.S.A; Lyles School of Civil Engineering, Purdue University, West Lafayette, IN 47907, U.S.A

Resume : Research interest in thermoelectric (TE) materials and devices has increased tremendously in recent years as they can directly convert heat energy into electrical energy. Additionally, III-nitrides such as GaN and its alloys have been considered as potential TE materials, for high-temperature power generation from waste heat harvesting, owing to their high-temperature stability, enhanced chemical stability and mechanical strength, superior electrical properties, and large-band gap range. In this work, a series of AlxGa1-xN thin films with x=0.20-0.60 were grown by metal-organic chemical vapor deposition (MOCVD) on sapphire (0001) substrate using AlN buffer layer. Furthermore, the impact of alloying and crystallographic defects on electrical and TE properties of AlxGa1-xN thin films were studied by employing temperature dependent van-der Pauw hall-effect, deep ultraviolet (DUV) photoluminescence (PL) spectroscopy (excitation at 245nm), and Seebeck characterization methods. The knowledge gained from this work will enable future developments of high efficient GaN-based TE materials for energy harvesting at high temperatures.

Authors : Mr. Omar Gómez Dr. Simon Hall Dr. Chris Bell
Affiliations : The Bristol Centre for Functional Nanomaterials, University of Bristol, BS8 1FD The School of Chemistry, University of Bristol, BS8 1TS The School of Physics, University of Bristol, BS8 1TD

Resume : Perovskites and perovskite-like materials are intensively investigated due to the variety of properties that they can exhibit. They have found use as multiferroics, cathode materials and even high temperature superconductors. Perovskite structures can be synthesized by a wide range of techniques: solid state reactions, sol-gel, hydrothermal, microwave assisted syntheses, and physical vapour deposition methods are among the most commonly used. These syntheses tend to be highly time and energy consuming however, raising the overall expense of the process. In addition, having control over the homogeneity of the sample can be a hard task to attain. Recently a new method of synthesis has been proposed implementing ionic liquids as an effective metal cation solvent. A brief analysis of the capability of this proposed technique is shown, as well as the ability to form SrNbOx pure phase crystals.

Authors : Aparabal Kumar, P. Banerji
Affiliations : Materials Science Centre, Indian Institute of Technology, Kharagpur 721302, India

Resume : Large value of thermoelectric figure of merit (ZT) is an indication of high efficiency of energy conversion in a thermoelectric material. In this study, doping by Pb at Sb site in Cu3SbSe4 was introduced for the enhancement of its ZT. Polycrystalline pellets of Pb-doped Cu3Sb1-xPbxSe4 (x = 0, 0.01, 0.03, 0.05 and 0.07) was synthesized using melt growth technique followed by spark plasma sintering at 573 K and 60 MPa for 5 min. The samples were used for structural characterization to examine the phase purity, to determine the crystal structure, and to measure the crystallite size. Electrical and thermal transport properties were investigated in the temperature range 300 - 650 K. Enhancement in electrical conductivity in the doped samples was explained using the concept of thermal excitation of dopant atoms, whereas the decrease in the value of lattice thermal conductivity was attributed to mass fluctuation. Single parabolic band model with acoustic phonon scattering approximation was used to explain the transport mechanism in the samples. The positive value of the measured Seebeck coefficient represents that holes are the major charge carriers in the transport process. It was found that the sample doped with x = 0.05 shows the optimum value of ZT ( 0.72 at 625 K) in this study.

Authors : Shengjie Peng, and Seeram Ramakrishna
Affiliations : Department of Mechanical Engineering, National University of Singapore, Singapore,117574

Resume : Nowadays, the lithium-oxygen battery has captured world-wide attention recently because of its extremely high theoretical energy density. A typical nonaqueous Li-O2 battery consists of a lithium−metal anode, organic electrolyte, and a porous air cathode exposed to gaseous O2 during cell operation. The air electrode is crucial to improve the electrochemical performance for rechargeable nonaqueous lithium–air batteries. Among the components of the air electrode, the catalyst is important in that it can enhance the charge reaction by reducing the voltage required to dissociate the reaction products (such as Li2O2) into lithium metal and oxygen. The electrocatalyst is currently being investigated with special attention being paid to solve the sluggish kinetics related to the main electrochemical reactions, as well as the instability of the discharge products. Recently, a variety of electrocatalysts, including noble metals, transition metal oxides and carbon-based materials, have been explored in Li-O2 cells with a high reversible capacity and a lower charge potential for oxygen evolution reaction (OER) than bare carbon. A problem for the cathode lies in that the solid discharge products are insoluble and thus precipitate in the pores of cathode, which gradually block the catalytic sites as well as the diffusion pathways of electrolyte and oxygen, especially for the inner part next to the separator, and eventually degrade the performance of Li-O2 batteries. Considering this point, how to improve the pore utilization and promote the O2 transport in the electrode plays an important role in determining the battery performance. Therefore, it is challenging and highly desirable to develop optimum electrocatalysts to efficiently catalyze Li-O2 reactions while simultaneously facilitate rapid oxygen and electrolyte diffusion. In this work, we present a facile solvothermal synthesis of 3D hierarchical spinel core-shell microspheres with a porous structure and applied as efficient 3D electrocatalysts in nonaqueous Li-O2 batteries. Such unique structure can improve the availability of the catalytic sites and facilitate the diffusion of electrons and reactants. Due to the synergistic effect of high catalytic activity of the NiCo2O4 and unique porous core-shell, the 3D hiercarchical NiCo2O4 catalyst shows superior specific capacity, rate capability, and cycle stability in Li-O2 batteries. Furthermore, other spinel oxides (e.g. MnCo2O4 and ZnCo2O4) are also have been synthesized through similar procedures, suggesting the generality and feasibility of this facile strategy. The superior catalytic performance of NiCo2O4 was further examined in Li-O2 batteries. It is found that the Li–O2 battery with the NiCo2O4 electrode exhibits rather stable specific capacities above 7000 mAh g-1carbon for five cycles and can keep specific capacities to be 6100 mAh g-1carbon after 10 cycles at a current density of 100 mA g-1carbon. Such performance can make NiCo2O4 core-shell microspheres as one of the best mixed metal oxides catalysts in Li-O2 batteries. Remarkably, it is found that our strategy could be extended to fabricate other spinel catalyst electrodes, such as MnCo2O4 and ZnCo2O4, suggesting the generality and feasibility of this facile strategy. In summary, we have demonstrated controlled synthesis of hierarchical spinel core-shell microspheres by a facile solvothermal method. The spinel microspheres constructed by porous nanoplates can act as high-performance catalysts in Li-O2 batteries. By taking advantage of the superior electrocatalytic activity and porous unique features, the as-prepared catalyst electrode exhibited low overpotentials, high rate capacity as well as excellent long-term cyclability. Significantly, this work offers exciting possibilities for the development of new functional materials in high-density storage devices

Authors : Gumjae Park, Chulho Lee, and Sang-Min Lee
Affiliations : Korea Electrotechnology Research Institute

Resume : Recently, various Si, and Sn based compound including transition metal oxide, multiphase alloy, and intermetallic compounds have been extensively studied as alternatives to the existing carbon based anode materials. Among alternative anode materials, transition metal phosphides (TMPs) have received much attention as anode materials for lithium ion batteries because of their high reversible capacity at relatively low potential [1]. However, these materials suffers from a relatively large capacity fading during cycling due to the large irreversible capacity and volume change. It is accompanied with the conversion reaction which is leading to decompose to LixM, LixP, and Mo after lithiation reaction. In order to solve this problem, numerous material concepts have been suggested and some of them prove to be effective in improving the cycle performance and structure stability. The effective ways to enhance is the use of active/inactive composite material [2] and nano-crystallization of active materials [3]. In addition to above method, it is also effective method to introduce of anode materials with intercalation reaction. Unlike the conversion reaction, intercalation reaction is reversible and not severe on structure change with lithium reaction. Among TMPs, Meta-stable phase such as SnP0.94 has been observed to be on intercalation reaction during charge-discharge process [4]. In this work, we developed a new type of MoP2-x (0≤ x ≤ 1) composite alloy to improve the structural stability and electrochemical properties by addition of nano-structured MoP in the pristine MoP2. MoP acts as buffer layer to suppress the volume expansion and intercalation reaction compound in MoP2-x composite. We investigated the differences in physical and electrochemical properties of various MoP2-x composite, examined using powder X-ray diffraction, SEM, and TEM, and galvanostatic charge-discharge test. We also investigated the volume expansion of MoP2-x composite during cycling, considering the influence of introducing nano-structured MoP layers in MoP2-x composte. References (1) D. C. S. Souza, V. Pralong, A. J. Jacobson, L. F. Nazar, Science 2002, 296, 2012. (2) G. Park, C. Lee, J. Lee, J. Choi, Y. Lee, S. Lee, J. Alloys compd. 2014, 585,534. (3) P. G. Bruce, B. Scrosati, J.-M. Tarascon, Angew. Chem. Int. Ed. 2008, 47, 2930. (4) Y. Kim, H. Hwang, C. S. Yoon, M. Kim, and J. Cho, Adv. Mater. 2007, 19, 92–96.

Authors : Linlin Li, and Madhavi Srinivasan
Affiliations : School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore, 639798. TUM-CREATE, 1 CREATE Way, #10-02 CREATE Tower, Singapore 138602.

Resume : As an alternative energy storage technology to the predominantly employed lithium-ion batteries (LIBs), sodium-ion batteries (SIBs) have revitalized increasing scientific attention for large-scale applications, mainly because of the low cost, large resource availability, and similar chemistry of sodium with lithium. However, the main bottleneck to the commercialization of SIBs is the limited choice of anode materials. It is well known that Na ions are about 55% larger in radius compared with Li ions, which significantly hinders the utilization of well-developed electrode materials in LIBs owing to the insufficient interlayer spacing. Therefore, it is difficult to find suitable materials that can accommodate Na ions and allow reversible ion insertion/deinsertion. Up to now, various alternative materials, including carbon, layered metal oxides, alloy-based materials and metal chalcogenides, have been explored as potential anodes for SIBs. Although some encouraging progress have been made, developing appropriate electrode materials with high capacity and good reversibility is less successful and still require further research. We demonstrate a simple solvothermal method to in situ decorate 2D CoS nanoplates on rGO nanosheets. The resulting CoS@rGO hybrid architecture offers unique characteristics, which is needed for advanced anode. Benefiting from the novel structure and improved electric conductivity, CoS@rGO hybrid composite exhibits high capacity (540 mAh g-1 at 1 A g-1), superior rate capability (636 mAh g-1 at 0.1 A g-1 and 306 mA h g-1 at 10 A g-1), and ultra-long cycle life (420 mAh g-1 at 1 A g-1 after 1000 cycles) as anode for SIBs. These results endow CoS@rGO composite as advanced anode for SIBs. Remarkably, a full cell, which is based on CoS@rGO hybrid anode and electrospun Na3V2PO4@carbon (NVP@C) cathode, has been assembled and manifests high capacity and outstanding cycle stability, indicating its huge potential as promising anode for SIBs industry. CoS@rGO hybrid composites has been prepared by a one-pot solvothermal strategy using Co(CH3COO)2 (Co(Ac)2), thiourea (Tu), and GO as precursors in ethanol medium at 180 °C for 12 h. As shown in the schematic illustration in Figure 1a, in situ directly growth of CoS@rGO composites is induced by the heterogeneous nucleation of CoS on graphene. During the reaction process, GO provides large amounts of defects/functional groups as nucleation sites for in situ growth of CoS nanplates. The presence of carboxyl and hydroxyl groups on the GO sheets can make the thiourea grafted on the GO through surface functional groups, as the amino groups in thiourea are activated by the C=S bonds. Moreover, Co2+ could incorporate on the GO sheet by electrostatic force. As a consequence, the absorbed Co2+ reacts with the gradual release of S2- ions deriving from the decomposition of Tu to form CoS nuclei that are tightly anchored onto graphene sheet with well dispersion. Meanwhile, GO sheets are reduced to rGO sheets with ethanol medium as a mild reductant. Thus, the continuous solvothermal reaction resulted in oriented alignment of CoS nanoplates grown on rGO sheets. This unique structure is expected to provide high accessibility to the electrolyte and fast sodium-ion transport pathways. In summary, the novel CoS@rGO hybrid composites with precisely controlled unique configurations have been successfully developed by an efficient in situ solvothermal technique. The well-defined CoS nanoplates with a thickness of around 10 nm are uniformly grown on rGO frames with strong adhesion, which provides structually stable host for Na-ion intercalation and deintercalation. Suprisingly, as anode for SIBs, an impressive high specific capacity (540 mAh g-1 at 1 A g-1), excellent rate capability (636 mAh g-1 at 0.1 A g-1 and 306 mA h g-1 at 10 A g-1), and extraordinarily cycle stability (420 mAh g-1 at 1 A g-1 after 1000 cycles) has been demonstrated by CoS@rGO for sodium storage. The 2D conductive framwork of rGO, ultrathin feature of CoS nanoplates, as well as the unique nanoarchitecture with enhanced electrolyte penetration, are responsible for the outstanding electrochemical performances of the CoS@rGO composite. Such intriguing electrochemical properties of CoS@rGO make it a promising anode materials for advanced SIBs.

Authors : Xanthippi Zianni (1), Eric Herbert (2), Christophe Goupil (2) & Yves D'Angelo (2,3)
Affiliations : (1) Dept. of Aircraft Technology, Technological Educational Inst. of Sterea Ellada, 34400 Psachna, Greece (2) DyCoE Team, LIED/PIERI, Paris Interdisciplinary Energy Research Institute, CNRS UMR 8236, Université Paris Diderot, France (3) CORIA/INSA, National Institute for Applied Sciences, CNRS UMR 6614, Normandy University, Rouen, France.

Resume : Composite materials are considered as prosperous for thermoelectric (TE) efficiency enhancement. The TE efficiency is determined by three transport properties: the electrical conductivity σ, the Seebeck coefficient S and the thermal conductivity κ, that define the TE figure of merit: σS^2/κ. In traditional TE materials these transport properties are interconnected and the figure of merit is kept limited. In composite materials, the three transport properties can be independent. The thermal conductivity is limited by enhanced scattering at interfaces and boundaries. The electrical conductivity typically decreases due to enhanced scattering of carriers and nanostructuring. The Seebeck coefficient though can increase significantly due to energy filtering in the presence of non-uniformities. In this case, the interplay between the three transport properties depends on the details on the nanostructure of the composite material. In some cases the composite material can be decomposed into interconnected parts. An equivalent TE network can then describe the properties of the composite material. We have used a TE network model extending Millman’s theorem, so that both current and energy continuity are satisfied locally. Each cell of the network is assumed to be in thermodynamic equilibrium and satisfy Onsager’s relations. We have applied this model to explore the paths of heat and charge conduction in a composite material and to identify preferential configurations for the TE efficiency. We will discuss two cases of model composite materials: (a) an ordered configuration of two TE phases, and (b) a random configuration of two TE phases.

Authors : Marketa Zukalova, Barbora Pitna Laskova, Arnost Zukal, Ladislav Kavan
Affiliations : J. Heyrovský Institute of Physical Chemistry, v.v.i., AS CR, Dolejškova 3, CZ-18223 Prague 8, Czech Republic

Resume : Until recently Li-ion batteries have attracted all the attention in energy storage. Due to limited resources of Li, Na as cheap and available alternative has attracted now an attention of many researchers. Among TiO2-based materials, TiO2(B) and Li-Ti ternary oxides (spinels, LTS) were recently found to be promising materials for Na storage exhibiting large capacities due to their suitable structure. We carried out a study of Na insertion behavior of both commercial materials with different particle size (LTS) and laboratory made ones (LTS, TiO2(B)). Above mentioned materials were characterized by XRD, adsorption measurements and tested by cyclic voltammetry (CV) of Li insertion and galvanostatic chronopotentiometry of Na insertion. LTS from Johnson Matthey (LTSJM) with 20% super P and LTS Altair exhibited the best charge capacities for Na storage. During galvanostatic testing in 1M NaPF6 in EC/DEC by charging rate 2C provided LTSJM+super P and LTS Altair+super P electrodes charge capacities of 88 and 105 mAh/g respectively. Unfortunately, both materials exhibited a capacity drop of about 30% after 50 cycles. To improve material conductivity and stability composites of LTS and TiO2(B) with graphene were prepared and tested by CV of Li insertion. The presence of graphene in LTSJM+super P increased its charge capacity from 143 to 169 mAh/g. This work was supported by the Grant Agency of the Czech Republic (contract No.15-06511S).

Authors : Shilpa, Basavanakote Basavaraja, Subhasish Majumder, Ashutosh Sharma
Affiliations : Shilpa : Chemical Engineering, Indian Institute of Technology Kanpur, India; Basavanakote Basavaraja : Indian Institute of Technology Kanpur, India; Subhasish Majumder : Materials Science Centre, Indian Institute of Technology Kharagpur, India ; Ashutosh Sharma : Indian Institute of Technology Kanpur, India

Resume : Zinc oxide (ZnO) has a high theoretical capacity for lithium storage, however it undergoes huge volume changes during charge/discharge resulting in particle pulverization and detachment from the current collector. In this work, novel anode architecture for Li-ion batteries is fabricated by encapsulating ZnO nanoparticles in the hollow core of glassy carbon–reduced graphene oxide (C–rGO) electrospun composite nanofibers. A one-step, co-axial electrospinning method is used to synthesize a mat of core–shell structured composite nanofibers composed of rGO embedded in poly(acrylonitrile) (shell) and a ZnO nanoparticle precursor with a carrier polymer (core). Subsequent calcination and carbonization produce a mechanically stable anode material, which is used directly as a free-standing anode without any binder and current collector. The ZnO–C–rGO nanofiber composite is characterized by SEM, TEM, RAMAN and XRD techniques. The electrochemical performance of the composite is studied by galvanostatic charge–discharge measurements at different current densities, slow scan cyclic voltammetry (CV) and impedance measurements. Incorporation of an rGO network in the glassy nanofiber shell enhances both the capacity and electrical conductivity of the mat electrode resulting in faster electron kinetics, and thus, an improved rate capability. The interior void spaces combined with the mechanical strength and flexibility of the C–rGO shell act as a structural buffer effectively relieving the volumetric stresses generated during charge–discharge cycles. The synergistic effect of the metal oxide, rGO and the core–shell design results in a high capacity of 815mAh/g at a current density of 50mA/g with capacity retention of almost 80% after 100 cycles, thus demonstrating significant potential as an anode substitute for next generation Li-ion batteries.

Authors : Sébastien Lemal, Daniel I. Bilc, Philippe Ghosez
Affiliations : Physique Th\'eorique des Mat\'eriaux, Universit\'e de Li\`ege (B5), B-4000 Li\`ege, Belgium; Molecular and Biomolecular Physics Department, National Institute for Research and Development of Isotopic and Molecular Technologies, RO-400293, Cluj-Napoca, Romania; Physique Th\'eorique des Mat\'eriaux, Universit\'e de Li\`ege (B5), B-4000 Li\`ege, Belgium;

Resume : Combining first-principles calculations based on density functional theory with an hybrid exchange-correlation functional and Boltzmann semi-classical transport theory, we investigate the properties of heavily n-type doped full Heusler Fe2YZ compounds. Using a supercell approach and including explicitly the dopant impurities, we recover in some cases giant thermoelectric power factors as previously predicted under doping within the rigid band approximation [Phys. Rev. Lett. 114, 136601 (2015)]. In other cases, however, we highlight that the system evolves toward a ferromagnetic half-metallic ground state so that the power factor is strongly modified. We rationalize the appearance of this magnetic instability, showing that it consistent with the Stoner model. The uncovered properties of the heavily doped phases of the studied full Heusler compounds appear promising for Seebeck and spin-Seebeck applications.

Authors : Marco Schleutker, Carsten Korte, Detlef Stolten
Affiliations : Institute of Energy and Climate Research - Electrochemical Process Engineering (IEK-3), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany,

Resume : Li/O2 and Li/S cells can be improved, if the anodic side with a nonaqueous electrolyte can be separated from the cathodic side with an aqueous electrolyte. A good possibility for such a separation is a solid Li+ electrolyte, because it can conduct the Li+ ions, but is impenetrably for the solvents and conducting salts of liquid electrolytes. In this study the interfacial charge transfer between the liquid electrolyte 1M LiPF6 in ethylene carbonate/dimethyl carbonate 1:1 vol.% (LP30) and the solid electrolyte Li7La3Zr2O12 (LLZO) is analyzed. A symmetric liquid/solid/liquid eight electrode cell which has two reference electrodes in each electrolyte chamber has been developed. Pure lithium acts as the working and counter electrode, respectively. While a constant current is provided to the cell, a concentration gradient of Li+ ions arises in the cell. It depends on the properties of the electrolytes (e.g. diffusion coefficient, mobility, etc.). The concentration gradient in the cell causes a potential gradient of the lithium which can be detected by the reference electrodes. An electrochemical potential difference of Li+ across the solid/liquid interface of both electrolytes can be measured. The exchange current density i0 and the symmetry factor α can be derived from a Tafel plot by measuring the potential step as a function of current density.

Authors : Alessandro Puri 1, Francesco d’Acapito 1, Pascal Pochet 2 3, Florian Preishuber-Pfluegl 4, Martin Wilkening 4
Affiliations : 1 CNR-IOM-OGG c/o ESRF LISA CRG 71 avenue des Martyrs CS 40220 FR - 38043 GRENOBLE Cedex 09; 2 Atomistic Simulation Laboratory (L_Sim) CEA Grenoble - INAC FR - 38041 GRENOBLE Cedex 09; 3 Université Grenoble-Alpes, Grenoble, FRANCE; 4 Graz University of Technology Inst. f. Chemistry & Technology of Materials Stremayrgasse 9 AT - 8010 GRAZ

Resume : BaSnF4 belongs to the material class MSnF4 (M = Pb, Ba, Sr) that shows very high anionic conductivity resulting from cation ordering in the crystal structure and hopping processes between fluorine defective sites. These systems are technologically interesting for energy storage devices applications such as solid-state fluorine batteries or sensors. Partial substitution of Ba with isovalent cations of different ionic radii can be used to increase F anion conductivity, resulting in solid solutions with enhanced conductivity compared to the pure material. Moreover, in presence of an aliovalent dopant, namely Rb, the formation energy of vacancies in the F sites can be lowered, with a corresponding increase in conductivity. A closely related issue regards the thermal stability of these materials. Recent studies have shown that annealing process may have a considerable effect in the ion conductivity. We have investigated this important point through XAS measurements at the Rb and Sr K absorption edges in (Rb, Sr) doped BaSnF4 samples. For each dopant an as-prepared sample plus samples annealed at 573 K for 2, 8 and 16 hours have been analysed. While for the Sr-doped set the as-prepared and annealed samples have very similar EXAFS spectra, in the Rb-doped case the as-prepared samples show important differences compared to the annealed ones. Structural modelling based on Density Functional Theory has also been carried out and the predictions compared with the EXAFS data.

Authors : Sangwook Lee, Fan Yang, Young-Woo Heo, Sefaattin Tongay, Junqiao Wu
Affiliations : School of Materials Science and Engineering, Kyungpook National University, Korea; Lawrence Berkeley National Laboratory, United States; Department of Materials Science and Engineering, University of California, Berkeley, United States; School for Engineering of Matter, Transport, and Energy, Arizona State University, United States; Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 3 Research Link, Singapore

Resume : Nanoscale heat management is growing in importance for device applications such as advanced high density electronics and thermoelectric devices as well as for fundamental physics. Especially, recent development in two-dimensional (2D) devices based on layered materials is increasingly demanding highly controllable heat transport in the layered materials, which is required to prevent the overheating of electronic components or to improve the thermoelectric performance. Many strategies to modulate the phonon transport of the 2D materials have been contrived by engineering impurity, geometry, stress/strain and thermal interface materials, or by using anisotropic thermal property of the layered materials. Black phosphorus (BP), one of the layered materials, is expected to have a highly anisotropic in-plane thermal conductivity. BP has attracted enormous attention as a promising single atomic, layered material for electronic, optic and optoelectronic applications, based on experimental demonstration of remarkable properties, such as high hole mobility (~ 1000 cm2/V-s) and desirable on/off current ratio (~10^5) in few layer based field-effect transistors, and tunable direct band gap from 0.3 eV (bulk) to > 1.4 eV (monolayer). Therefore, the information on the anisotropic thermal property of BP is highly desired to design BP-based high density 2D devices. Moreover, BP is considered as a potential candidate of high performance thermoelectric material, based on numerous theoretical works predicting high thermoelectric power, and countertrend of anisotropy in thermal and electrical transport; one order larger electrical conductivity along AC direction, while higher thermal conductivity along ZZ direction. Here, we show anisotropic in-plane thermal conductivity of BP at a wide temperature range, by direct heat flow through suspended single crystal BP nanoribbon, using a suspended-pad-type micro-device. The BP nanoribbons that are axially oriented to ZZ or AC axis are prepared from exfoliated BP flakes via micro-fabrication processes. The measured thermal conductivity shows strong temperature dependence. The thermal conductivity anisotropy ratio, ZZ to AC, at 300 K is ~2. Based on the scattering constants for the anharmonic three-phonon process, the anisotropic phonon dispersions of the acoustic modes are attributed to the main factor leading to the highly anisotropic thermal conductivity.

Authors : Hsiao-Chien Wang1, Wen-Chun Yen2, Jian-Shiou Huang3, Henry Medina1, Yu-Lun Chueh1.
Affiliations : 1.Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, 300, Taiwan; 2.Giga Solar Materials Corporation, Hsinchu, 303, Taiwan; 3.Taiwan Semiconductor Manufacturing Company Limited, Hsinchu, 300, Taiwan

Resume : With increasing focus on portable power storage device, developing high performance batteries draws more and more attention. Lithium (Li) based batteries are one of the most promising batteries due to its huge power density. The conventional anode material used in Li-ion batteries nowadays is graphite. However, the theoretical specific capacity of graphite may not meet the need of large electricity consumption of vehicles. Although Si is found to have enormous theoretic specific capacity, 300%~400% volume change when batteries are under charging might result in pulverization of material and decade of battery cycle life. In this research, we use glancing angle deposition (GLAD) technique to create uniformly-distributed helix Si nanorod structure. The Si helix nanorod is identified as amorphous phase which is also preferred to form LixSi alloy to achieve higher capacitance. In addition, the bonding state and morphology changes of Li and Si after charging/ discharging can be checked by XPS and TEM analysis respectively. With modulation of tilt angles of GLAD, porosity is controllable in different Si nanostructures. In this work, various rotation numbers are chosen for comparison. Based on area density fitting, porosity increases with increasing rotation number of Si nanorod. We observed that adequate porosity can effectively alleviate massive stress of volume expansion and reduce the crack possibility of Si nanorods which enable the device to survive after hundreds of charge/ discharge cycles. After optimizing helix Si nanorod structure, the volumetric specific capacity of 2019.2 mAh/cm3 was evaluated. Furthermore, even after 100 cycle tests, the volumetric specific capacity still sustain above 350 mAh/cm3. In the future, GLAD system is believed to achieve a great effort on improving the specific capacity of Si based anode materials in the system of Li-ion batteries.

Authors : K. Chakir, C. Bilel, M.M. Habchi, A. Rebey, and B. El Jani
Affiliations : University of Monastir, Faculty of Sciences, Unité de Recherche sur les Hétéro–Epitaxies et Applications, 5019 Monastir, Tunisia

Resume : The dependence of carrier effective mass of GaNxAs1-x, InNxP1-x, InNxAs1-x, and InNxSb1-x alloys on nitrogen content is theoretically investigated using a 10-band k.p model. The electron effective mass m*e at the bottom of conduction band in GaNxAs1-x and InNxP1-x exhibits a gradual increase as a function of N concentration in the range 0-1% and a decrease for x between 1 and 5 %. However, the behavior of m*e in InNxAs1-x and InNxSb1-x shows a strongly decrease in all studied x-range. Our theoretical results are compared with the available data reported in the literature. On the other hand, contrary to heavy-hole effective mass m*hh, the light-hole effective mass m*lh in all studied alloys is significantly affected by nitrogen states which modify the non-parabolicity of the LH band. The modification of the carrier effective mass affects the transport and mobility properties of the III-N-V alloys. Keywords: Diluted III-N-V alloys; 10-band k.p model; carrier effective mass. * Corresponding author:

Authors : E. Besozzi, D. Dellasega, M. Passoni, M.G. Beghi
Affiliations : Dipartimento di Energia, Politecnico di Milano, Milano, Italy Istituto di Fisica del Plasma “P.Caldirola”, Consiglio Nazionale delle Ricerche, Milano, Italy

Resume : This work is an experimental and numerical investigation of the thermomechanical properties of nanostructured tungsten (W) coatings grown by Pulsed Laser Deposition. W coatings are exploited in several applications, e.g. thermal management and as protective layers in Tokamaks. They are usually deposited on substrates with different thermomechanical properties, so that, when thermal loads are applied, the properties mismatch can lead to the coating failure and delamination. In addition, coatings thermomechanical properties are severely affected by the structure at the nanoscale, morphology and elemental composition. The mechanical behaviour is obtained by surface Brillouin spectroscopy as function of different film structures, from nanocrystalline (n-W) to amorphous (a-W), as monitored by X-ray diffraction, and tantalum (Ta) concentration. The a-W is characterized by a loss of stiffness by about 60% and an increase of local ductility by 50% with respect to n-W. Upon annealing, it starts to crystallize at temperatures of one-half the bulk W recrystallization one. The addition of Ta atoms in solid solution regime is also accompanied by a softening of the material, hindering crystallites growth and promoting local ductility. Laser irradiation will be performed to induce fast thermal loads within the coatings. In order to simulate temperature and thermal stresses profiles during irradiation, a numerical model based on the finite difference method has been developed.

Authors : I. Guizani, K. Chakir, C. Bilel, M.M. Habchi, A. Rebey*, B. El Jani
Affiliations : Université de Monastir-Unité de Recherche sur les Hétéro-Epitaxies et Applications (URHEA) Faculté des Sciences de Monastir, 5000 Monastir, Tunisie

Resume : We have theoretically studied optical properties of p-doped GaNAsBi/GaAs Single Quantum Well in order to reach the 1.55µm telecommunication wavelength. The calculation are carried out by solving selfconsistently the band (16×16) Kane Hamiltonien combined with the Poisson equation for the hole charge density. We have investigated the effect of p doping density in the well on the subband energies, potential Fermi level and the confining hole density distribution for specific couple (well width Lw,Bi composition y), with respect of confinement conditions. The increase of doping density blueshifts the fundamental transition. Furthermore, the case of doped barrier has been discussed. Based on these results, potential applications in long wavelength range are proposed

Authors : Alexandra M.I. TREFILOV, Elena C. SERBAN, Sanda VOINEA, Adriana BĂLAN, Ioan STAMATIN
Affiliations : University of Bucharest, Faculty of Physics, 3Nano-SAE Research Centre, Bucharest-Magurele, Romania

Resume : Proton exchange membranes (PEM), a main component of PEM fuel cells (FC), influence both FC cost and performance. Nafion is considered the most popular proton conductor in the FC industry, although it comes with limitations in terms of ionic conductivity and thermal stability. We use resorcinol-formaldehyde (RF) polymer gels as dopants to produce a hybrid cation exchange membrane. We investigate the conduction mechanism modifications induced by RF organic clusters forming a distributed network within the perflourosulfonated acid (PFSA) matrix. RF concentration is controlled by the PFSA impregnation time in a resorcinol, p-toluenesulfonic acid, and formaldehyde solution. The composite membranes are characterized by FT-IR for identifying specific structural features, as well as TGA and DMA for studying thermal stability and degradation processes. PFSA-RF hybrid membranes show improved thermal stability (up to 40% raise) and ionic conductivity (up to 50% raise) at a relative humidity of 80% for low RF content, compared to PFSA reference membranes.

Authors : I. Ornelas, J. Pilo, E. Carvajal, M. Cruz–Irisson
Affiliations : Instituto Politécnico Nacional. Escuela Superior de Ingeniería Mecánica y Eléctrica–Culhuacán

Resume : The great improvement achieved for the solar conversion efficiency of dye–sensitized solar cells is linked to the use of the CH3NH3PbI3 hybrid perovskite as light harvester. Having that perovskite three different structural phases, a first–principle theoretical study was performed on all of them for this work, even knowing that just one of the three phases is the relevant to photovoltaic applications. The electronic band structures, densities of states and charge distributions were analyzed after geometry optimization of each structure with different orientations of the molecule which occupy the A–site of the perovskite, because molecular orientation and vibration reflect on the electronic properties of the compound. Structural phases and electronic properties calculation were made using the generalized gradient approximation and the Perdew–Burke–Ernzerhof functional, as implemented in the DMol3 code. Temperature dependence of the CH3NH3PbI3 phase transitions was ignored but the energies associated to each cubic, tetragonal and orthorhombic phases were considered in order to contrast our results against the experimental reports. Acknowledgements: This work was partially supported by COFAA and the projects IPN–SIP–2016–1770 and 252749 and 257139 from CONACYT. I. Ornelas and J. Pilo want to acknowledge the graduate fellowship from CONACYT.

Authors : Sira Suren, Soorathep Kheawhom
Affiliations : Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330 Thailand

Resume : In this work, transparent thin film Zn-MnO2 batteries were fabricated using an inexpensive screen-printing technique. Both anode and cathode electrodes were fabricated as micro-electrode arrays with feature size of 50 um. Thus, the electrodes appeared transparent. Moreover, a transparent alkaline polymer gel electrolyte film prepared by polymerization of acrylate, potassium hydroxide and water was used a quasi-solid-state electrolyte, functioning as both an electrolyte and an insulator/separator. Three patterns of the electrodes with different percentages of opening area (75%, 80% and 85%) were investigated. The open-circuit voltages of the batteries fabricated were 1.34 V. Ohmic loss zones of 75% and 80% batteries were 0.01 - 1.5 uA, while ohmic loss zone of 85% battery was 0.01 - 1.0 uA. The battery with 80% of opening area provided an average transparency of 90% without much sacrifying battery performance.

Authors : S. Sayah, F. Ghamouss, J. Santos-Peña, F. Tran-Van, D. Lemordant
Affiliations : Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l’Energie (PCM2E)

Resume : The new composite anode Si0.32Ni0.14Sn0.17Al0.04C0.35 exhibits a high specific capacity as well as fast kinetics of charge and discharge [1]. However, due to the side reactions occurring at the electrolyte/electrode interphase, the electrode reversibility is not yet optimal. Therefore, the main objectives of this work are to examine the reactions occurring at the electrode/electrolyte interface and then to evaluate the impact of the electrolyte composition on the performances of this composite anode. It is now well known that the performances of Li-ion intercalation electrodes are closely linked to the nature of the electrode/electrolyte interphase which depend in turn on the composition of the electrolyte. In many commercial Li-ion batteries using conventional electrolytes, such interphase is stabilised and improved by formulating electrolyte with specific additives. Such species act as SEI (Solid Electrolyte Interphase) improvers since they are easily reduced at the anode before Li+ intercalation during the first charge of the battery. This results in the formation of a thin, insoluble and Li+ conductive passivation layer which prevents further decomposition of the electrolyte and improves the reversibility of the electrode. We have explored a series of SEI builder additives: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite (ES), propylene sulfite (PS), fluoroethylene carbonate (FEC) and di-fluorethylene carbonate (F2EC). The impact of these additives on the SEI formation at the Si0.32Ni0.14Sn0.17Al0.04C0.35 has been studied as a function of their amount using electrochemical methods (CV, GCPL and EIS) and surface characterization techniques (XPS, SEM, Raman spectroscopy). Results indicate that reversibility and stability of the composite anode can be enhanced by a careful choice of the solvent and the SEI improver additive. Alternatively to the classical ternary EC/PC/3DMC mixture , Room Temperature Ionic liquids containing bis(trifluoromethylsufonyl)imide anion and di-alkyl pyrrolidium, di-alkyl piperidinium or tetra-alkylammonium cations have been used as electrolytes solvent suppressing therefore side reactions due to traditional solvent decompositions and improving the electrode reversibility [2] [3]. (1) Z. Edfouf, F. Cuevas, M. Latroche, C. Georges, C. Jordy, G. Caillon, T. Hézèque, J.-C. Jumas, M. T. Sougrati, "Nanostructured Si/Sn–Ni/C composite as negative electrode for Li-ion batteries", J. Power Sources, 196 (2011) 4762-4768. (2) W. Zhang, F. Ghamouss, A. Darwiche, L. Monconduit, D. Lemordant, R. Dedryvère, H. Martinez, “Surface film formation on TiSnSb electrode : impact of electrolyte additives”, Journal of Power Sources 268 (2014) 645-657. (3) W. Zhang, F. Ghamouss, A. Mery, D. Lemordant, R. Dedryvère, L. Monconduit, H. Martinez, “Improvement of the stability of TiSnSb anode under lithiation using SEI forming additives and room temperature ionic liquid/DMC mixed electrolyte”, Electrochimica Acta, 170 (2015) 72-84.

Authors : Jin-Ming Chen, I-Li Chen, Yu-Chen Wei, Kueih-Tzu Lu, Tsan-Yao Chen, Chi-Chang Hu
Affiliations : National Synchrotron Radiation Research Center, HsinChu 30076, Taiwan. National Tsing Hua University, HsinChu 30013, Taiwan. E-mail:

Resume : Binary oxides with atomic ratios of Ru/Ti = 90/10, 70/30, and 50/50 were fabricated by H2O2-oxidative precipitation with the assistance of the cetyltrimethylammonium bromide (CTAB) template, followed by a thermal treatment under 200oC. The characteristics of electron structure and local structure extracted from X-ray absorption spectroscopic (XAS) and transmission electron microscopic (TEM) analyses indicate that incorporation of Ti into the RuO2 lattice produces not only the local structural distortion of RuO6 octahedra in (Ru-Ti)O2 with an increase in the central Ru-Ru distance but also a local crystallization of RuO2. Among these three binary oxides, (Ru70-Ti30)O2 exhibits a capacitance improvement about 1.4 fold relative to the CTAB-modified RuO2, mainly due to enhanced crystallinity of the distorted RuO6 structure rather than the surface area effect. Upon increasing the extent of Ti doping, the deteriorated supercapacitive performance of (Ru50-Ti50)O2 results from the formation of localized nano-clusters of TiO2 crystallites. These results provide insight into the decisive role of Ti doping in RuO2 that boosts the pseudocapacitive performance for RuO2-based supercapacitors. The present result is crucial for the design of new binary oxides for supercapacitor applications with extraordinary performance.

Authors : Sira Suren, Soorathep Kheawhom
Affiliations : Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330 Thailand

Resume : Zinc-air battery is a promising energy storage device because of its cost-effectiveness and high energy density. One effective method of improving the performance of zinc-air battery is to increase the surface area of the zinc particles used in its anode. However, as the surface area of the anode increases, the corrosion rate of the zinc anode generally becomes more significant. This side effect consumes electrolyte, lowers the efficiency of the zinc electrode utilization and eventually shortens battery lifetime. This work, therefore, investigates the improvement in self-discharge of zinc anode by coating Al2O3 on surface of zinc particles. The effects of Al2O3 concentrations and sintering temperature of Zn-Al2O3 were investigated. Anode and cathode electrodes were then fabricated using inexpensive screen printing technique. The anode and cathode current collectors were printed using commercial nanosilver conductive ink on a polyethylene terephthalate substrate and a polypropylene membrane, respectively. Air cathode made of blended activated carbon with MnO2, was fabricated. Anode electrode was fabricated by using synthesized Zn-Al2O3 particles. Performance of the fabricated zinc-air battery was then studied. The results showed that to coat pristine zinc particles with Al2O3 significantly suppress the corrosion rate of the zinc anode electrode without scarifying the performance of the battery.

Authors : Jaime Ortún-Palacios 1, Sarah Fadda 2 3, Antonio Mario Locci 3*, Francesco Delogu 3, Santiago Cuesta-López 1
Affiliations : 1 ICCRAM. International Research Center in Critical Raw Materials for Advanced Industrial Technologies. University of Burgos, Plaza Misael Bañuelos s/n, 09001 Burgos, Spain; 2 Centre for Process Systems Engineering, Department of Chemical Engineering, Imperial College London, London SW7 2AZ, U.K.; 3 Università degli Studi di Cagliari, Dipartimento di Ingegneria Meccanica, Chimica e dei Materiali,Via Marengo 2, 09123 Cagliari, Italy; *Correspondence should be addressed to Antonio Mario Locci;

Resume : Several techniques as density functional theory (DFT), molecular dynamics and phase field calculations were used to study the mechanisms underlying point defect annihilation at interfaces of nanostructured metallic multilayer composites (NMMC). This covered atomistic scale in enough detail. However, the overall mechanistic situation remained largely unknown. In this context, it was highly desirable to develop a continuum approach that describes long-term evolution of point defects in NMMC subjected to radiation. In order to provide a contribution along this line, Fadda et al. [1] modeled the dynamic behavior of vacancies and interstitials in continuum scale. They used nanostructured metallic monolayers of Cu and Nb as case study. A continuum spatial distribution of sinks either neutral or variable-biased was used to describe interfaces. This enables modeling grain boundaries and incoherent precipitates, i.e., non-coherent interfaces, as neutral sinks, and coherent precipitates, i.e., coherent interfaces, as variable-biased sinks [2]. Production, recombination, transport and annihilation of point defects at interfaces were defined by means of non-stationary balance equations. The effect of variation in layer thickness, temperature, production rate of point defects and surface recombination coefficient on annihilation processes at interfaces were studied. The present work focuses on modifying the model mentioned above in a way that experimental results obtained in Cu/Nb, Cu/V and Cu/Ni NMMC by Mao et al. [3], which showed that the vacancy concentration profile and the efficiency of heterogeneous interfaces as point defects sinks in Cu also depended on the properties of Nb, V or Ni respectively, agree qualitatively with those obtained after such modification. To this end, boundary equations have been modified according to β-α-β NMMC (α = Cu and β = Nb, V or Ni) used as new case study [4]. The rest of model equations have also been adapted to the system studied. We expect to find out if Cu/Nb NMMC is very efficient in removing point defects due to diffusion of these in that system, because of the special interface characteristics or both. The set of partial differential equations and ordinary differential equations corresponding to the model has been implemented in the COMSOL Multiphysics software. We have been adjusting several model parameters to obtain results as accurate as possible. References [1] Fadda S., Locci A.M., Delogu F., Modeling of Point Defects Annihilation in Multilayered Cu/Nb Composites under Irradiation, Advances in Materials Science and Engineering, Volume 2016 (2016). [2] Was G.S., Fundamentals of radiation materials science – Metals and alloys, Springer, (2007). [3] Mao S., Shu S., Zhou J., Averback R.S., Dillon S.J., Quantitative comparison of sink efficiency of Cu-Nb, Cu-V and Cu-Ni interfaces for point defects, Acta Materialia, 82, (2015), 328-335. [4] Brailsford A.D., Bullough R., The rate theory of swelling due to void growth in irradiated metals, Journal of Nuclear Materials, 44 (2), (1972), 121-135.

Authors : Mihai Sturza 1,3, Jared M. Allred 1, Christos D. Malliakas 1,Daniel E. Bugaris 1, Fei Han 1, Duck Young Chung 1, Sabine Wurmehl 3 and Mercouri G. Kanatzidis 1,2,
Affiliations : 1-Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States 2-Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States 3-Leibniz Institute for Solid State and Materials Research Dresden IFW, Institute for Solid State Research, 01069 Dresden, Germany

Resume : Effecting and controlling ferromagnetic-like properties in semiconductors has proven to be a complex problem, especially when approaching room temperature.Here, we demonstrate the important role of defects in the magnetic properties of semiconductors by reporting the structures and properties of the iron chalcogenides (BaF)2Fe2−xQ3 (Q = S, Se), which exhibit anomalous magnetic properties that are correlated with defects in the Fe-sublattice. The compounds form in both long-range ordered and disordered polytypes of a new structure typified by the alternate stacking of fluorite (BaF)22+ and (Fe2−xQ3)2− layers.The latter layers exhibit an ordered array of strong Fe−Fe dimers in edge-sharing tetrahedra. Given the strong Fe−Fe interaction,it is expected that the Fe−Fe dimer is antiferromagnetically coupled, yet crystals exhibit a weak ferromagnetic moment that orders at relatively high temperature: below 280−315 K and 240−275 K for the sulfide and selenide analogues, respectively. This transition temperature positively correlates with the concentration of defects in the Fe-sublattice, as determined by single-crystal X-ray diffraction. Our results indicate that internal defects in Fe2−xQ3 layers play an important role in dictating the magnetic properties of newly discovered (BaF)2Fe2−xQ3 (Q = S, Se), which can yield switchable ferromagnetically ordered moments at or above room temperature. Hence, the magnetic properties can be fine-tuned by controlling the defect chemistry. This type of property is important to fields such as spintronics, where semiconducting phases with controllable ferromagnetic moments are of interest.

Authors : M. Boukhari 1,*, A. Barski 1, F. Rortais 1, C. Vergnaud 1, M. Jamet 1, P. Bayle-Guillemaud 1, P.-H. Jouneau1, E. Bellet-Amarlic1, E. Hadji 1, V. Favre-Nicolin 1, Y. Liu 2, E. Prestat 3, S. Haigh 3, D. Taïnoff 2 and O. Bourgeois 2
Affiliations : 1 Univ. Grenoble Alpes, CEA, INAC, F-38000 Grenoble, France 2 Institut Néel, CNRS, UPR 2940, 38052 Grenoble, France 3 School of Materials, University of Manchester, Manchester, United Kingdom *e-mail of presenting author:

Resume : Thermoelectric materials have recently attracted great interests. Among them, nanostructured materials are very promising because they can exhibit the properties of a “phonon glass electron crystal” material. In our presentation, we will show that nanostructured GeMn is one of the best candidates for thermoelectric applications. Molecular Beam Epitaxy (MBE) growth of GeMn layers under particular growth conditions leads to the formation of Ge3Mn5 nanoclusters embedded in a perfectly crystallized germanium matrix. Beside the thermoelectric properties of this nanostructured GeMn, the structural properties of Ge3Mn5 nano-inclusions have been also investigated using HRSTEM and XRD. The chemical composition has been studied using STEM-EELS and STEM-EDX techniques. Thermal conductivity measurements by 3-omega technique show that the thermal conductivity of nanostructured GeMn is 20 times lower than in the bulk Ge crystal. Doping level of this nanostructured GeMn can be tuned by ion implantation in order to achieve both N-type and P-type doping. This approach opens a way to the fabrication of (Ge,Mn) based thermoelectric devices.

Authors : Hideyuki Mizuno, Stefano Mossa, Jean-Louis Barrat
Affiliations : Univ. Grenoble Alpes, LIPHY, F-38000 Grenoble, France; Univ. Grenoble Alpes, INAC-SPRAM, F-38000 Grenoble, France; Univ. Grenoble Alpes, LIPHY, F-38000 Grenoble, France and Institut Laue-Langevin - 6 rue Jules Horowitz, BP 156, 38042 Grenoble, France

Resume : Large-scale automated search of new chemical compounds with optimized functionalities is a fascinating area of materials science. How different stable topological organization, including ordered and disordered structures, impact properties of materials with the same chemical composition at fixed external thermodynamic conditions is also a very intriguing issue. Consider heat transfer, a process of paramount importance in the design of metamaterials for various technologies, like thermo-electricity. The value determined in the amorphous structure with exactly the same chemical composition is considered as a lower limit for the thermal conductivity of any material. Indeed phonons strongly interact with disorder, and their lifetimes reach the minimum time scale allowed by thermal fluctuations. Smart design at the nano-scale, however, is known to allow reducing the thermal conductivity even below the amorphous limit, as demonstrated in recent breakthrough experiments. In this talk I will address this point. We have studied [1] by classical molecular dynamics computer simulation simple systems, formed by binary mixtures of soft spheres with different masses, for a few values of the mass ratios. The vibrational spectra and the low temperature thermal conductivity have been investigated in the two cases where the masses are distributed at random positions (glass) or organized in a fully ordered intercalated structure (super-lattice). I will show that, by controlling the width of the ordered domains, the thermal conductivity in the direction of the replication pattern can be tuned to reach a value lower than that associated to the completely disordered structure. In this case, the different domains act as filters in complementary non-overlapping regions of the vibrational spectrum, therefore significantly suppressing the total phonons transport in the direction of the replication pattern. I will elucidate the critical role played by the interfaces, and show how to directly modify these latter to achieve this remarkable result. [1] “Beating the amorphous limit in thermal conductivity by superlattices design” H. Mizuno, S. Mossa, and Jean-Louis Barrat Scientific Reports 5, 14116 (2015) - doi:10.1038/srep14116

Authors : Mahmoud Hezam, Abdulaziz Alfarhood, Majed Almalki, Abdullah Aldwayyan, Mohammad Alduraibi
Affiliations : Mahmoud Hezam1,2; Abdulaziz Alfarhood3; Majed Almalki4;Abdullah Aldwayyan3; Mohammad Alduraibi3,5 1King Abdullah Institute for Nanotechnology, King Saud University, Riyadh 11451, Saudi Arabia 2Laboratory of Quantum Optoelectronics, Institute of Condensed Matter Physics, École Poly-technique Fédérale de Lausanne, Lausanne CH-1015, Switzerland 3Physics and Astronomy Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia 4Ministry of Education, Riyadh, Saudi Arabia 5National Center for Applied Physics, King Abdulaziz City for Science and Technology, KACST, P.O. Box 6086, Riyadh 11442, Saudi Arabia.

Resume : Vertically aligned ZnO nanowire arrays have been promising for their use in dye-sensitized solar cells (DSSCs). Among the various available growth techniques, hydrothermal growth in zinc nitrate/hexamine aqueous solution at 90C has been widely preferred as a low-cost, low-temperature technique. However, homogeneous nucleation in the solution during the growth process has been a problem that exhausts the precursor materials, preventing the growth to continue for a longer time. The growth mechanism of ZnO nanowire arrays using hydrothermal growth was investigated in this work by using different growth heating environments; namely a water bath and an electric oven. ZnO quantum dots were dip-casted on an FTO substrate to seed the vertical growth of nanowires. Both samples, in a water bath and in an electric oven, showed similar crystalline quality and morphological dimensions (20-30 nm diameter, 300-400 nm length). Also, the ZnO nanowire arrays in both samples were successfully grown with good homogeneity, and excellent uniformity over a wide substrate area. We show that, although the heterogeneous growth of vertically aligned ZnO nanowires on the seed layer did not show any difference between the two heating media (confirmed by XRD and SEM), the homogeneous nucleation showed a large difference between the two . In an electric oven, homogeneous nucleation resulted in a high density of ZnO microwires, whereas in a water bath, homogeneous nucleation was reduced resulting in micro/nanowires of different dimensions.

Authors : Kan Zhang Jong Hyeok Park
Affiliations : epartment of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749, Republic of Korea

Resume : Improving the inherent poor electrical conductivity of lithium iron phosphate (LiFePO4, LFP) has been considered as most efficient strategy towards high capacity for lithium ion batteries. However, conventional methods using carbonaceous materials suffer from non-conformal structure or insufficient electrical conductivity. Here, we report an order carbonaceous materials coating composed interior N-doped carbon and exterior reduced graphene oxide (RGO) for LFP, which exhibited a specific capacity beyond the theoretical value, ultra-high rate performance, and excellent long-term cyclability. It was found that the interior conformal N-C coating enhances the intrinsic conductivity of LFP nanorods (LFP NR) and the exterior RGO coating acts as an electrically conducting secondary network to electrically connect the entire electrode.

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Battery I : Pascal Pochet
Authors : Normand Mousseau
Affiliations : Département de physique and RQMP, Université de Montréal (Québec) Canada

Resume : From a computational point of view, materials by design has been largely focused on identifying compounds with specific electronic properties. While this approach is still in its infancy, recent successes clearly show that computational screening can accelerate significantly materials discovery. Yet, in most cases, a static characterization is far from sufficient to ensure the viability of proposed materials as kinetic properties, defining stability and evolution, can modify completely the materials' structure and behaviour. Using various examples, I will show how expanded computing powers and new approaches are now transforming how we characterize the potential energy landscape and kinetic properties of materials. Challenges remain, for sure, but it is now possible to beyond a static view of materials and what is we find then is, most often than not, very surprising.

Authors : Martin D. Mayo, Kent. J. Griffith, Chris J. Pickard, Clare. P. Grey, Andrew J. Morris
Affiliations : Department of Physics, University of Cambridge, UK; Department of Chemistry, University of Cambridge, UK; Department of Materials, University of Cambridge, UK; Department of Chemistry, University of Cambridge, UK; Department of Physics, University of Cambridge, UK.

Resume : Phosphorus, in several allotropic variations, is emerging as a high capacity anode candidate for lithium and sodium batteries. The theoretical capacity for Li3P/Na3P is 2596 mA·h·g-1, far exceeding carbon and on par with the best known lithium and sodium battery anodes. To date, some composites of carbon with red or black phosphorus, or phosphorene have been investigated; however, the amorphous or poorly crystalline nature of these composites has hindered the understanding of phosphide intermediates and reaction mechanisms. We use high-throughput computation and the ab initio random structure searching method (AIRSS) to predict the structure of lithium and sodium phosphides, then predict the properties of these systems using DFT, including NMR chemical shielding. We identify that specific ranges in the calculated shielding can be associated with specific ionic arrangements, results which play an important role in the interpretation of NMR spectroscopy experiments. Since the lithium-phosphides are found to be insulating even at high lithium concentrations we show that Li-P- doped phases with aluminium have electronic states at the Fermi level suggesting that using aluminium as a dopant can improve the electrochemical performance of P anodes.

Authors : Kokou Gawonou N’TSOUAGLO, Asma Marzouk, Jorge Seminario, Perla B. Balbuena, Normand Mousseau, Fedwa El-Mellouhi
Affiliations : Qatar Environment and Energy Research Institute, Doha, Qatar; Qatar Environment and Energy Research Institute, Doha, Qatar; Department of Chemistry, Texas A&M University, College Station, TX 77842-3012, USA; Department of Chemical Engineering,Texas A\&M University, College Station, Texas 77843, USA; Département de physique and Regroupement québécois sur les matériaux de pointe, Université de Montréal, Québec, Canada; Qatar Environment and Energy Research Institute, Doha, Qatar.

Resume : Recent years witnessed considerable scientific and technological interest in rechargeable batteries for energy storage intended for several futuristic applications such as electrical vehicles. In addition to experimental studies, numerical and theoretical methods have become fundamental tools for the study of physical and chemical phenomena happening in rechargeable Li-ion batteries. Much effort was given to graphitic anodes to understand how and with what energy barrier lithium diffuses from one site to another. Also to elucidate edge effects on the characteristics of lithium diffusion in graphite. Efforts include a broad range of methodologies such as density functional theory (DFT), ab-initio molecular dynamics (AIMD), classical molecular dynamics (MD) and kinetic Monte Carlo (KMC). The KMC method, introduced 40 years ago is a stochastic approach that can be used to reach long time scales using a fixed and prebuilt catalogue containing information about the diffusion mechanisms identified beforehand. This standard KMC applied to materials science is limited to on-lattice configurations, which are not sufficient to study complex systems and off-lattice positions when elastic effects are important. The development of new KMC methods was of considerable scientific interest to overcome this limitation. This is the case of kinetic ART (k-ART), for example, which uses a very efficient transition-state searching method, ART nouveau, coupled with a topological tool, NAUTY, to offer an off-lattice KMC method with on-the-fly catalog building to study complex systems, such as ion-bombarded and amorphous materials, on timescales of a second or more. Here, we will show an on-the-fly off-lattice KMC method k-ART to study the diffusion mechanism into graphite sheets over long time scales and to characterize the surface effect on lithium diffusion in graphite. The method enables to simulate diffusion of lithium from site to site and evaluate possible reaction barriers as the system evolves and in the presence of structural defects.

Authors : Nicola Seriani
Affiliations : The Abdus Salam ICTP

Resume : Great research efforts are under way to develop cathode materials for Li-ion batteries able to improve battery performance in terms of voltage, energy density, kinetics, cyclability, and price. In this talk, I will show how first-principles simulations based on density functional theory can be used to predict the effect of low amounts of aluminium dopants on relevant functional properties of a cobalt-free oxide. The results show that this lithium-manganese-nickel oxide with low Al concentration is indeed promising for practical applications, leading to increased voltage and energy density, and band electronic conductivity. Moreover, the fundamental insight obtained might be useful for other systems as well.

Authors : One-Sun Lee
Affiliations : Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, PO Box 5825, Doha, Qatar

Resume : There have been significant scientific and technological attentions to lithium-ion batteries (LIB) for many years because of their long cycle life, high energy density, and wider operating temperature range. LIB is a recyclable battery in which lithium ions move from cathode to anode through electrolyte during charging and back to cathode when discharging. Ethylene carbonate (EC) is one of the most common electrolyte because of its high compatibility with graphite electrodes, but the major disadvantage of EC is its high melting point of 36.4°C. Therefore, EC is used with other co-solvent such as dimethyl or diethyl carbonate to increase the melting point. In contrast, propylene carbonate (PC) is stable at lower temperature with melting point of –48.8°C despite the structural similarity to EC. Even though PC-based electrolyte would be more advantageous, however, the graphite of anode exfoliates in PC-based electrolyte that causes battery failure. Therefore, the understanding of the behavior of electrolytes is necessary step to design new batteries with better performance. To understand the different behavior of EC and PC electrolytes at the atomistic level, we performed molecular dynamics simulations of electrolyte intercalated graphene sheets. We observed no diffusion of electrolyte between graphene sheets when interlayer distance is less than 6 Å, but both of EC and PC form monolayer between graphene sheets with comparable density when interlayer distance is 7 ~ 8 Å. Because of the size difference, the intercalated PC molecules induce longer separation distance between graphene sheets compared to that of EC. The longer separation with PC intercalant induces more frequent sliding-exfoliation movement. We found that the exfoliation diffusion coefficient of the graphene sheet with PC intercalant is ~200 times larger than that with EC intercalant. One graphene diffuses and exfoliates from other graphene through sliding displacement rather than vertical separation because of steric interaction with electrolyte molecules in the bulk phase. For calculating the free energy changes of exfoliation, we constructed potential of means force using steered molecular dynamics simulations, and found that the energy barrier of exfoliation of EC intercalated graphene sheets is ~45 kcal/mol where it is ~4 kcal/mol for PC intercalated graphene sheets. We also analyzed the static and dynamic properties of electrolyte confined between two graphene sheets. The self-diffusion coefficient of confined PC is larger than that of EC, but smaller in the bulk phase. We also found that the decaying of the dipole rotation autocorrelation of confined electrolyte is slower than that in the bulk phase. The dynamic properties of the graphene in two different electrolytes reported in this paper can be used for designing new anode materials with better performance.

10:00 Coffee Break    
Authors : Guobo Zeng, Markus Niederberger
Affiliations : ETH Zurich

Resume : Graphene and its derivatives have attracted great attention owing to its highly appealing properties since its first isolation in 2004; however, it has been lately occasionally criticized as ‘graphene fever’ due to the shortage of ‘killer’ applications. Among all potential applications, electrochemical energy-storage devices, particularly lithium-ion batteries (LIBs), are one of the most popular fields for graphene. Despite huge efforts, graphene battery performance is still far from satisfactory in terms of capacity, rate-performance and long-term stability. Here we present a general and facile way to fabricate hierarchical graphene-based aerogels as binder-free anodes for ultra long-life LIBs. In this approach, different types of active anode materials can be easily incorporated as spacer/pillar between graphene layers, e.g. spinel-type metal oxides, or MoxSy/C hybrids. Benefitting from the hierarchical porosity of reduced graphene oxide (rGO) aerogel and its mechanical stability, the hybrid system synergistically enhances the intrinsic properties of each component, yet robust and flexible. As a result, the composite aerogels demonstrate outstanding electrochemical performance and ultra-long cyclability. For instance, the MoxSy/C/rGO composite aerogels were found to enable high capacity (1060 mAh g-1 at 0.35 A g-1), fast rate performance (425 mAh g-1 at 10 A g-1) and ultra-long stability. At 5 A g-1, the capacity can be retained at 336 mAh g-1 (71.3% of the initial) after 10,000 cycles. The excellent results pave an avenue for practical application for graphene in battery industry, and the versatile strategy developed here can be easily extended to the co-assembly of rGO with other functional materials for diverse applications as e.g. supercapacitors or in catalysis.

Authors : Fitri Nur Indah Sari, Jyh-Ming Ting
Affiliations : Materials Science and Engineering Department of National Cheng Kung University

Resume : 2D structure materials are one of the promising material for use in electrochemical capacitor. There are several kind of 2D structure material, such as graphene, MXenes phase, and transition metal dichalcogenides (TMD). In here, we are focus on TMD material which is MoS2. There are two part of the fabrication of 2D structure of MoS2, which are by exfoliation from the bulk MoS2 or directly synthesis of 2D structure of MoS2. In the present study, we prefer to synthesis of 2D structure of MoS2 instead of exfoliation part. We utilized the various carbon template to forming the 2D structure of MoS2 such as graphene oxide (GO), reduced graphene oxide (RGO), N-doped graphene oxide (NDG), and carbon clothes with a facile method, microwave-assisted hydrothermal (MAH). Various degree oxidation of graphene would give nanoflower assembled by nanosheets morphology and carbon clothes would give nanoflakes morphology. These 2D structures would give excellent double layer capacitance. The effect of the time reaction and concentration of MoS2 precursor also were discussed. Physical and chemical properties were be investigated by using X-ray diffraction for the crystallinity, scanning electron microscope (SEM) and transmission electron microscopy (TEM) for the morphology, X-ray photoelectron spectroscopy (XPS) to confirm the chemical content, thermogravimetric analysis (TGA) to know the wt. % of MoS2 in the template. Electrochemical properties of materials were be investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic.

Authors : Elena Zvereva, Damien Caliste, Pascal Pochet.
Affiliations : Laboratoire de Simulation Atomistique (L_Sim), SP2M, UMR-E CEA/Grenoble, INAC, Grenoble, F-38054, France. A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russia.

Resume : Lithium ion-batteries play an important role in rechargeable batteries technologies due to a number of advantages such as high energy storage and reduced gas emission. During the first charge cycle reduction of electrolyte leads to formation of a layer which adheres well to the anode, prevents further degradation and provides Li ions transport into the anode. Accessible experimental data reveal molecular composition of this solid electrolyte interphase (SEI), but almost nothing is known about its structural organization and how the SEI is connected with graphite and forms mutual interface between two materials. The latter is a crucial point determining stability and properties of the SEI and efficient battery operation as a result. Modeling of a “SEI - graphite” interface is not a trivial task due to lack of important structural details. Moreover such interface cannot be set simply as the sterical adjacency of two materials. Chemical and physical interactions between them must be taken into account. We demonstrate our approach to design step by step the SEI close to graphite. Performed within DFT framework, various types of graphite – SEI interfaces and their connections have been evaluated using various criteria such as the formation energy, the electrostatic potential, the dipole moment magnitude etc. The PBE functional, Grimme's dispersive forces and the wavelet basis set were applied using the BigDFT code (Genovese L. et al. J. Chem. Phys. 2008, 129 (1), 014109).

Authors : Hyun Jung, Kang Seop Yun, Kwang-Ryeol Lee, and Sang Soo Han
Affiliations : Center for Computational Science, Korea Institute of Science and Technology, Seoul, Republic of Korea

Resume : For the practical use of silicon nanowires (Si NWs) as anodes for Li-ion batteries, understanding their lithiation and delithiation mechanisms at the atomic level is of critical importance. Here, we report the mechanisms for the lithiation and delithiation of pristine Si and SiOx NWs determined using a large-scale (~100,000 atoms) molecular dynamics (MD) simulation with a reactive force field (ReaxFF). The ReaxFF is developed in this work using first-principles calculations. Our ReaxFF-MD simulation shows that an anisotropic volume expansion behavior of Si NWs during lithiation is dependent on the surface structures of the Si NWs; however, the volumes of the fully lithiated Si NWs are almost identical irrespective of the surface structures. During the lithiation process, Li atoms penetrate into the lattices of the crystalline Si (c-Si) NWs preferentially along the <110> or <112> direction, and then the c-Si changes into amorphous LixSi (a-LixSi) phases due to the simultaneous breaking of Si-Si bonds as a result of the tensile stresses between Si atoms. Before the complete amorphization of the Si NWs, we observe the formation of silicene-like structures in the NWs that are eventually broken into low-coordinated components, such as dumbbells and isolated atoms. On the other hand, during delithiation of the LixSi NWs, we observe the formation of a small amount of c-Si nuclei in the a-LixSi matrix below a composition of Li1.4Si~Li1.5Si, in which the volume fraction of formed c-Si phases relies on the delithiation rate. Our ReaxFF-MD simulation also reveals that SiOx NWs with thin surface oxide layers indeed provide smaller volume expansion rather than pristine NWs during lithiation. Here, oxide layers are more anchored than LixSi/Si interfaces during lithiation, which suppresses volume expansion of the NWs more effectively. And we observe that after lithiation of the SiOx NWs Li4SiO4 and Li2O clusters are formed in the oxide layers in which their concentrations is gradually increased during lithiation. Li atoms of Li4SiO4 clusters are moveable, in other words they can diffuse into c-Si and then form LixSi phases. Simultaneously, the dissociated SiO44- clusters bind to other Li atoms and then Li4SiO4 clusters reform. Moreover, we investigate solid-electrolyte interface (SEI) formation behaviors on Si and SiOx anodes by the ReaxFF-MD simulation, where various electrolytes (e.g. mixtures of EC/PC, EC/DEC and EC/DMC etc) along with a VC additive are considered. Our simulation is confirmed by several reported experiment. We expect that the developed ReaxFF will provide helpful guidelines in designing Si-based anodes to obtain better performing Li-ion batteries.

Authors : Lu Jin, Guobo Zeng, Hua Wu*, Markus Niederberger,Massimo Morbidelli*
Affiliations : Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zurich, 8093 Zurich, Switzerland Laboratory for Multifunctional Materials, Department of Materials, ETH Zurich, 8093 Zurich, Switzerland

Resume : Lithium-ion batteries (LIBs) have been commercially applied in various portable electronic devices nowadays. Tremendous efforts have been devoted to explore new materials for both cathode and anode, and the operating techniques to controllably construct the admired structure. Engineering the surface properties of any new electrode material, including decreasing the particle size, modifying surface functions, controlling the morphology, in order to enhance the electrochemical compatibility with specific electrolyte and facilitate the electron transfer and ion diffusion, is of significance to improve the battery performance. A promising strategy is to develop composite material with adjustable surface chemistry, for example, the carbonaceous materials is greatly explored and intensively studied due to the superior electrochemical properties. However, the methodologies reported in the literature are often applicable only to specific active materials, involving rather complicated preparation routes that are unfavorable for large-scale production. Herein, we propose a generic methodology to generate hierarchical architecture for the active materials of LIB electrodes. Specifically, the nano-sized active material (<10 nm) are carbon-coated and encapsulated inside a conductive matrix derived from polymers, forming submicron-scale spheres. The carbon matrix inside the spheres improves the conductivity and mechanical properties and separates individual nanoparticles (NPs) to avoid their aggregation. Mesopores are generated within the carbon spheres through scarifying partial of the polymer component, necessary for facilitating the diffusion of Li ions in and out of the active material and for accommodating possible volume changes. The inter-space among the carbon spheres generates continuous channels, necessary for ease of electrolyte infiltration. Such a design concept is generic, applicable for various cathode/anode materials. To demonstrate the applicability of the proposed methodology, we have selected anatase TiO2 serving as active materials to be integrated within carbon matrix by applying the aforementioned approach. The as-synthesized TiO2 NPs are <10 nm and in-situ encapsulated into sub-micron poly-(styrene-acrylonitrile) (PSAN) spheres. The precursor of the anode material is obtained by drying properly dense-packed PSAN spheres, and the active anode material is obtained by pyrolysis of the precursor under desired conditions, where the poly-acrylonitrile (PAN) forms graphite-like carbons and the poly-styrene (PS) is sacrificed to contribute to mesopores inside each sphere. The LIBs based on such prepared active anode material exhibits good rate and cycling performance. A reversible capacity of 173 mAh g-1 at a current density of 500 mA g-1 lasts stably along 600 cycles with negligible fading. The high cycling stability demonstrates the advantages and applicability of the proposed methodology in preparation of electrode active materials. It should be also mentioned that the applied preparation route can be well utilized for large-scale production of high performed LIBs.

Authors : Yi-Chen Hsieh, Yi-Hsuan Chen, Wen-Chun Yen, Stuart R. Thomas, Henry Medina, Yu-Lun Chueh
Affiliations : Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, 300, Taiwan; Giga Solar Materials Corporation, Hsinchu, 303, Taiwan

Resume : Owing to its high specific capacity (3579 mAh/g), silicon has become one of the most promising anode material candidates for use in lithium ion batteries. However, the poor cycle lifetime, caused by ~400% volume change during alloying is currently the biggest challenge toward their commercial application. The addition of graphene offers one potential method to overcome this problem. Due to its excellent mechanical properties, graphene is well suited to act as a buffer layer during large volume expansion. Hence, a facile route toward the optimization of graphene reduction is required. We demonstrate two different approaches leading to more efficient and low cost processes to reduce graphene oxide within few minutes. First, the proposed method, so-called “dry method” utilizes silicon carbide as an efficient microwave susceptor heat source. The second method, called “solution method” uses graphene oxide solution with the addition of a reducing agent. In both cases, under microwave radiation, graphene oxide undergoes a rapid heating and reduction to graphene. To characterize our materials, we utilize Fourier transform infrared spectroscopy (FTIR) and X-Ray photoelectron spectroscopy (XPS), the loss of C=O peaks and OH peaks confirm the reduction of graphene oxide and carbon-to-oxygen ratio is 30. The cell performance of our reduced graphene oxide shows capacity values of 1700mAh/g after 50 cycles compared to the 372mAh/g of commercial graphite anode material. Furthermore, by using the solution method, additional precursors can be easily combined into the solution for further material upgrade. We believe this work presents a highly promising technique toward the low-cost production of reduced graphene oxide suitable for future Si based Li-ion battery applications.

12:00 Lunch Break    
Battery II : Normand Mosseau
Authors : Ivano E. Castelli, Martin H. Hansen, Jan Rossmeisl
Affiliations : Department of chemistry, University of Copenhagen, Copenhagen, Denmark; Center for Atomic-scale Materials Design, Technical University of Denmark, Kgs. Lyngby, Denmark; Department of chemistry, University of Copenhagen, Copenhagen, Denmark

Resume : We perform atomic-scale simulations of electrolyte/electrode interfaces [1,2] to study structure and electrochemical properties of electrolytes that are of interest for the Li-ion battery and automotive industry, like Ethyl Methyl Carbonate (EMC) and LP57, which is a combination of EMC and Ethylene carbonate (EC). Ab-initio molecular dynamics (AIMD) and density functional theory (DFT) are used to calculate the structure of the electrolyte at different concentrations and chemical potentials of Li atoms and PF6 anions, and electrode potentials. We also investigate the effect of additives, like vinylene carbonate (VC). Several observable atomic-scale properties, such as phase diagrams and electrostatic potentials, are calculated for our model system, LP57|Au(111). [1] J. Rossmeisl, K. Chan, R. Ahmed, V. Tripkovic, and M. E. Bjorketun, Phys. Chem. Chem. Phys. 15, 10321 (2013). [2] Z. Zeng, M. H. Hansen, J. P. Greeley, J. Rossmeisl, M. E. Bjorketun, J. Phys. Chem. C 118, 22663 (2014).

Authors : Yi-Hsuan Chen, Yi-Chen Hsieh, Wen-Chun Yen, Yu-Lun Chueh
Affiliations : Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, 300, Taiwan; Giga Solar Materials Corporation, Hsinchu, 303, Taiwan

Resume : With a high theoretical specific capacity of 3579 mAh/g, silicon has become one of the most favorable anode materials for lithium ion battery. Although the capacity value of Si is almost ten times larger than the commercial graphite anode; its poor cycle life caused by ~400% volume change when completely lithiated, is the major obstacle for commercial usage. One possible solution to overcome this issue is the use of porous Si. With a much higher surface-to-volume ratio, porous silicon can soak up lithium ions more easily and provide enough space to accommodate larger volume expansion, in turn improving the device cycle life. In this work, we propose a novel method using metal-assisted chemical etching of silicon powder increasing the porosity with high efficiency in a low cost process. Initiating the reaction at a temperature below 0 ºC, the reagent is placed in a metallic acid solution, facilitating pore nucleation and propagation within the particle. To characterize our materials, we utilize scanning electron microscope (SEM) to observe the porous morphology. The size of void space is estimated to be about 10~20 nanometers. In addition, Brunauer-Emmett-Teller (BET) analysis shows increased surface area after the porous formation. The Li-ion battery anode based on our porous Si particles offers an enhanced capacity with over 30% increase compared to anode prepared by intrinsic silicon powder. Furthermore, owing to its excellent mechanical properties, graphene can also act as a buffer layer further improving the Si based battery performance. In addition to the improved capacity and cycle life, we believe the combination of porous silicon powder and reduce graphene has the potential of large scale production for industrial applications.

Authors : Hucheng Song†, Hongxiang Wang†, Linwei Yu†*, Jun Xu†, Zhongwei Yu†, Lijia Pan†, Yi Shi†, Haoshen Zhou‡ and Kunji Chen†
Affiliations : †National Laboratory of Solid State Microstructures and School of Electronics Science and Engineering/Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China ‡ College of Engineering and Applied Sciences, Nanjing University, Nanjing 210093, China

Resume : Seeking high rate, high mass-loading and durable anode materials for lithium ion batteries (LIBs) has been a crucial aspect to promote the use of electric vehicles and other portable electronics. Silicon (Si) has been well-known as an outstanding candidate for LIBs, with a high lithium storage capacity of 4200 mAh/g and a relatively low lithium insertion potential. However, the process of lithium ions (Li-ion) insertion comes with a huge volume change as large as 420% that will cause a radical pulverization/fracture in the Si host and rapid capacity fading. A common strategy to address this issue is to explore various nanostructured Si materials, including nano particles, nanowires (NWs) and nanotubes, which can help to accommodate the large volumetric change during charge/discharge cycling. Among them, nanowire core-shell or hierarchical nano-branch structures have attracted particular interests, where the NW-core can be optimized to serve as efficient electric pathway, while the outer sidewall-coated Si thin film shell or SiNW branches enjoy a large interface for fast Li-ion interaction or insertion. In this presentation, we will first report a novel alloy-forming approach to convert amorphous Si (a-Si) coated copper-oxide (CuO) core-shell nanowires (NWs) into hollow and highly-interconnected Si-Cu alloy (mixture) nanotubes [1, 2]. The conformal coating of a thick a-Si (>120 nm) layer, in a fine-tuned plasma enhanced deposition, helps to forge a beneficial multipath network over the CuO NWs. Upon a simple H2 annealing, the CuO cores are reduced and diffuse out to alloy with the a-Si shell, producing highly-interconnected hollow Si-Cu alloy nanotubes, which can serve as high capacity and self-conductive anode structures with robust mechanical support. A high specific capacity of 1010 mAh/g (or 780 mAh/g) has been achieved after 1000 cycles at 3.4 A/g (or 20 A/g), with a capacity retention rate of ~84% (~ 88%), without the use of any binder or conductive agent. Remarkably, they can survive extremely fast charging rate at 70 A/g for 35 runs (corresponding to one full cycle in 30s) and recover 88% capacity. Then, we propose also a new hierarchical structure of fine-tuned crystalline Si (c-Si) nanowires (NWs) grafted upon ultra-long tin dioxide (SnO2) NW trunks [3], where the latter frame up a large, conductive and stable architecture to: i)host a high mass load of high capacity c-Si NWs medium for Li-ion storage, and ii) guarantee a good electric contact and fast charging process. The Si NWs branches are produced via a low-temperature vapor-liquid-solid (VLS) growth mediated by Sn catalyst droplets produced by a simple H2 plasma treatment upon the SnO2 trunks. Compared to other NW anodes structures, with different nanostructured storage mediums, the c-Si/SnO2 NWs hierarchical structure demonstrates an outstanding performance with a high mass-load (~1.5 mg/cm2 ) and a high areal capacity (~1.8 mAh/cm2) after 100 cycles, without the use of any additional polymer, conductive agent or binders. Finally, we will present our latest progresses in combing the hierarchical nanowire/nanotube structures to achieve simultaneously a high rate, high capacity, high mass-loading and durable nanostructured anode material to fulfill the true potential of Si-loaded LIB applications. References [1] Advanced Functional Materials, DOI: 10.1002/adfm.201504014 (2015), Highly-connected silicon-copper alloy mixture nanotubes as high rate and durable anode materials for lithium ion batteries, Hucheng Song, HongXiang Wang, Zixia Lin, Xiaofan Jiang, Linwei Yu*, Jun Xu*, Zhongwei Yu, Xiaowei Zhang, Yijie Liu, Ping He, Lijia Pan, Yi Shi, Haoshen Zhou and Kunji Chen [2] Nanoscale, advance article, DOI: 10.1039/C5NR06985H (2015), Highly cross-linked Cu/a-Si core–shell nanowires for ultra-long cycle life and high rate lithium batteries, Hongxiang Wang, Hucheng Song, Zixia Lin, Xiaofan Jiang, Xiaowei Zhang, Linwei YU*, Jun XU, Lijia Pan, Junzhuan Wang,* Mingbo Zheng, Yi Shi and Kunji Chen [3] Nano Energy 19, 511 (2016), Hierarchical Nano-branched c-Si/SnO2 Nanowires for High Areal Capacity and Stable Lithium-Ion Battery, Hucheng Song, HongXiang Wang, Zixia Lin, Linwei YU*, Xiaofan Jiang, Zhongwei Yu, Jun XU*, Lijia Pan, Mingbo Zheng, Yi Shi, and Kunji Chen

Authors : Dong-Woong CHOI(1)(2), Kwang-Leong CHOY(1)*
Affiliations : (1) UCL Institute for Materials Discovery, (2)Department of Chemistry University College London, WC1E, 7JE, United Kingdom *Corresponding author:

Resume : Silicon dioxide (SiO2) and zirconium dioxide (ZrO2) are earth abundant materials. SiO2 is studied as the potential replacement of silicon (Si), and ZrO2 is revealed as the material with buffering ability which can alleviate volume change of the host materials in lithium ion batteries (LIBs). This paper reports the novel nanocomposite anode materials of SiO2/ZrO2 (SSZ) with three different Si/Zr ratios of 0.5, 1, and 2.

Authors : Julia Amici, Mojtaba Alidoost, Juqin Zeng, Carlotta Francia, Silvia Bodoardo, Nerino Penazzi
Affiliations : Department of Applied Science and Technology (DISAT), Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino, Italy.

Resume : The demand for high-energy storage systems is constantly increasing, as is the interest to explore alternatives to commercially available batteries. The rechargeable Li-air battery represents an exciting opportunity to design batteries that may satisfy some of the requirements of our future by coupling the light Li metal with the inexhaustible source of O2 of the surrounding air, resulting in high theoretical specific energy density. Currently, most of the researches on the Li-air battery comprise a cell fed with pure O2 allowing that way to maintain long-term operation, owing to the high O2 concentration free of contaminants. However, for many practical applications such as EV, air is the only viable option to supply the battery. In this context, moisture and gases other than O2 may cause side reactions and corrosion. Herein, we report a facile strategy to fabricate an effective oxygen selective membrane with poly(vinylidene fluoride co-hexafluoropropylene) (PVDF-HFP) via non-solvent induced phase separation, casted as a 240 micron thin sheets. The use of different additives helps enhancing the barrier properties as well as the membrane specificity toward O2. For instance, sacrificial silica nanoparticles (SiO2 NPs) were incorporated into the precursor solution to create a controlled alveolar-like structure inside the membrane and then load it with polydimethylsiloxane (PDMS) under vacuum. Galvanostatic charge-discharge tests in a potential/time controlled mode confirmed the ability of the cell with the membrane to reach, in ambient air, nearly the same performances that a dry oxygen fed cell.

15:30 Coffee Break    
Authors : Javier Vazquez-Galvan, [a] * Cristina Flox [a] and Joan Ramon Morante [a,b]
Affiliations : [a] Department of Advanced Materials for Energy Catalonia Institute for Energy Research Jardins de les Dones de Negre, 1, 08930 Sant Adria de Besos, Barcelona. [b] Departament d’Electronica, Facultat de Fisica, Universitat de Barcelona, Spain. *Corresponding author

Resume : Nowadays there is a scientific break trough finding a novel metal free redox flow battery based on bio-inspired organic molecules. It is due to low cost, environmental friendliness, as well as these compounds does not suffer from resource constraints as occurs with metals (i.e. lithium, cadmium or nickel). We have focused on quinone-based batteries, showing different molecules for cathode and anode in aqueous and also organic solvent in order to compare its electrochemical properties, voltage range and capacity. For that reason, we have been carried out 3 electrode, RDE (rotating disk electrode) and battery cycling. Therefore obtain an optimum organic redox flow battery by means of large voltage window, active species solubility, not forgetting about capacity and efficiencies. Comparatively, we were able to test some different molecules, as benzoquinones for cathode materials and anthraquinones for anode materials, in methanosulphonic acid as aqueous solvent. Although we could test them and obtain some relevant results in a 3 electrode cell, with a potential window up to 1.2 V, their solubility still remain inferior to build a battery to cope with lithium ion batteries. On that behave we switch to some organic solvents, as DMSO. Soluble amount of active material reaches 10 to 20 times more in these conditions, which lead us to a charge-discharge polarization curves exhibiting a good performance with our laboratory design flow cell (voltage above 2 V and 60% EE). It can be concluded that the metal-free redox flow batteries is a unique opportunity to boost this technology into the market as a cost-effective alternative (below 100$ kW/h) to the available products.

Authors : Afshin Pendashteh *, Jesus Palma, Marc Anderson, Rebeca Marcilla
Affiliations : Electrochemical Processes Unit, IMDEA Energy Institute, Avda. Ramon de la Sagra 3, Parque Tecnologico de Mostoles, 28935 Mostoles, Spain.

Resume : Fast, rich redox reactions in metal oxides have sparked an increasing interest for their utilization in electrochemical capacitors to boost up the available energy in traditional electrochemical double layer capacitors (EDLCs). In this regard, mixed transition metal oxides, specifically cobaltites, have attracted great attention due to their high specific capacitances.1 However, toxicity, relative high-cost, and scarcity of cobalt are considered main concerns of its employment as electrode material in energy storage applications. All these inspired researchers to partially substitute and reduce Co-content, resulted in development of high performance electrode materials such as NiCo2O4, CuCo2O4, etc.2,3 Therefore, introducing and developing materials with lower cobalt but superior or comparable energy storage performance is of great interest (i.e. ternary cobaltites). NiCoMnO4 is a spinel in which two third of metal sites in the lattice has been occupied by Ni and Mn ions which are known as high energy materials in their simple oxide analogues.4,5 However, to the best of our knowledge, the electrochemical properties of this particular spinel have never been examined in alkaline solutions for energy storage applications. Herein, we report facile hydrothermal synthesis of NiCoMnO4 nanoparticles and their evaluation as positive electrode materials for aqueous asymmetric supercapacitors.6 Structural and compositional features of the prepared samples were illuminated by X-ray diffraction (XRD), energy dispersive electron diffraction (EDX), and X-ray photoelectron spectroscopy (XPS), revealing the purity and presence of various oxidation states in the spinel phase. Transmission electron microscopy (TEM) shed light on morphological aspects of the samples and demonstrated very fine nanoparticles with clear crystallite domains. N2 sorption measurements showed a high specific surface area of 175 m2.g-1 with an average pore width centered in mesoporous region. The electrochemical behavior of the sample as a supercapacitor electrode material was investigated through different techniques including cyclic voltammetry (CV), galvanostatic charge/discharge, and electrochemical impedance spectroscopy (EIS) in 3 M KOH solution. NiCoMnO4 nanoparticles showed a high specific capacitance of 510 F.g-1 at a current density of 1 A.g-1, capable of retaining 285 F.g-1 at 20 1 A.g-1 (~56% capacitance retention). Two-electrode asymmetric devices based on NiCoMnO4 nanoparticles as positive electrode and reduced graphene oxide nanosheets as negative electrode materials were assembled and subjected to different electrochemical evaluations. NiCoMnO4//RGO hybrid devices showed a high real specific energy of 20 and a maximum specific power of 37.5 References: [1] C. Yuan, H. B. Wu, Y. Xie and X. W. Lou, Angewandte Chemie International Edition, 2014, 53, 1488-1504. [2] C. Yuan, J. Li, L. Hou, X. Zhang, L. Shen and X. W. Lou, Advanced Functional Materials, 2012, 22, 4592-4597. [3] A. Pendashteh, S. E. Moosavifard, M. S. Rahmanifar, Y. Wang, M. F. El-Kady, R. B. Kaner and M. F. Mousavi, Chemistry of Materials, 2015, 27, 3919–3926. [4] Y. Ren, Z. Ma and P. G. Bruce, Journal of Materials Chemistry, 2012, 22, 15121-15127. [5] S. Vijayakumar, S. Nagamuthu and G. Muralidharan, ACS Applied Materials & Interfaces, 2013, 5, 2188-2196. [6] A. Pendashteh, J. Palma, M. Anderson, R. Marcilla, RSC Advances, 2016, Under Review.

Authors : Prem Prakash Dahiya, Subhasish Basu Majumder
Affiliations : Materials Science Centre, Indian Institute of Technology Kharagpur

Resume : Layered-layered composites of xLi2MnO3-(1-x)LiMn0.375Ni0.375Co0.25O2 type shows electrochemical capacity ~300mAhg-1 which is above all the commercially available cathode materials. These composites have got potential for application in hybrid electric vehicles and electric vehicles where high energy density is required. These composites are poor in rate performance and cycleability, mainly because of structural transformation, low electronic and ionic conductivity. Li2MnO3 part transform into cubic spinel which causes capacity and voltage fade with cycling. The structural transformation involves movement of transition metal cations to lithium sites and as a result lithium ion mobility lowers down. Modification to the molecular stoichiometry by doping or surface coating of composite has led to considerable improvements in electrochemical performance of these composite cathodes. We have tried doping Li2MnO3 component with Zr on manganese site. Crystalline and phase pure samples were obtained using self-combustion synthetic route. Zr doped 0.5Li2MnO3-0.5LiMn0.375Ni0.375Co0.25O2 composites shows 86% capacity retention after 50 cycles compared to un-doped composite that is 76%. As the amount of dopant is increased, the first cycle capacity starts to fall but the capacity retention is maintained. The optimum amount of Zr doping was found to be 2 mol% at manganese site. xLi2Zr0.02Mn0.98O3-(1-x)LiMn0.375Ni0.375Co0.25O2, x = 0.25 and 0.75 composite show first cycle capacity 198mAhg-1 and 220mAhg-1 with 84% and 86% capacity retention after 50 cycles respectively. These samples exhibited lesser extent of spinel transformation compared to un-doped composite as confirmed from dQ/dV of discharge profiles after 50 cycles of galvanostatic charge-discharge.

Authors : Adèle Ferrand, Trang N.T. Phan, Renaud Bouchet, Sébastien Maria, Didier Gigmes
Affiliations : Aix Marseille université - Institut de Chimie Radicalaire - UMR 7273

Resume : The multiplication of the portable electronic market and also the development of environment-friendly transport motivate strongly the research in the field of the electric storage. Among different battery technologies, Lithium-Metal Batteries is very well positioned thanks to the high energy density of lithium vs its weight and volume. However, the main problem using Li metal, as an anode associated with a liquid electrolyte is the risk of dendrite growth during charge/discharge cycles. This can lead to internal short circuits possibly followed by dramatic explosion and fire. To overcome these drawbacks, solid polymer electrolytes (SPE) combining both high conductivity and suitable mechanical properties to prevent the dendritic growth are perfect candidates. Recently, we shown the remarkable potential of single-ion block copolymer based on polystyrene derivatives and poly(ethylene oxide) as SPE for Lithium-Metal battery technology. In order to constantly improve the SPE properties and to get a better insight in their mode of action, we present in this work the preparation and the use of a large series of SPE based on triblock copolymers. The triblock copolymers are composed of PEO as central block and polymethacrylate or polyacrylate backbone bearing Sulfonyl(trifluoromethylsulfonyl)imide group as external blocks. The thermal and mechanical properties, the conductivity data as well as the electrochemical performance of these block copolymers were measured and compared.

Authors : Vladimir P. Oleshko
Affiliations : Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD 20899 USA

Resume : Plasmons are major collective excitations of valence electrons occurring in solids in the low-loss range (0 to 50 eV). Since valence electron states are primarily responsible for many intrinsic materials properties, plasmons externally induced e.g., by focused electron beams, can be used as an invaluable tool to probe optical, mechanical, cohesive, transport and thermal properties and phase compositions of nanoscale materials with a sub-nm lateral resolution. For materials with preferentially covalent and metallic bonding, which constitute the vast number of energy storage systems, the universal binding-energy relation (UBER) describes relationships between the cohesive energy, Ecoh, the bulk modulus, Bm, and the volume plasmon energy, Ep (valence electron density). The origin of universality and scaling lies in the nature of electron-ion interactions and in the essential exponential decay of electron density with interatomic distance. This opens opportunities to predict physical properties of materials and then to select materials with desired properties by measuring Ep. We will describe how to utilize these relations in order to determine and map nanoscale physical properties of prospective energy materials. Some applications will be illustrated by selected examples, including correlations between Ep, elastic moduli and microhardness, Hm, for nanophase silicon, Si-Li alloys, and conductive carbons used in composite electrodes for high-performance electrochemical batteries.

Authors : Elise Deunf†, Eric Quarez†, Philippe Moreau†, Nicolas Dupré†, Dominique Guyomard†, Frank Dolhem§,⊥, Philippe Poizot*,†,‡
Affiliations : †Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, 2 rue de la Houssinière, B.P. 32229, 44322 Nantes Cedex 3, France. ‡Institut Universitaire de France (IUF), 103 bd Saint-Michel, 75005 Paris Cedex 5, France. §Laboratoire de Glycochimie, des Antimicrobiens et des Agroressources (LG2A), FRE CNRS 3517, Université de Picardie Jules Verne, 33 rue Saint-Leu, 80039 Amiens Cedex, France. ⊥Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France.

Resume : The routine access to power sources is an essential factor for developing our technology-oriented society and ensuring a better quality of life. In this context, while the implementation of renewable energy sources is in progress, electrical energy storage (EES) systems are set to play a central and potentially critical role in the next-generation energy infrastructure. Rechargeable (or secondary) batteries, which are already widely used for powering electrified vehicles and electronic devices of all kinds, appear also as particularly relevant for this future scenario. However, faced with such worldwide battery demand and beyond technical requirements in terms of capacity, energy density, cyclability, safety or cost, issues concerning the resource availability or the recyclability have also to be further addressed. A rapid overview shows that (i) chemistries currently employed are only based on inorganic elements for which some are scarce, expensive and energy greedy at the process level and (ii) none of them seems capable of satisfying our ongoing needs. Hence, it is an urgent need to accelerate progress and innovations in the development of new and potentially “greener” electrochemical storage devices. Based on the tailoring of naturally abundant chemical elements (C, H, N, O, S, in particular), organic chemistry provides great opportunities for finding innovative electrode materials able to operate in aqueous or nonaqueous electrolytes. Along this line, significant progress has been achieved these last ten years on redox-active organic compounds.1–3 Indeed, such greener and low-polluting systems were highlighted by the finding of efficient organic small-molecules and polymers that reach the performance of conventional inorganic composites, bringing them to the attention of the energy storage community.4–9 Nowadays the search of new organic materials is a burgeoning field and one of the remaining challenge relies on finding efficient insertion compounds for negative ions. Indeed, the accommodation of anionic counterions into composite materials is difficult due to their large size compared to the light metal cations (Li+, Na+, Mg+ ...). Reported examples beyond graphite intercalation compounds are rare and this lack of advanced materials for oxidative insertion (p-doping) is recently raising interest for promoting rechargeable batteries with anionic shuttle.10,11 For the first time, organic small molecules were applied as anionic insertion materials. The p-doping of these active compounds is based on the electrochemical activity of neutral amino groups that can (de)insert anion upon (dis)charging. Solvent-host features, intrinsically coming from their lamellar morphologies, were evidenced by spectroscopic, crystallographic and microscopic techniques. The (de)insertion reaction of anions were evaluated with typical battery electrolytes and showed good electrochemical performances vs lithium, with capacities > 75 mAh.g-1 at average operating voltages > 3.2 V vs Li+/Li.12 (1) Armand, M.; Grugeon, S.; Vezin, H.; Laruelle, S.; Ribière, P.; Poizot, P.; Tarascon, J.-M. Nat. Mater. 2009, 8 (2), 120–125. (2) Chen, H.; Armand, M.; Demailly, G.; Dolhem, F.; Poizot, P.; Tarascon, J.-M. ChemSusChem 2008, 1 (4), 348–355. (3) Renault, S.; Gottis, S.; Barrès, A.-L.; Courty, M.; Chauvet, O.; Dolhem, F.; Poizot, P. Energy Environ. Sci. 2013, 6 (7), 2124–2133. (4) Oyaizu, K.; Nishide, H. Adv. Mater. 2009, 21 (22), 2339–2344. (5) Poizot, P.; Dolhem, F. Energy Environ. Sci. 2011, 4 (6), 2003–2019. (6) Liang, Y.; Tao, Z.; Chen, J. Adv. Energy Mater. 2012, 2 (7), 742–769. (7) Song, Z.; Zhou, H. Energy Environ. Sci. 2013, 6 (8), 2280–2301. (8) Janoschka, T.; Hager, M. D.; Schubert, U. S. Adv. Mater. 2012, 24 (48), 6397–6409. (9) Haeupler, B.; Wild, A.; Schubert, U. S. Adv. Energy Mater. 2015, 5 (11), 1402034. (10) Aubrey, M. L.; Long, J. R. J. Am. Chem. Soc. 2015. (11) Reddy, M. A.; Fichtner, M. J. Mater. Chem. 2011, 21 (43), 17059–17062. (12) Deunf, E.; Moreau, P.; Quarez, E.; Dolhem, F.; Guyomard, D.; Poizot, P. Submitted.

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Catalysis I : Gus Hart
Authors : Wolfram Jaegermann
Affiliations : Technische Universität Darmstadt, Institute of Materials Science, Surface Science Division, Petersenstrasse 32, D-64287 Darmstadt, Germany

Resume : From a theoretical analysis of the boundary conditions of efficient production of H2 by photoelectrochemical cells we propose buried p-i-n multijunction structures of highly absorbing thin film compound semiconductors as only (?) promising device structures. Results obtained so far with single absorber layers show that they do not provide the needed photovoltage for H2O splitting. But efficient thin film tandem or multijunction devices of suitable thin film materials with absorber layer bandgaps between 0.8 and 2.4 eV are not yet available besides very expensive 3-5 and medium efficient µc/-Si multijunction cells. Buried junction photoelectrochemical cell structures are needed to provide stable and loss free electrochemical contacts, which are based on electronically and chemically adjusted passivation layer(s) and electronically aligned co-catalysts. Because of these boundary conditions research and development of advanced thin film absorber materials for tandem and multijunction photovoltaics and efficient photoelectrochemical cells follow the same directions and are limited by the same shortcomings. Based on our past and present work on established and novel absorber materials we have identified a number of challenges for material’s development which must be addressed in future work. I will concentrate on two problems for which no easy solution is given yet as the kinetic control of nucleation and growth also at low substrate temperatures and the engineering of interface and contact properties. In most cases the bulk electronic properties of absorber materials are not of reasonable quality when the material growth is at lower sample temperature. But in these cases the morphology of the films shows the preferential morphology as flat films without detrimental pin-holes. For improving the electronic quality of the films annealing steps at elevated temperatures are applied which often lead to a detrimental restructuring of the crystallites in the film forming larger grains and pin-holes or grain boundary shunts and therefore deteriorates the conversion efficiencies. With respect to interface engineering dissimilar contacts are applied in most cases which are not appropriately adjusted in their chemical and electronic properties. As a consequence interface defects and only low built-in potentials due to the Fermi level pinning result. For electronic passivation of surface/interface states specifically engineered interfaces must be developed based on non-abrupt interdiffused or reactively adapted heterojunctions. With such multijunction solar cells based on thin film absorber materials promising research and development routes to highly competitive PV and PEC cells are given which need, however, systematic materials research strategy combining theoretical design concepts and high throughput experimental validation.

Authors : Lei Wang and Patrik Schmuki
Affiliations : Department of Materials Science and Engineering, WW4-LKO, University of Erlangen-Nuremburg, Martensstr. 7, D-91058 Erlangen, Germany.

Resume : Aligned Ta3N5 nanotube (NT) photoanodes are formed by anodic oxide-tube growth on a Ta substrate, followed by a thermal conversion of the oxide to nitride in NH3. Here we introduce, prior to ammonolysis, a reductive heat treatment (in Ar/H2) to induce the controlled growth of a suboxide/subnitride (TaxNy) layer at the metal/Ta3N5-NT interface. This subnitride layer promotes electron transfer to the back contact and provides a drastic increase in solar conversion efficiency in photoelectrochemical water splitting, that is, a solar photocurrent of 4.2 mA cm-2 at 1.6 VRHE for the Ar/H2-treated Ta3N5 NTs is obtained under AM 1.5G simulated sunlight (100 mW cm-2) in 1 M KOH. Further modification with Co(OH)x co-catalyst leads to a record photocurrent of 11 mA cm-2 at 1.6 VRHE.

Authors : V. Celorrio;1 E. Dann;1 L. Calvillo;2 G. Granozzi;2 A. Aguadero;3 D. Kramer;4 A. Russell;5 David J. Fermín1
Affiliations : 1School of Chemistry, University of Bristol, Cantocks Close, Bristol BS8 1TS, UK. 2Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131 Padova, Italy. 3Department of Materials, Imperial College, London SW7 2AZ, U.K. 4Engineering Sciences, University of Southampton, SO17 1BJ Southampton, U.K. 5School of Chemistry, University of Southampton, Highfield, Southampton, U.K.

Resume : Oxygen reduction reaction (ORR) has been extensively studied due to its important role in energy conversion systems such as fuel cells and metal air batteries. Suntivich et al. reported that perovskite oxides could be optimized for ORR catalysis from molecular orbital principles. An M-shaped relationship between activity and the d-electron number per B cation was found. At the same time, a volcano shape plot is exhibited between the activity of oxides and the eg-filling of B ions, having a value of 1 for maximum activity. In this work, a structure-reactivity relationship is established for the oxygen reduction reaction (ORR) at carbon supported lanthanum based oxides employing rotating ring-disc electrodes. Highly phase pure LaCrO3, LaMnO3, LaFeO3, LaCoO3 and LaNiO3 nanoparticles were synthesised by an ionic liquid route, offering fine control over phase purity and composition. RRDE experimental data clearly reveal that LaMnO3 is by far the most active catalysts of the family. The nature of the active site is also discussed, concluding that the high activity of LaMnO3 is connected to changes in the redox state of the B-site close to the formal ORR potential. In order to strengthen our working hypothesis, the activity of LaxCa1-xMnO3 as a function of x is as well been studied. These results show that the onset potential for ORR decreases as x decreases. This trend is qualitatively consistent with the conclusion that Mn(III) is more active than Mn(IV). However, this issue is a lot more subtle as the extent of A-site segregation also decreases as x decreases, leading to more surface Mn sites in the case of CaMnO3, consistent with the larger voltammetric features and confirmed by quantitative XPS analysis.

Authors : Anna Regoutz, Ignacio Villar-Garcia, Gwilherm Kerherve, David J. Payne
Affiliations : Department of Materials, Imperial College London, Royal School of Mines, London, SW7 2AZ, UK

Resume : CO2 is a source for the production of carbon based fuels, such as methanol, and presents an attractive alternative to fossil fuels. Copper is an ideal catalyst for the reduction of CO2, as it is able to direct reactions through stable intermediates, e.g. CO. An important question concerns the influence of oxygen on the catalytic activity and whether oxides are formed on the surface. As this system is an excellent material for the reduction of CO2 a detailed understanding of the basis of its catalytic activity is essential and absolutely necessary for any further development. X-ray photoelectron spectroscopy (XPS) is used widely in the solid-state sciences but due to its nature as an ultra high vacuum technique (pressure 10-9 mbar) it is not possible to study gas-solid interfaces. High-pressure XPS (HPXPS) is an advanced method which allows the measurement of solid samples at elevated pressures of between 1 and 30 mbar. This work presents results on the interaction of CO2 and CO2/O2 with the surface of polycrystalline Cu followed by HPXPS. Cu2p core levels, as well as the Cu Auger lines are used to investigate the state of the Cu surfaces. The C1s and O1s core levels are used to track the interaction between CO2/O2 and Cu and are compared to CO2/O2 gas phase measurements. Ultimately, the presented results provide a starting point for the detailed understanding of these catalysts and lead to the identification of possible ways to further improve and develop their properties.

Authors : Sandra Haschke, Yanlin Wu, Julien Bachmann, Muhammad Bashouti, Silke Christiansen, Dima Pankin and Alina Manshina
Affiliations : SH, YW, JB: Department of Chemistry and Pharmacy, Friedrich Alexander University of Erlangen-Nürnberg, Germany; MB: Max Planck Institute for the Science of Light, Erlangen, Germany; SC: Helmholtz Center Berlin, Germany; DP, AM: Center for Optical and Laser Materials Research, Saint-Petersburg State University, Russia;

Resume : The ability to electrolyze water into its elements in benign conditions at low cost will imply the exclusive use of cheap, abundantly available materials, instead of most advanced catalysts. Here, we demonstrate that iron oxide, the most abundant and least expensive transition metal compound, can be used as a catalytically active surface for the four-electron water oxidation to O2 at neutral pH which represents the kinetic bottleneck of the overall reaction. The geometric effects of nanostructuring a pure Fe2O3 surface on its electrochemical water oxidation performance were systematically explored. Atomic layer deposition was used to coat the inner walls of cylindrical “anodic” nanopores ordered in parallel arrays with a homogeneous Fe2O3 layer. The chemical nature of our iron oxide electrode surface was investigated by means of Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction. Combining electrochemical treatments and annealings with the “anodic” pore geometry can deliver an effective turnover increase by two to three orders of magnitude with respect to a smooth, planar Fe2O3 surface. However, the current density depended on the pore length in a non-monotonic manner. An optimal length was found that maximized turnover by equating the rate of transport in the electrolyte with that of charge transfer across the interface. Further optimization of the catalyst performance was achieved by bulk and surface doping of iron oxide.

10:00 Coffee break    
Authors : Qiang Fu †, Luis César Colmenares Rausseo ‡, Umberto Martinez §, Paul Inge Dahl ‡, Juan Maria García Lastra †, Per Erik Vullum ‡, Ingeborg-Helene Svenum ‡, and Tejs Vegge †
Affiliations : † Department of Energy Conversion and Storage, Technical University of Denmark, Fysikvej, 2800 Kongens Lyngby, Denmark ‡ SINTEF Materials and Chemistry, NO0-7465 Trondheim, Norway § QuantumWise A/S, Fruebjergvej 3, Postbox 4, 2100 Copenhagen, Denmark

Resume : Antimony-doped tin dioxide (ATO) is considered a promising support material for Pt-based fuel cell cathodes, displaying enhanced stability over carbon-based supports. In this work, the effect of Sb segregation on the conductance and catalytic activity at Pt/ATO interface was investigated through a combined computational and experimental study. It was found that Sb-dopant atoms prefer to segregate toward the ATO/Pt interface. The deposited Pt catalysts, interestingly, not only promote Sb segregation, but also suppress the occurrence of Sb3+ species, a charge carrier neutralizer at the interface. The conductivity of ATO was found to increase, to a magnitude close to that of activated carbon, with an increment of Sb concentration before reaching a saturation point around 10%, and then decrease, indicating that Sb enrichment at the ATO surface may not always favor an increment of the electric current. In addition, the calculation results show that the presence of Sb dopants in ATO has little effect on the catalytic activity of deposited three-layer Pt toward the oxygen reduction reaction, although subsequent alloying of Pt and Sb could lower the corresponding catalytic activity. These findings help to support future applications of ATO/Pt-based materials as possible cathodes for proton exchange membrane fuel cell applications with enhanced durability under practical applications.

Authors : Richard D Tilley Lucy Gloag
Affiliations : School of Chemistry, University of New South Wales, Sydney, NSW, 2052, Australia

Resume : Bimetallic nanoparticles have emerged as the new, leading edge of heterogeneous catalysts by enabling the combination of multiple materials in different compositions and arrangements to achieve both enhanced and selective catalytic performance. Three dimensional nanoparticles offer an exciting opportunity for bimetallic nanocatalysts; unlike two dimensional nanoparticles that lie flat on a substrate, the faceted surface features can be readily accessed by protruding outwards from a catalyst support. In this work, we present the synthesis and characterisation of three dimensional Pd-Ru and Au-Ru core-branched nanostructures with highly faceted surface features. The key to the formation of these novel structure is a three stage growth mechanism, which will be critical to the development of the next generation of complex nanostructures for oxygen evolution reaction electrocatalysis.

Authors : Amrita Bhattacharya[1], Saswata Bhattacharya[2]*
Affiliations : [1] Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany, [2] Department of Physics, Indian Institute of Technology Delhi, New Delhi, India *

Resume : Complex binary hydrides involving light metals (e.g Li, Mg, Ca etc.) have been extensively studied as possible hydrogen storage materials because of their high gravimetric storage capacity. In particular, lithium nitride/imide/amide have been found to exhibit strong affinity for hydrogen. Unfortunately, though these materials can store sufficiently high amount of hydrogen, the desorption kinetics is poor for its on-board practical application. Making nano-structures of such materials ease the hydrogen release from the system. However, quest for designing new materials demands the accurate description of all their (meta)-stable structures under operational conditions. Unfortunately, not a single theoretical work (till date) related to designing hydrogen storage materials has addressed the challenging problem of the (meta)-stability of the materials under operational conditions. We find[1] from hybrid density functional theory and ab initio atomistic thermodynamics that the behavior of small LixNy clusters are very different than their bulk. Most importantly, while in bulk lithium nitride, the Li-rich phase [i.e. Li3N] is the stable stoichiometry; in small LixNy clusters, N-rich phases are more stable at thermodynamic equilibrium. Finally we find that these N-rich clusters are promising hydrogen storage material because of their easy adsorption and desorption ability at respectively low (≤ 300K) and moderately high temperature (≥ 600K). [1]A. Bhattacharya, S. Bhattacharya J. Phys. Chem. Lett. 6, 3726 (2015).

Authors : ENESCA Alexandru; ISAC Luminita, BOGATU Cristina, PERNIU Dana, COSNITA Mihaela, DUTA Anca
Affiliations : Transilvania University of Brasov, R&D Centre: Renewable Energy Systems and Recycling, Romania

Resume : Solid state solar cells, derived from ETA cells are well known and represent a Vis-active heterostructures with at least one n-p hetero-junction. Most of these heterostructures involve TiO2 (as n-type window layer, with high chemical stability) and a p-type material, mainly a chalcogenide (as Vis-absorber). Following this concept the paper proposes the design principles of a Vis-active photocatalyst, for advanced oxidation processes, aiming at efficient wastewater treatment, targeting re-use. Basically, the heteorstructure should be a photovoltaic assembly with additional design pre-requisites: high stability in the working environment, high photo-corrosion resistance, etc. As case-studies, two heterostructures are analysed: TiO2/CIS and CIS/SnO2/TiO2; the heterostructures were deposited via spray pyrolysis and the optimised multilayers were characterised considering typical photovoltaic properties (I-V curves, photo-current) and typical photocatalytic properties in methylene blue removal, selected as standard pollutant (Total Organic Carbon and Total Nitrogen removal efficiencies). Correlations between these two groups of properties allows a reliable design of Vis-active photocatalysts, with high mineralization efficiencies in optimised conditions (92% of TOC removal). Additional, the effect of electrolyte addition (supporting the current flow in the local micro-electrochemical cells) is analysed by adding various amounts of NaCl (0.5….8%) in the aqueous pollutant system.

Authors : Stefanie Schlicht, Sandra Haschke, Julien Bachmann, Yuri Petrov, Alina Manshina
Affiliations : Friedrich Alexander Universität Erlangen-Nürnberg; SPSU Interdisciplinary Resource Center for Nanotechnology

Resume : The preparation of nanostructured iridium oxide electrodes for the electrochemical oxygen evolution from water is explored. Due to its good electric conductivity and high catalytic activity, iridium oxide is used as active surface for the four-electron water oxidation to oxygen, which represents the kinetic bottleneck of the splitting of water. The use of anodic aluminum oxide templates, which are created according the usual two-step anodization procedure, lead to a well-defined and tunable geometry of electrodes. The coating of the inner walls of the cylindrical and parallel nanopores with iridium oxide catalyst is performed by atomic layer deposition from (1,3-cyclohexadiene)(ethylencyclopentadienyl)iridum and ozone, whereas the mechanism of the reaction can be monitored in situ by a piezoelectric crystal microbalance. The morphology of the generated nanostructured electrodes is characterized by scanning electron microscopy and helium ion microscopy and its elemental composition is confirmed by energy-dispersive X-ray spectroscopic analysis. The electrochemical characterization in acidic media is performed by cyclic voltammetry, bulk electrolysis and electrochemical impedance spectroscopy. This preparative method allows for a systematic tuning of the electrode’s geometric surface area by variation of the nanopores’ diameter and length. The electrocatalytic current densities vary accordingly.

Authors : Niklas Lindahl, Eleonora Zamburlini, Ligang Feng, Henrik Grönbeck, Ifan Stephens, Ib Chorkendorff, Christoph Langhammer, Björn Wickman
Affiliations : Department of Physics, Chalmers University of Technology; Center for Individual Nanoparticle Functionality, Technical University of Denmark; Department of Physics, Chalmers University of Technology; Department of Physics, Chalmers University of Technology; Center for Individual Nanoparticle Functionality, Technical University of Denmark; Center for Individual Nanoparticle Functionality, Technical University of Denmark; Department of Physics, Chalmers University of Technology; Department of Physics, Chalmers University of Technology

Resume : Fuel cells can provide clean energy from hydrogen fuel and air. The main challenges for further improvement of the efficiency of polymer electrolyte membrane fuel cells are the activity and stability of the catalysts, typically Pt, used for the oxygen reduction reaction. Experiments on polycrystals and cluster-deposited nanoparticles have shown that Pt alloyed with rare earth (RE) metals has about 5 times improved specific activity compared to pure Pt, due to the formation of a strained Pt overlayer which changes the binding energies to the reactants. We have developed a generic method for single target co-sputtering of PtRE alloys. The method enables efficient fabrication of thin films with varying compositions and thicknesses down to few nanometers, while being compatible with mass-fabrication. To validate our approach we have measured the ORR-activities of PtY thin films with different thicknesses and compositions, which we found to be similar to the specific activities of polycrystals and to the mass activities of nanoparticles of the same alloy material. Characterization by XPS and EDX, before and after ORR-measurements, has confirmed the formation of a Pt-overlayer on the alloy thin films.

12:00 Lunch break    
Poster II (Parallel with Catalysis II) : NN
Authors : Arik Yochelis, Nir Gavish
Affiliations : Department of Solar Energy and Environmental Physics, Swiss Institute for Dryland Environmental and Energy Research, Blaustein Institutes for Desert Research (BIDR), Ben-Gurion University of the Negev, Sede Boqer Campus, Midreshet Ben-Gurion 84990, Israel; Department of Mathematics, Technion--Israel Institute of Technology, Technion City 32000, Israel

Resume : Room temperature ionic liquids are attractive to numerous applications and particularly, to renewable energy devices. As solvent free electrolytes, they demonstrate a paramount connection between the material morphology and Coulombic interactions: unlike dilute electrolytes, the electrode/RTIL interface is a product of both electrode polarization and spatiotemporal bulk properties. Yet, theoretical studies have dealt almost exclusively with independent models of morphology and electrokinetics. In this work, we develop a novel Cahn-Hilliard-Poisson type mean-field framework that couples morphological evolution with electrokinetic phenomena. Linear analysis of the model shows that spatially periodic patterns form via a finite wavenumber instability, a property that cannot arise in the currently used Fermi-Poisson-Nernst-Planck equations. Numerical simulations in above one-space dimension, demonstrate that while labyrinthine type patterns develop in the bulk, stripe patterns emerge near charged surfaces. The results qualitatively agree with empirical observations and thus, provide a physically consistent methodology to incorporate phase separation properties into an electrochemical framework.

Authors : Saheed Bukola†£, Belabbes Merzougui* ‡, Mohammad Qamar†
Affiliations : †Center of Nanotechnology (CENT), King Fahd University of Petroleum and Minerals, Dhahran, 31261, Eastern Province, Saudi Arabia ‡Qatar Environment and Energy Research Institute (QEERI), Qatar Foundation, Doha 5825, Qatar £Current address: Department of Chemistry, Clemson University, Clemson, 29634, USA

Resume : ABSTRACT: The production of hydrogen from abundant seawater is among the approaches being considered to better utilize renewable energy (e.g., solar and wind). The potential of “hydrogen economy” as the 21st century energy source target has made the search for viable alternatives to platinum (Pt) electrocatalyst an important area of research and development. The high cost of platinum and its instability in the electrochemical power systems for hydrogen generation are still predominant challenges [1-3]. Thus, the success would be consequent upon developing cost effective, stable and highly active Pt-free electrocatalysts. In this regard, a series of nanostructured catalysts based on cobalt-doped molybdenum carbide (Co-MoC) supported on carbon has been developed for electrolytic hydrogen evolution reaction (HER) from brine. The catalysts were synthesized by simple impregnation of metal salts on carbon support and followed by pyrolysis in CH4 atmosphere. The obtained catalysts showed impressive HER activities in both brine and alkaline media. The overpotential for these developed Co-MoC/C catalyst series was close to that of a commercial Pt/C catalyst, ranging from 63 to 89 mV and 15 to 148 mV in brine and alkaline solutions respectively. Such results for HER on Pt-free based materials seems to be very interesting, especially in brine media. Results reveal electrochemical desorption following the Volmer-Heyrovsky mechanism as the rate determining step. The superior HER activities of Co-MoC/C catalysts will be presented and discussed in details taking in consideration their properties, such as mesopore surface areas, composition, nanocrystallites, and low charge transfer resistances as confirmed by electrochemical impedance technique. KEYWORDS: electrocatalyst, hydrogen evolution reaction, brine water, molybdenum carbide, sustainable fuel REFERENCE: [1] Harnisch, F.; Sievers, G.; Schrӧder, U. Tungsten Carbide as Electrocatalyst for the Hydrogen Evolution Reaction in pH Neutral Electrolyte Solutions, Appl. Catal. B. Environ. 2009, 89, 455–458. [2] Wang, M.; Sun, L. Hydrogen Production by Noble-Metal-Free Molecular Catalysts and Related Nanomaterials, ChemSusChem. 2010, 3, 551–554. [3] Han, A.; Jin, S.; Chen, H.; Ji, H.; Sun, Z.; Du, P. A Robust Hydrogen Evolution Catalyst Based on Crystalline Nickel Phosphide Nanoflakes on Three Dimensional Graphene/Nickel Foam: High Performance for Electrocatalytic Hydrogen Production from pH 0–14, J. Mater. Chem. A. 2015, 3, 1941–1946.

Authors : Vivek Ramakrishnan, Kim Hyun, and Bee Lyong Yang*
Affiliations : School of Advanced Materials and System Engineering, Kumoh National of Institute of Technology, Yangho-dong, Gumi-si, Gyeongsangbuk-do, South Korea

Resume : Multi-junction photo-electrode for overall water splitting is always challenging on the basis of electronic and thermodynamic requirements. A tandem nanostructure consisting of n-type and p-type semiconductors for overall water splitting is always desirable without external bias. It is very well known that titanium dioxide (TiO2) nanostructures reported to have high chemical stability, low cost, abundance as well as the favorable band edge alignment with water redox potentials which make them a potential candidate as photo-anodes for water oxidation which have been extensively studied. Cobalt oxide systems (Co3O4 and CoO) are well studied in the field of photo-catalysis. The p-type Co3O4 and CoO have a band gap of 2.1 and 2.6 eV respectively. Co3O4 based systems have got wide variety of applications such as heterogeneous catalysis, Li-ion batteries, photo-catalysis, solar absorbers etc. It is reported that when microcrystalline CoO is changed to nano-crystalline state, band gap position changes drastically, enabling it for overall water splitting.1 The p-type CoO nanostructures could be an efficient photocathode. So by coupling CoO with TiO2 with specific nanostructures could be crucial for overall water splitting. In the present work, we will compare the photo-catalytic activity of different configurations of combined systems constituted by CoO nano-structure with TiO2 nanorods grown on FTO substrate. TiO2 nanorods were grown on FTO by hydrothermal synthesis. Cobalt oxide nanoparticles were deposited on TiO2 nanorods by electrodeposition followed by Rapid Thermal Annealing. The detailed structural investigation of as-prepared system with improved photoelectrochemical properties will be reported.

Authors : Roby Sonia, Bihag Anothumakkoola, Sreekumar Kurungot
Affiliations : Academy of Scientific and Innovative Research, Delhi India National Chemical Laboratory, Pune, India

Resume : The present work deals with the synthesis of a thin and flexible solid-state supercapacitor by using a hybrid electrode derived from buckypaper (BP) and polyethylenedioxythiphene (PEDOT). Electrode with low sheet resistance and charge transfer resistance could be accomplished by confining PEDOT along the surface of the carbon nanotubes (CNTs) of BP followed by effectively creating the electrode-electrolyte interface by infiltrating lithium chloride-polyvinyl alcohol (LiCl-PVA) gel electrolyte. The PEDOT growth along the CNT surface could be achieved by the interfacial polymerization of the monomer, i.e.,ethylenedioxythiophene (EDOT), which leads to a surface aligned growth of PEDOT and one dimensional confinement over the surface of CNTs. The critical role played by the hydrophilic interaction between the carboxylic functional groups on the surface of CNTs and the oxidizing agent iron perchlorate (Fe(ClO4)3) is found to be helping the system to establish a uniform and aggregate-free growth pattern of PEDOT. By carefully manipulating the composition of PEDOT in the paper, flexible electrode with an ultralow sheet resistance of 2.1 Ω □-1 and Equivalent Series Resistance (ESR) of 1.2 Ω has been achieved. The prepared solid-state supercapacitor has a thickness of 146 µm and the system delivered a volumetric capacitance of 11 Fcm-3and an areal capacitance of 310 mFcm-2, which is expected to be the highest in its class. The strategy adopted here is scalable and the process can be conveniently applied to prepare large area PEDOT modified BP in short span of time.

Authors : Ji-Eun Lee, Dong Ha Kim*
Affiliations : Department of Chemistry and Nano Science, Ewha Womans University, Seoul, South Korea

Resume : The design of novel catalysts requires not only reducing the amount of Pt used but also enhancing catalytic activity and stability for efficient catalysts of electrode on both anode and cathode. It has been reported that metallic core@shell nanostructures have numerous advantages and potential uses in electronics, magnetics, catalysts and optics. Their versatility in a wide range of applications stems from their unique physical and chemical properties directly related to particle size, shape, interparticle distance and surface properties. Composites consisting of functional polymers and metal nanoparticles are of great interest due to their combined properties with improved dispersion of metal nanoparticles and high surface area. We suggest novel core@shell nanoparticles based on AuNPs decorated with polymer which can serve as templates for tailored nanostructures. Concretely, AuNPs having polymer shell on the surface were first fabricated. Then, they were mixed with selected metal precursor solutions followed by reduction using reducing agent. The metal NPs thus incorporated were distributed uniformly in the polymer shells. We systematically investigated the structural development during the sequential synthetic process and compared the performance with respect to metal-decorated core-shell nanostructures. The core-shell nanostructures showed a viable and efficient electrocatalytic activity for both anode and cathode in electrodes of fuel cell or metal air-battery.

Authors : Daniela Ion-Ebrasu, Stanica Enache, Amalia Soare, Mihai Varlam, Ioan Stefanescu
Affiliations : National Institute for Cyogenics and Isotopic Technologies ICSI-Rm. Valcea, Uzinei Street No. 4, 240050, Romania; tel. +40250733890

Resume : In this paper we report on the development of nano-sized ruthenium/niobium catalysts obtained by DC magnetron sputtering in Ar atmosphere, without using oxygen during deposition. Residual contamination with oxygen renders the films composite, consisting of ruthenium/niobium oxide-like structure conglomerates. The catalytic activity of the ruthenium/niobium oxide layer is investigated by voltammetric methods whereas the structural, electrical and optical properties are studied by XRD, frequency dependent impedance, UV-Vis transmission techniques, and Scanning Electron Microscopy (SEM-EDS) experiments. Scanning Electrochemical Microscopy (SECM) for the catalytic reaction analysis at solid-liquid interfaces is applied.

Authors : B. Bouhafs, A, Cherifi and A. Bezza
Affiliations : University of Tlemcen, Faculty of Sciences, Theoretical Physics Laboratory. Algeria

Resume : Various bio-sensing systems have been suggested to be an efficient tool to investigate optical interactions and manipulating electromagnetic fields spatially distributed in the vicinity of an interface between a conductor and a dielectric. However, electromagnetic fields associated to surface-plasmons (SPs), resonant phenomena, have been analyzed both theoretically and numerically considering real dielectric gaps (with or without a periodic modulation) stacked between metallic films. Thus, properties of SPs have been controlled by the change of the metal film thickness and refractive index of a dielectric which is assumed to be the sensing medium. In the present work, we suggest a new tunable plasmonic cavity, consisting of a transparent conductor, i.e. indium tin oxide (ITO) embedded between two left-handed materials (LHMs) that exhibits high confinement energy of surface plasmon resonance (SPR) when geometric parameters are properly optimized. Here, each of the later LHMs is simulated by its complex permittivity and magnetic permeability expressed in a dependent-wavelength. Using the electromagnetic theory based on transfer matrix-method to express interface’s response, we carried out detailed analysis to design high performance of the nano-cavity by exploiting the advantage of the absorption effect of ITO gap. In addition, the performance of the designing SP sensor has been quantified in terms of sensitivity and detection accuracy. Finally, taking the sensing medium as glucose solution, in a spectral TM reflectance-mode, potential applications recognized to the designed sensor are discussed. Keywords: Imaging Sensor, Left-handed Materials, Dielectric Gap, Surface Plasmon Resonance, Performance Parameters, TM Reflectance-Mode

Authors : N. Bsiri (a), M. A. Zrir (b), A. Bardaoui (a), M. Bouaїcha* (a)
Affiliations : (a) Laboratoire de photovoltaϊque, Centre de recherches et des technologies de l’énergie, Technopole de Borj-Cédria, BP 95, Hammam-lif 2050, Tunis, Tunisia (b) Aix-Marseille Université, CINAM, Campus de Luminy Case 913, 13288 Marseille, France

Resume : Pure and chromium doped titanium dioxide (TiO2) thin films at different atomic percentages (0.5 %, 1.3 % and 2.9 %) have been elaborated on ITO/Glass substrates by sol-gel and spin-coating methods using titanium (IV) isopropoxide as a precursor. The surface morphology of films was investigated by scanning electron microscopy (SEM), the structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and high resolution transmission microscopy (HRTEM). SEM and HRTEM show homogenous and polycrystalline films. XRD patterns indicate a phase transition from anatase to anatase-rutile leading to expand the absorption band of TiO2 molecules around 520 cm-1 in FTIR spectra. The optical constants such as the refractive index (n), the extinction coefficient (K) and the band gap (Eg) as well as the film thickness are determined using spectroscopic ellipsometry technique and Fourouhi-Blommer dispersion model. Results show three major changes; i) the thickness of pure TiO2 layer is 54 nm, which linearly decreases when the layer is doped with chromium and reaches 33 nm for a doping concentration of 2.9 %, ii) the band gap energy (Eg) is also linearly reduced from 3.24 eV to 2.79 eV when the Cr-doping agent increases, and, iii) a phase transition from anatase to anatase-rutile is observed causing an increase in values of n() for wavelength greater than 350 nm.

Authors : Hyunchul Oh, Michael Hirscher
Affiliations : Gyeongnam National University of Science and Technology, Jinju, Gyeongnam, 52725 Republic of Korea; Max Planck Institute for Intelligent Systems, Stuttgart D-70569, Germany

Resume : Hydrogen has 3 isotopes-protium(normal hydrogen), deuterium and tritium. Among them, deuterium and tritium are used as energy source of nuclear fusion reaction which requires the separation of these hydrogen isotopes. Since hydrogen isotopes share their size, shape and thermodynamic properties, separation of these isotope mixtures is one of the challenges in modern separation technology. Recently, confined space of porous media has received increased attention as an efficient method for hydrogen isotope separation, and this is so-called quantum sieving[1]. Despite many theoretical calculations[2], however, it has been difficult to identify a feasible microporous material up to now. Among various porous materials, the novel class of microporous framework materials (COFs, ZIFs and MOFs) is considered as the most promising approach for isotope sieving due to ultra-high porosity and uniform pore size which can be tailored in these materials. In the work, we focused on the investigation of the fundamental correlation between D2/H2 molar ratio and pore size at optimized operating conditions by using different nanoporous frameworks. It reveals that the D2/H2 molar ratio is strongly depending on pore size, pressure and temperature. The smaller pore size and the lower P, T, the higher separation factor can be obtained[3]. Afterwards, two strategies for satisfying industrial requirements are introduced. Firstly, one way of increasing the operating pressure is presented by using cryogenically flexible COFs[4]. Secondly, a different chemical affinity of isotopes on strong adsorption sites is demonstrated in order to increase the operating temperature for isotope separation[5]. Finally, deuterium separation from a diluted isotope mixture is experimentally demonstrated by applying a temperature swing process. References [1] J. J. M. Beenakker et al., Chem. Phys. Lett., 232 (1995) 379-382. [2] G. Garberoglio, Chem. Phys. Lett., 467 (2009) 270-275. [3] H. Oh et al., J. Mater. Chem. A, 1 (2013) 3244-3248. [4] H. Oh et al., Angew. Chem. Int. Ed., 52 (2013) 13219-13222. [5] H. Oh et al., ACS nano, 8 (2014) 761-770.

Authors : Hyunchul Oh, Michael Hirscher
Affiliations : Gyeongnam National University of Science and Technology, Jinju, Gyeongnam, 52725 Republic of Korea; Max Planck Institute for Intelligent Systems, Heisenbergstrasse 3, D-70569 Stuttgart, Germany.

Resume : For most (nano)porous materials, it is prerequisite to determine their textural properties, especially for applications in hydrogen gas storage. Indeed, the measurement of gas adsorption on porous materials is mature research field for the purpose of specific surface area (SSA), pore size distribution (PSD), specific pore volume (SPV) and porosity determination. Since the adsorption behavior of hydrogen below its critical temperature (~33 K) is not of great interest for storage application up to now, the BET measurement is typically done by nitrogen as a probe gas at near its liquefaction temperature (~77 K), and then the analyzed textural properties are separately translated into the estimation of the hydrogen capacity and physisorption mechanism. However, for materials possessing small pores and surfaces with high curvatures like MOFs, the nitrogen molecule may be sometimes too large to reach entire porous frameworks, possibly resulting in the erroneously calculated SSA. Therefore, the determination of textural properties from adsorption of hydrogen carried out below its critical temperature would be valuable to understand the fundamental hydrogen physisorption behavior for improving the hydrogen storage properties and also provide more accurate textural properties compare to the nitrogen adsorption. Furthermore, although a linear relationship between hydrogen storage capacity and SSA or SPV is well-known, their specific role of extremely high SSA or SPV materials (over 4500 cm2/g or 2.0 cm3/g) on storage capacity at high hydrogen loading have only been theoretically predicted, but not yet experimentally elucidated. In the study, to determine the accurate SSA experimentally and to establish the relation on storage capacity with respect to SSA and SPV at extremely high hydrogen loading, we investigated the hydrogen adsorption isotherms at 19.5 K on 11 microporous and mesoporous MOFs. The BET method is then applied to theses isotherms. In this way, the correlation between the hydrogen uptake approached almost theoretical value and the practical hydrogen uptake at 77 K as a function of SSA and SPV can be established. Through this single-step measurement, the direct observation of hydrogen adsorption properties is shown which translates directly into the determination of textural properties. In addition, the obtained textural properties from hydrogen BET are compared in detail with the nitrogen BET measurements.

Authors : Ji Chan Park, Dong Hyun Chun, Jung-Il Yang, Ho-Tae Lee, Heon Jung
Affiliations : Clean Fuel Laboratory, Korea Institute of Energy Research

Resume : Fischer-Tropsch synthesis (FTS) has known as an effective method to convert mixtures of CO and H2 gasses produced from fossil resources such as coal and natural gas to liquid fuels. In particular, high-temperature FTS (HT-FTS), which is normally conducted at temperatures of 300-350°C, is a key technology for producing automotive gasoline components. Traditionally, iron-based nanocatalysts, normally prepared by wetness impregnation method with metal-oxide supports, have been applied to HT-FTS catalysis. In general, the monoclinic Hägg carbide(Fe5C2) has been considered as an active species among several iron carbide phases (ε-Fe2C, ε'-Fe2.2C, Fe7C3, θ-Fe3C, etc.). Many researches for the active Hägg carbide formation have been also conducted by controlling the activation condition of inactive iron-oxides. Recently, carbon materials (e.g., activated carbon (AC), carbon nanofibers (CNFs), carbon nanotubes (CNTs), and graphene), have been used as catalyst supports in HT-FTS, because of their high specific surface area, chemical inertness, and controllable surface and pore structures. Herein, we introduce carbon based iron-carbide nanocatalysts which contain Fe5C2 particles around 5 ~ 20 nm in carbon structures, exhibiting extremely high activity and selectivity for the production of gasoline in high-temperature Fischer-Tropsch reaction.

Authors : Ryan Lacdao Arevalo, Mary Clare Sison Escano, Hideaki Kasai
Affiliations : Faculty of Science, Technology, and Mathematics, Philippine Normal University, Manila 1000, Philippines Graduate School of Engineering, University of Fukui, 3-9-1 Bunkyo, Fukui 910-8507, Japan Department of Precision Science & Technology and Applied Physics, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan

Resume : The direct borohydride fuel cell has gained considerable research attention due to its promising potential to generate high power density for portable power applications. However, its practical implementation is hindered by the lack of an efficient anode catalyst. Among the pure metals which were used as electro-catalysts for the electro-oxidation of borohydride, Au was found to be uniquely capable of producing almost 100% coulombic efficiency. However, in addition to the high cost of Au, large overpotential is necessary to achieve an appreciable rate of borohydride oxidation. Interestingly, theoretical and experimental findings have shown that the use of 3d transition metals as alloying elements can improve the performance of Au for the electro-oxidation of borohydride. In this symposium, we provide first principles mechanistic insights into the rational design of electro-catalyst for borohydride oxidation based on the alloys of Au and 3d transition metals (Au3M with M = Cr, Mn, Fe, Co, Ni). [1-2] We found that the elementary reactions that comprised the eight-electron complete borohydride oxidation to metaborate are promoted at lower electrode potential by the Au-3d metal alloy surfaces compared to pure Au. The activated and possibly limiting elementary reaction steps are the dehydrogenation of adsorbed species such as BH3*, BH2OH* and BH(OH)2*. These results provide insights into the design of anode catalysts for direct borohydride fuel cell. References: [1] R.L. Arevalo, M.C.S. Escaño, H. Kasai, ACS Catal. 3 (2013) 3031-3040. [2] R.L. Arevalo, M.C.S. Escaño, H. Kasai, J. Phys. Chem. C 117 (2013) 3818-3825.

Authors : Ahmed Ziani, Moussab Harb and Kazuhiro Takanabe
Affiliations : King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Division (PSE), Thuwal, 23955-6900 (Saudi Arabia)

Resume : By combining theoretical and experimental studies, we report a detailed analysis of the photophysical properties of α- and β-SnWO4 semiconductors. The SnWO4 thin films were synthesized by different annealing treatments. Absorption coefficient, effective mass and dielectric constants for these materials were obtained both experimentally and calculation employing DFT/HSE06. The obtained results show distinctive optoelectronic properties between these materials: e.g., the α-SnWO4 shows an indirect bandgap of 1.52 eV with high charge mobilities, whereas the β-SnWO4 shows a direct bandgap of 4.1 eV with a larger electron and hole effective masses. The finding essentially leads to clear guideline of these materials to be distinctively utilized for totally different applications.

Authors : Aditya Banerji, Anuja Das, Rabibrata Mukherjee
Affiliations : Instability and Soft Patterning Laboratory, Department of Chemical Engineering, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal 721302, India

Resume : We report a novel strategy to generate surface wrinkles with dimensions ranging from sub-micron to micron length-scales formed as a result of spontaneous buckling of an ultra-thin metal film thermally deposited on a viscoelastic polymer layer which forms due to significant mismatch in the thermal and mechanical properties of the constituent layers. We explore the dependence of the buckle morphology on the extent of viscous characteristics of the polymer layer, which is largely uninvestigated. Significant variation in the dimensions of the buckles has been achieved by varying the viscoelasticity of the polymer on tailoring the duration of thermal pre-curing of PDMS, a well-studied viscoelastic polymer whereby the buckles formed has a higher wavelength and amplitude in case of PDMS with greater viscous nature. Partial loss of the accumulated stress due to viscous dissipation results in a lower effective stress responsible for buckling which leads to the observed morphology. The relative magnitude of the stress loss depends on the viscoelasticity of the PDMS layer. This approach serves as a facile technique to fabricate multi-length scale surface structures having tremendous potential in enhancement of light harvesting efficiency in optical devices due to increased internal light scattering from the buckled metal surface when used as an electrode, amplifying the light absorption in those regions of the solar spectrum which otherwise shows minimal light absorption.

Authors : Hee Yeon Yang, Jaeho Shim, Kyu Seung Lee and Dong Ick Son*
Affiliations : Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Jeonbuk 565-905, Korea

Resume : We report core-shell quantum dot (QDs) structures synthesized of ZnO-nanocarbon using a simple chemical method. The outer nanocarbon shell was analysed by high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectra. The stable oxygen bridge bonds between the ZnO core QDs and the oxygen-related functional groups on the nanocarbon shell facilitated the efficient photoinduced charge separation of the core@shell QDs structure. The quenching ratio and Föster resonance energy transfer efficiency were significantly increased due to the conjugation of nanocarbon, as confirmed by photoluminescence (PL) and time-resolved photoluminescence measurements (TRPL). The efficient electron transfer between the ZnO core and the nanocarbon shell resulted in the improvement of the photocatalytic activity and the photoelectrochemical response.

Authors : Santosh K. Singh, Sreekumar Kurungot*
Affiliations : Physical & Materials Chemistry Division CSIR-National Chemical Laboratory, Pune 411 008, India

Resume : Day to day increase in demand of energy increasing because of continuous increase in population and most of the population is dependent on fossil fuel. Since regular uses of these fossil fuels are getting deteriorating it and creating environmental issues. To solve these scarcity of energy and to overcome these environmental issues, the energy storage and generation devices with eco-friendly nature are getting an ample attention from researchers. In order to these energy devices, fuel cell, supercapacitor, Zinc-air batteries might be one of the most eligible candidate. But to make these devices, an efficient and low cost catalysts needed so that devices fabricated with these low cost materials can be easily promoted. The multifunctional materials which can be used for oxygen reduction (ORR) and evolution reaction (OER) and supercapacitors are very crucial for the energy generation from fuel cells, supercapacitor, water splitting and rechargeable zinc-air batteries.1 In case of bifunctional electrocatalyst for ORR and OER, the sluggish kinetics and stability of the catalysts are main technical barrier for the development and commercialization of those fuel cell and zinc-air battery technologies. So far, platinum and its derivatives with other non-noble transition metal are the best catalyst towards ORR and RuO2, IrO2 are state-of-the-art catalysts for OER. However, high cost and rare earth availability of these elements are hampering its extensive and large scale application. Therefore, an extensive research is being done by the researchers to develop highly efficient, low cost, and earth-abundant catalysts for both ORR and OER, to overcome the issues of high cost and low performance of conventional noble metal catalysts. There are many ways to develop these catalysts but a major attention of research and development is towards transition metals supported on highly conducting carbon (graphene, CNT, CNF and CNHs) due to their excellent electrocatalytic activity. Particularly non-noble transition metal supported on nitrogen doped carbon species i.e. metal@N-carbon exhibits prominent electrocatalytic activity towards ORR and OER. However, the synthesis of these catalysts at large scale is very difficult and it involves higher energy consumption which greatly limits their practical applications.2 Here in this report we have synthesized Co3O4 supported nitrogen doped graphene (NGr) catalysts by using very simple and scalable hydrothermal method. The synthesized catalysts are supported with three types of morphologies of Co3O4 (cubic, blunt edged cubes, spherical). Among these synthesized catalysts spherical Co3O4 supported catalyst have shown good activity towards ORR. Moreover, The catalyst supported with blunt edged Co3O4 nanocubes have shown excellent activity towards OER because of exposure of low surface energy (111) planes.3 The synthesized blunt edged Co3O4 nanoparticles supported on NGr (Co3O4-BC/NGr-12h) catalyst is showing overpotential of 280 mV @ 10 mAcm-2 current density in 1M KOH solution. Moreover spherical structured Co3O4 supported on NGr (Co3O4-SP/NGr-24h) hybrid exhibited better oxygen reduction activity (onset potential: 0.03 V (vs. Hg/HgO) with improved stability even after 5000 potential cycles, in a 0.1M KOH.4 Finally, to show the real application of the prepared catalyst, we have fabricated the zinc-air battery device with the ORR active material using as a cathode. References: 1. Liang, H.-W.; Zhuang, X.; Brüller, S.; Feng, X.; Müllen, K. Nat Commun 2014, 5, 1-7. 2. Zhang, J.; Zhao, Z.; Xia, Z.; Dai, L. Nat. Nano 2015, DOI: 10.1038/NNANO.2015.48. 3. Singh, S. K.; Dhavale, V. M.; Kurungot, S. ACS Appl. Mater. Inter. 2014, 7, 442. 4. Singh, S. K.; Dhavale, V. M.; Kurungot, S. ACS Appl. Mater. Interfaces, 2015, 7, 21138.

Authors : Jaekwang Lee
Affiliations : Pusan National University

Resume : Compared with their bulk counterparts, two-dimensional materials can sustain much higher elastic strain (up to ~10%), at which optical quantities such as bandgaps and absorption spectra governing optoelectronic device performance can be modified with relative ease. Using first-principles density functional theory, we show how uniaxial tensile strain can be used to optimize electronic and optical properties of transition metal dichalcogenide lateral (in-plane) heterostructures such as MoX2/WX2 (X = S, Se, Te). In addition we show that a lateral MoS2/MoSe2 heterostructure develops a continuously varying direct bandgap across the heterojunction, which is a particularly useful characteristic for broad absorption across the solar spectrum. Consequently, we expect these strain-engineered lateral heterostructures to be promising for optimizing optoelectronic device performance by selectively tuning the energetic and spatial distributions of the bandgap.

Authors : Igor Meshkovskiy. Semyon Plyastsov
Affiliations : ITMO University

Resume : Goal of the present research is investigation of photoelectric and photomagnetic response of ITO (indium tin oxide) films under the UV laser irradiation. The ITO films were prepared by magnetron sputtering. Thickness of the ITO films was 300nm. Films were irradiated by UV laser light with 248 nm wavelength in laser pulse energy range from 10 mJ to 150 mJ using KrF excimer laser. Metallic electrodes were deposited on the films. Information about the topography was obtained using atomic force microscopy and scanning electron microscopy. Structure of the films was investigated by X-ray diffraction. It was shown that under the UV light the voltage appears between metallic contacts. The electric current was observed through resistive load. For the first time the anisotropy of photoelectric response electric field was observed. The appearance of magnetic field under the laser light irradiation was observed for the first time. The dependence of the voltage on the laser pulse energy was linear in whole measured energy range. For the description of the observed phenomenon the following physical was offered: electric voltage could be associated with non-uniform distribution of the average crystallite size along the film surface, and therefore mean free path of the charge carriers. Photomagnetic response could be associated with collective behavior of large number of charged particles, created due to high intensity laser irradiation. Investigated phenomenon could be used for creation of new optoelectronic devices, for e.g. modulators, optical detectors etc. Particularly, due to linear dependence of photoelectric response on the laser pulse energy, this phenomenon is attractive for manufacturing of simple and cheap excimer laser pulse energy detectors.

Authors : G. Lefevre, H. Kohlmann, A. Sayede
Affiliations : 1 Inorganic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany 2,3 Université d’Artois, UCCS - CNRS UMR 8181, Faculté des Sciences Jean Perrin, 62307 Lens, France

Resume : Hydrogen is a promising energy carrier, compatible with the sustainable energy concept. In this context, solid-state hydrogen-storage is the key challenge in developing hydrogen economy. The capability of absorption of large quantities of hydrogen makes intermetallic systems of particular interest. In this report, efforts have been devoted to the theoretical investigation of palladium-arsenic system. Beside hydrogen-storage considerations, a reinvestigation of cristal structures of this system was advisable. This binary system has been studied by an ab initio evolutionary algorithm for structure prediction and results are in good agreement with experimental data. On the compounds under consideration, particular attention has been paid to AsPd5 alloy, for which experience results were avalaible. Again, our calculations are in excellent concordance, demonstrating the efficience of evolutionary algorithm methods within the first-principles framework of density functional theory (DFT). A similar structure predicition has been performed to find possible hydrides. This analyse revealed one hypothetic stable hydride, experimentally unknown. We then aimed to provide explanation for this divergence and found clarification by considering the steps of hydride formation. Focus is finally made on investigation of hydrogen induced modifications to the structural and electronic properties of AsPd5.

Authors : Aarti Tiwari, Tharamani C. Nagaiah, Ankur Bordoloi
Affiliations : Dr. Tharamani C. Nagaiah; Aarti Tiwari Department of Chemistry Indian Institute of Technology Ropar Rupnagar, Punjab-140001, India E-mail:; Dr A. Bordoloi Refinary Technology Division CSIR- Indian Institute of Petroleum Dehradun-248005, UK, India

Resume : Tungsten oxide (WOx) clusters in the nano regime were synthesized over the mesoporous nitrogen-rich carbon (MNCx) employing a hard-template method for exploring its applicability as a cathode catalyst in low temperature fuel cells. The electrochemical analysis of the WOx/MNCx composite revealed a decent onset potential of 0.083 V (vs. SHE) along with a high oxygen reduction current density of 3.05 mA/cm2. WOx/MNCx is a potential cathodic catalyst owing to its low overpotential compared to the expected 0.401 V (vs. SHE) in oxygen saturated alkaline medium and high stability in the prevalent highly alkaline medium even on switching the potential from kinetic limited to diffusion limited region in the time scale of hours. It predominantly followed a preferable direct 4-electron pathway as evident by the detected peroxide content of less than 10%. These results were concluded by a host of electrochemical analysis performed viz. cyclic voltammetry, rotating dis electrode (RDE), rotating ring dis electrode (RRDE), chronoamperometric and electrochemical quartz crystal microbalance (EQCM) studies. These results suggest the competency of our composite catalyst versus the state-of-art 20% Pt/C catalyst as a non-precious cathodic electrocatalyst towards oxygen reduction reaction for successful application in low temperature alkaline fuel cells.

Authors : Yoan Greiner (phd student), Didier Fasquelle (assistant professor), Manuel Mascot (assistant professor)
Affiliations : Unité de Dynamique et Structure des Matériaux Moléculaires, Université du Littoral Côte d'Opale, 50 rue Ferdinand Buisson, 62228 Calais Cedex, France

Resume : High temperature Solid Oxide Fuel Cell (SOFC) is the most efficient and environmentally friendly energy conversion element used for generating electricity from an electrochemical reaction. The basis cell is a stack composed of a porous anode, a dense electrolyte, a porous cathode and interconnection. Typical operating temperature for SOFC are 800°C-1000°C, which generally leads to the material damage and decrease of the fuel cell lifetime by long-term operating mode. Therefore research trends to develop intermediate temperature SOFC (IT-SOFC) for lowering operating temperatures, typically from 600°C-800°C. But at these lower temperatures, the problems are the electrical efficiency decreases and ohmic loss increases. In order to compensate these problems, the research trends towards materials with better electrochemical properties or by changing the microstructure of the cathode to improve mass transfer and charge transfer. The cathode is a very important layer in the SOFC stack since it displays polarization resistance whose reduction makes quite an important challenge to be addressed. Strontium-doped Lanthanum Manganite (LSM) perovskite oxides possess many interesting properties such as good electronic conductivity, electro-catalytical activity, colossal magneto-resistivity and large magnetic moment. LSM has been extensively used as cathode material for high temperature SOFC. LSM presents several advantages such as good compatibility with along with high thermal and chemical stability. However, LSM-based cathode exhibits poor ionic conductivity and cathode polarization resistance dominates at intermediate temperature (<800°C). It is difficult to improve LSM cathode performance because in this type of material, electrochemical reaction occurs mainly at triple phase boundary where electrolyte, electrode and gas are in close contact. The microstructure of the cathode might play an important role in the performance of SOFC cathode, improving oxygen reduction that might, in turn, be related to grain size, tortuosity and porosity. In this study, we exploit LSM magnetic properties through application of a magnetic field that aligns LSM grains along the cross-section direction resulting in decrease of cathode polarization resistance. The magnetic field is applied during the drying process after deposition over a Gadolinium-doped Ceria (GDC) electrolyte. The microstructure of the LSM is analysed by scanning electron microscopy. The magnetic field produces without any ambiguity an important microstructure change. The performance of LSM cathode is investigated over a [700°C-800°C] temperature range by impedance spectroscopy. The measured electrode area specific resistance (ASR) of a LSM/GDC/LSM symmetric half-cell without and with magnetic field is 0.30 Ωcm² and 0.20 Ω.cm² respectively at 800°C. The ASR value has decreased by 33% after magnetic field application. This behaviour can be attributed to LSM grain reorientation, microstructure change and tortuosity of LSM cathode. The magnetic field effect has been further investigated with a composite cathode that displayed very promising results.

Authors : Ting-Hsuan Lai, Yung-Jung Hsu*
Affiliations : Department of Materials Science and Engineering, National Chiao Tung University

Resume : The introduction of metal has been demonstrated as efficient strategy to enhance the charge separation of semiconductor and thereby improve the photocatalytic activity. On the other hand, extensive focuses has been placed on the use of yolk@shell nanocrystals in catalysis applications. The unique structural features of interior, confined voids provide yolk-shell nanocrystals with homogeneous environment for reactant molecules, which is particularly favorable for catalytic reactions. Here we demonstrated the use of Au@Cu2Se yolk-shell nanocrystals as the photocathode for efficient photoelectrochemical water splitting. The samples were prepared by using Au@Cu2O core@shell nanocrystals as the growth template. The growth of yolk@shell nanocrystals was achieved by performing the selenization treatment on Au@Cu2O. Due to the higher diffusion rate of Cu2+ compared to Se2-, abundant voids would be generated inside the structure, leading to the formation of yolk@shell structures. To demonstrate the practical use of yolk@shell nanocrystals, the samples were employed as the photoelectrode in photoelectrochemical water splitting. The results showed that Au@Cu2Se yolk-shell nanocrystals exhibited substantially higher photocurrent of water reduction (-35µA/cm2) than the other counterpart samples such as pure Cu2O (-16µA/cm2), pure Cu2Se (-24µA/cm2) and Au@Cu2O (-26µA/cm2). This superiority was attributed to the pronounced charge separation caused by Au introduction as well as the homogeneous reaction environment rendered by the yolk@shell structures.

Authors : Sung-Min Kim, Yu-Guen Jo, Sang-Yul Lee
Affiliations : Center for Surface Technology and Applications, Department of Materials Engineering, Korea Aerospace University, Goyang-si, Gyeonggi-do, 412-791, Republic of Korea

Resume : Ag is a promising candidate as an indispensable catalysts in alkaline medium due to its unique capability to resist against the corrosive environment and to enhance the ORR activity. Here, we have demonstrated shape-controlled synthesis of Ag catalysts by tailoring the reduction kinetics with adjusted electron densities in plasma. With low electron density of 7.11022 m-3, the Ag nanowires with the corrugated structure induced by twinning and stacking faults formation were observed along the entire longitudinal <111> direction of nanowires. Whereas, with high electron density of 13.71022 m-3, the Ag dendrites constructed via the coalescence between Ag nanoparticles could be obtained. These different kinetically-controlled growth behaviors were essential for achieving the shape transition between the nanowires and dendrites. From the linear sweep voltammetry, the Ag nanowires exhibited the highest kinetic current density with a value of 17.2 mA cm-2, and the electron transfer number was calculated to be 3.54, which is the indicative of a four-electron ORR pathway. This improvement in ORR activity could be mainly attributed to the lattice strain, derived from defective structures.

Authors : Sung-Min Kim, Ki-Tae Bae, Sang-Yul Lee
Affiliations : Center for Surface Technology and Applications, Department of Materials Engineering, Korea Aerospace University, Goyang-si, Gyeonggi-do, 412-791, Republic of Korea

Resume : Nitrogen-doped onion-like carbon was synthesized using an arc discharge in a liquid phase in the presence of different ammonia concentrations. The nitrogen-doped onion-like carbon was investigated as a catalyst support material for a catalytic oxygen reduction reaction. With increasing ammonia concentrations up to 5 M, the nitrogen doping degree increased to 1.7 at.%, which created a highly defective onion-like structure. The edge and defective sites induced from nitrogen atoms effectively facilitated the nucleation of Pt clusters, which led to the stable dispersion and small size of Pt nanoparticles, as revealed via X-ray photoelectron spectroscopy, X-ray diffraction, Raman spectroscopy and electron microscopy. From the results of the electrochemical characterization, the Pt nanoparticles supported on the nitrogen-doped onion-like carbon with a nitrogen content of 1.7 at.% exhibited the highest electrochemically active surface area, specific current density and half-wave potential. The enhanced oxygen reduction could be ascribed to the defective outermost layers and the electronic modification. Moreover, even after an accelerated durability test with 5,000 cycles, the nitrogen-doped onion-like carbon with a nitrogen of 1.7 at.% exhibited less degradation, indicating the excellent durability.

Authors : Jing-Mei Li and Yung-Jung Hsu
Affiliations : National Chiao Tung University

Resume : In this work, a more accurate, reliable method was proposed to evaluate the photoelectrochemical performance of semiconductor electrode toward water splitting. Conventionally, chronoamperometric measurements are conducted at a relatively fixed bias, e.g. 0 V vs. reference electrode, to monitor the photocurrent generation, which has been regarded as a direct index for performance comparison among different electrodes. Considering that the open-circuit potential of the cell varies from electrode to electrode, the direct photocurrent comparison at a relatively fixed bias may misrepresent the actual difference among samples. Here we studied the photoelectrochemical properties of the samples by applying two distinct external bias values, one at 0 V vs. Ag/AgCl deriving from the conventional practice and the other at 0.1 V vs. open-circuit potential representing the exactly fixed potential applied. Three experimental groups were designed to address the arguments, which included the influence of heat treatment for ZnO nanowire arrays, the quantitative effect of Au for Au nanoparticle-decorated ZnO nanowires and the global comparison between ZnO and TiO2 nanowires electrodes. Different trends in photocurrent generation were observed at the two distinct biases, with the results from 0.1 V vs. open-circuit potential being in conformity with the general considerations. The demonstrations from this work suggested that applying an exactly fixed potential from the open-circuit potential shall provide a more fair ground for accurate photoelectrochemical performance evaluation without under- or over-estimation.

Authors : Di-Yan Wang, Cheng-Hung Li,
Affiliations : Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan

Resume : The design of active and stable semiconducting composites with enhanced photoresponse from visible light to near infrared (NIR) is a key to improve solar energy harvesting for photolysis of water in photoelectrochemical cell or photocatalytic reaction. In this study, we prepared earth abundant semiconducting composites consisting of iron pyrite and Titanium oxide as a photoanode and photocatalyst for hydrogen evolution reaction. The detailed structure and atomic compositions of FeS2/TiO2 photoanode was characterized by high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (XRD), inductively coupled plasma with atomic emission spectroscopy (ICPAES) and Raman spectroscopy. Through the proper sulfurization treatment, the FeS2/TiO2 photoanode exhibited high photoresponse from visible light extended to near infrared range (900 nm) as well as stable durability test for 4 hours. We found that the critical factors to enhance the photoresponse are on the elimination of surface defect of FeS2 and on the enhancement of interface charge transfer between FeS2 and TiO2. Our overall results open a route for the design of sulfur-based binary compounds for photoelectrochemical applications.

Authors : DongHoon Song,MinJoong Kim,EunAe Cho
Affiliations : Dep. of Material Science and Engineering KAIST

Resume : Hydrogen produced by electrolysis is one of the promising means by which to store electricity coming from renewables and to address its intermittency. With the growing global electricity share from renewable energy sources, large-scale storage systems are required. Alkaline electrolysis can be a sustainable solution for the large-scale energy storage system. However, high overpotential and slow kinetics particularly of the oxygen evolution reaction (OER) still remains as a hurdle to limit efficiency of the system. To enhance efficiency of alkaline electrolysis cells, catalysts which have high electrocatalytic activity for OER should be developed. Platinum-like behavior of Tungsten carbide in surface catalysis was first reported by Levy and Boudart in 1973. In addition, tungsten carbide was reported to have Pt-like electronic structure by Colton in 1975. After that, tungsten carbide has been studied widely and expected to substitute noble metal catalysts which are used in many electrochemical reactions. Here, we studied tungsten carbide as a support for 3d-transition metals and make bi-metallic surfaces for developing a high activity OER catalyst. First, WC-Co was synthesized by heat treatment. Carbon nitride (g-C3N4) and tungsten chloride were used as a carbide precursor and cobalt acetate was also used for helping carbonization of tungsten. After heat treatment, acidic leaching process was followed to eliminate cobalt. Through additional mixing with Nickel precursor and heat treatment, Ni/WC was synthesized and to compare electrocatalytic activity Ni/C was also prepared. In addition, many different Ni/WC which have different Ni to WC ratios were synthesized and measured in electrochemical way. Finally, the optimal ratio was determined and it show better electrocatalytic activity than precious catalysts and any other non-noble catalysts. Cyclic voltammetry was measured to evaluate OER activity in 1 M KOH in potential range from 1 to 1.8 V. Pure WC and Ni/C have 394 mV and 413 mV overpotentials at 10 mA∙cm-2 respectively. In Metal/WC cases, Cobalt/WC shows only 417 mV. But Nickel/WC shows 340 mV overpotential at 10 mA∙cm-2 and higher electrocatalytic activity for OER than RuO2 in alkaline media.

Authors : C. López-López1, J. Kettle2, L. Andres3, M.F. Menéndez3, P. Sánchez3, R. Aninat1,E. Sánchez1, J.M. Delgado-Sánchez1
Affiliations : 1 Abengoa, Campus Palmas Altas, C/ Energía Solar 1, 41013 Sevilla (Spain) 2 School of Electronic Engineering, Bangor University, Dean Street, Bangor, Gwynedd, Wales, UK LL57 1UT 3 ITMA, Parque Tecnológico de Asturias, 33428 Llanera (Asturias)

Resume : Organic photovoltaics (OPVs) have attracted remarkable interest during the last decade because of their potential for low cost, printability and flexibility. Recent research has led to the report of power conversion efficiency (PCE) of over 10%. Nearly all reports involving OPV are based on a glass or polymeric substrate. However, for integration into building structures and exploitation by the building industry, other substrates need to be considered. Steel is one of the most suitable substrate materials for PVs, because their mechanical flexibility, robustness, thermal and chemical stability and excellent barrier properties against environmental factors. Several publications have analysed the OPV performance in which steel is used as back contact layer; however for industrial scale up, the substrate will need to be electrically isolated from the solar cell and therefore a dielectric barrier layer covering the steel surface is mandatory. This layer must exhibit multiple properties; firstly it must electrically isolate the steel substrate from the solar cell; secondly, it must planarise the surface to avoid pinholes and shunts; and finally it must avoid impurity diffusion from the steel substrate into the semiconductor layers. Herein we study the performance of OPV technology built on stainless steel coated with different barrier layers. This reports the first OPV fabricated onto a planarised steel substrate. In addition, the key performance parameters of an OPV are correlated with the variation in substrate/barrier layer properties. Additionally, the barrier layers proposed in this work will add certain optical functionalities to enhance the performance of the finished solar cell device.

Authors : E. Gagaoudakis1,2, E. Aperathitis2, G. Michail2, V. Binas2, M. Panagopoulou3, Y. S. Raptis3, D.Tsoukalas3 and G. Kiriakidis1,2
Affiliations : 1Physics Department, University of Crete, P.O. Box 2208, 71003 Heraklion, Crete, Greece 2Institute of Electronic Structure & Laser (IESL), Foundation for Research and Technology (FORTH) Hellas, P.O. Box 1385, Heraklion 70013, Crete, Greece 3 School of Applied Mathematical and Physical Sciences, National Technical University of Athens, GR 157 80, Zografou Campus, Athens, Greece

Resume : Thermochromic materials change their transparency upon heating. The most studied thermochromic material is VO2, which undergoes a semiconductor to metal transition at a critical transition temperature Tc of 68oC. Below Tc VO2 is a semiconductor having a monoclinic structure and high IR transmittance, while above Tc it turns to metal with a rutile structure and high IR reflectance. In this work, VO2 thermochromic films were produced by rf sputtering technique using vanadium metal target. The O2 content in Ar/O2 plasma was 1 - 3%, while substrate temperature was 300oC. Film thickness was ranging 40 - 300nm. Three different types of glasses were used as substrate that is fused silica, Pilkington Float Glass and flexible Corning® Willow® glass with thickness 1mm, 4mm and 0.2mm, respectively. Thermochromic properties of films were identified measuring their transmittance at temperature well below and well above Tc. According this, variation of IR transmittance ΔTr, luminous transmittance Tlum, Tc and width of transmittance hysteresis loop ΔT can be calculated. Thermochromic properties were also verified by T-dependant micro-Raman technique. In as far as Pilkington Float Glass substrate is concerned, it was observed that only films with thickness below 50nm were thermochromic, having Tc=46oC, ΔT=9oC, ΔTr=15% and Tlum=46%, while films with thickness more than 100nm turned to thermochromic only after ex-situ annealing. In contrast, films deposited on fused silica glass were thermochromic, independent of their thickness, having Tc lower than 40oC and ΔT lower than 10oC. Finally, thermochromic VO2 films were deposited on flexible glass, for first time, having Tc=51oC, ΔΤ=12οC, ΔTr=36% and Tlum=40%.

Authors : Kai-Ling Ng, Kieran Fahy , and Anthony Kucernak
Affiliations : Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, United Kingdom.

Resume : The current technologies used in low temperature electrolysers and fuel cells rely on PGMs (platinum group metals) as catalysts in order to catalyse the reactions occurring in these devices. These materials are critical raw materials (CRMs) due to their low earth abundance and limited supply availability. Hence there is a critical need to avoid an increasing dependence on PGMs in the future. We aim to develop a cheap, stable and supported high surface area metal phosphide (MP) catalyst from readily-available, non-precious transition metals, via a facile synthesis method, to replace PGMs. Besides lower cost, alloying transition metals with phosphides has the advantages of increasing the stability and corrosion resistance of the pure transition metal [1]. In this work, solid-state microwave and high temperature pyrolysis methods were employed for the facile synthesis of supported MP catalysts via systematically varied phosphate anion-to-carbon (x(PO4)y/ zC) ratios. The electrochemical stability and catalytic activities of the MP catalyst obtained were analysed by testing in both alkaline and acidic solutions, using a rotating disc electrode and a PEMFC fuel cell test station. Physical characterisation was performed using XRD, TEM, SEM and XRF. The results obtained from using different transition metals, phosphate anion-to-carbon ratios and synthesis methods were correlated with the physical characteristics of the MP catalysts and their catalytic activities, to gain an insight into their catalytic performance. Reference: A. Alexander and J. S. J. Hargreaves, Chem. Soc. Rev., 2010, 39, 4388-4401 (DOI: 10.1039/b916787k).

Authors : Y. Mordekovitz, L. Shelly, S. Sagi and S. Hayun
Affiliations : Ben Gurion University of the Negev

Resume : Understanding the adsorption and desorption energetics of atoms and molecules on surfaces and the chemical reactions between them during catalytic processes is important for the development of new and more effective catalysis. Presently, the importance of oxygen exchange materials (e.g. CeO2, perovskites) for thermochemical splitting of H2O is in focus. In the present study, the effect of Nd3+ on the water adsorption and surface energetics of CeO2 was investigated. Nanoscale Nd doped CeO2 powders have been synthesized by a surfactant-based method. The as synthesized nano powders were found to be homogeneous solid solutions with a fluorite structure, where the lattice parameters increase linearly with Nd content. The water adsorption enthalpy and coverage found to increases with the dopant level, which imply increasing in the surface enthalpies and production of hydrogen. Interestingly, the measured surface enthalpies via differential scanning calorimetric method found to decrease with Nd content, and the grain size after coarsening decreased as well. The reasons for this behavior will be discussed.

Authors : Mohammad Mahdi Tavakoli,1 Qingfeng Lin,1 Siu-Fung Leung1, Ga Ching Lui1, Hao Lu,2 Liang Li,2 Bin Xiang3 and Zhiyong Fan1
Affiliations : 1 Department of Electronic and Computer Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China. 2 College of Physics, Optoelectronics and Energy, Jiangsu Key Laboratory of Thin Films, Soochow University, Suzhou, 215006, P. R. China. 3 Department of Materials Science & Engineering, CAS Key Lab of Materials for Energy Conversion, University of Science and Technology of China, Hefei, Anhui 230026, China.

Resume : Utilization of nanostructures on photovoltaic devices can significantly improve device energy conversion efficiency by enhancing device light harvesting capability as well as carrier collection efficiency. However, improvements in device mechanical robustness and reliability, particularly for flexible devices, have rarely been reported with in-depth understanding. In this work, we have fabricated high efficiency and flexible organometallic perovskite solar cells on plastic substrates with inverted nanocone (i-cone) structures. Compared with the reference cell that was fabricated on a flat substrate, it was shown that device power conversion efficiency could be improved by 37%, and reached up to 11.29% on i-cone substrates. More interestingly, it was discovered that the performance of an i-cone device remained more than 90% of the initial value even after 200 mechanical bending cycles, which is remarkably better than for the flat reference device, which degraded down to only 60% in the same test. Our experiments, coupled with mechanical simulation, demonstrated that a nanostructured template can greatly help to relax stress and strain upon device bending, which suppresses crack nucleation in different layers of a perovskite solar cell. This essentially leads to much improved device reliability and robustness and will have significant impact on practical applications.

Authors : Anna Brisou, P. Hubert Mutin, Alexandra Chaumonnot, Damien P. Debecker
Affiliations : Anna Brisou and Alexandra Chaumonnot: Catalysis and Separation Division, IFP Energies nouvelles, Rond-point de l’échangeur de Solaize, BP3, 69369 Solaize, France; P. Hubert Mutin : Institut Charles Gerhardt, Université de Montpellier, CC1701, Place Eugène Bataillon, 34095 Montpellier Cedex 5, France; Damien P. Debecker : Institute of Condensed Matter and Nanoscience, Université catholique de Louvain, Croix du Sud 2/17, 1348 Louvain-La-Neuve, Belgium

Resume : 1. Introduction The energy and environmental challenges of the 21th century require finding solutions to limit the use of fossil hydrocarbons. One possibility consists in using biomass to obtain products for applications in the petrochemical and chemical industry. Thus the development of catalysts with specific acid-base properties and hydrothermal stability is required [1]. The aim of this work is to investigate several binary and ternary mixed oxides families combining Si with other metal oxides (Nb, Ta, Zr, W, Ti) using a non-conventional synthetic route named "non hydrolytic sol-gel" (NHSG) which permits a good control of the homogeneity, a key point to obtain new porous acido-basic materials [2]. 2. Experimental In a glove box, metal chloride precursors were mixed to SiCl4, CH2Cl2 and iPr2O in an autoclave. The mixture was heated at 110 °C for 4 days and the resulting gel was dried and calcined in dried air at 600 °C for 5 h. Formulations from 0.65 to 11 at. % of metal M in the mixed oxide (calculated according to : nM/(nM+nSi)*100) were studied. The samples are denoted MxSi-600 for binary oxides and MxM’x’Si-600 for ternary oxides, where M and M’ are either Nb, Ta, Zr, W or Ti, x and x’ are the nominal at. % of the metal and 600 refers to the calcination temperature. The solids were characterized by N2-physisorption, XRD, ICP-AES, XPS, FTIR, adsorption of pyridine (Py-FTIR) and NH3-TPD. Hydrothermal stability tests were performed in the gas phase at 400 °C. The catalysts were tested in a model catalytic reaction of dehydration and hydrogen transfer between cyclopentanol and cyclohexanone in the gas phase at 200 °C, to probe their acidic and basic character as well as their stability under these conditions [3]. 3. Results and discussion The solids synthesized by NHSG are XRD-amorphous and have a well-controlled composition, showing that no precursor is lost during synthesis, drying or calcination. Most of the mixed oxides have a similar composition in the bulk and at the surface. The samples are mostly mesoporous, displaying high specific surface areas (300-800 m2/g) and large pore volumes (up to 2 cm3/g). Py-FTIR shows the existence of both Brönsted and Lewis acid sites on the investigated mixed oxides, while the NH3-TPD shows that these acid sites are weak or medium strength. The reactivity of the mixed oxides has been evaluated by a model catalytic reactions of dehydration (DEH) taking place on acid sites and hydrogen transfer (HT) taking place on acid-base pairs between cyclopentanol and cyclohexanone. Both the acid-catalysed DEH reaction and acid-base pairs-catalysed HT reaction are seen to be catalyzed by these mixed oxides, except for the WO3-SiO2 sample which catalyzes only DEH. Additionally, the stability of the catalysts with time on stream (vs. coking) can be assessed. For example, WO3-SiO2 is the most stable and active catalyst for the dehydration reaction. 4. Conclusions Porous binary and ternary mixed oxides combining silica with Nb, Ta, Zr, W and Ti oxides with high specific surface areas and well-controlled compositions have been synthesized via the innovative NHSG technique [4]. These solids display acidic and basic properties, with mostly weak and medium strength Brönsted and Lewis acid sites. They are good candidates for the use in catalysis to transform some interesting biobased compounds particularly in gas phase. The study will be pursued by characterizing more precisely the materials by TOF-SIMS, MET-EDX, CDCl3-FTIR, chemisorbtion of CO and CO2, CO2-TPD and comparing them to model acidic and basic material (SiO2-SO3H, Silica alumina, MCM-41, SBA-15, Hydrotalcite, MgO). Moreover, further mixed oxides formulations are to be investigated in order to develop innovative catalytic materials and study the potential synergies generated in highly homogeneous ternary mixed oxides. 5. References [1] L. Jin, C.-h. Kuo, S.L. Suib, Chapter 11 - Heterogeneous Catalysts for Biomass Conversion, in: S.L. Suib (Ed.) New and Future Developments in Catalysis, Elsevier, Amsterdam (2013) 253-270. [2] D.P. Debecker, V. Hulea, P.H. Mutin, Mesoporous mixed oxide catalysts via non-hydrolytic sol–gel: A review, Applied Catalysis A: General, 451 (2013) 192-206. [3] S. Carre, N.S. Gnep, R. Revel, P. Magnoux, Characterization of the acid–base properties of transition aluminas by model reaction, Applied Catalysis A: General, 348 (2008) 71-78. [4] French Patent 15/56.665

Authors : Ang Li, Dr Davies Rob P, Dr Petit Camille
Affiliations : Imperial College London

Resume : Abstract Coal contributed 43% of CO2 emission, oil is responsible for 36% and natural gas is 20%, hence natural gas considered as potential fossil fuel as future source of energy. It has potential to produce an enormous amount of heat of combustion around 50.0MJ/kg with 44.5MJ/kg gasoline. Natural gas mainly contained methane but also involving carbon dioxide which affect the heating value and causing pipeline and equipment corrosion. Thus, in order to optimise the quality of natural gas, capture carbon dioxide is very important. This project is to use UiO-66 metal-organic- frameworks (MOFs) by adding amine groups inside the MOF pores to modulate the behaviour of MOFs , in order to separate the carbon dioxide from methane.

Authors : Francisco J. Garcia-Garcia, Francisco Yubero, Juan P. Espinós, Agustin R. González-Elipe, Richard M. Lambert
Affiliations : Instituto de Ciencia de Materiales de Sevilla (CSIC-Univ. Sevilla), Spain

Resume : Un-doped ~ 5 micron Ni-YSZ porous thin films were prepared by reactive pulsed DC magnetron sputtering and characterized by SEM, XRD, RBS, TOF-SIMS, STEM and XPS. Pre-calcination of the amorphous unmodified precursor layers on a YSZ substrate followed by reduction produced a film consisting of uniformly distributed tilted columnar aggregates of composite material separated by ~ 80-140 nm channels. Similarly prepared and correspondingly characterized anode films doped with 1.2 at. % Au were also porous and contained highly dispersed gold present as Ni-Au alloy particles whose surfaces were strongly enriched with Au (XRD, HAAD STEM, XPS). With hydrogen as fuel, the performance of the undoped thin film anodes was comparable to that of 10-20 times thicker typical commercial anodes. With a 1:1 steam/carbon feed, the un-doped anode cell current collapsed immediately and fell to zero after ~ 60h. In striking contrast, the initial performance of the Au-doped anode was much higher and remained unaffected after 170 hours. Under deliberately very harsh conditions (steam/carbon = 1:6) the performance of the Au-doped anodes decreased progressively, almost certainly due to deposited carbon. Even so, the cell maintained some activity even after 3 days operation in dramatic contrast with the un-doped anode, which died after only three hours operation. The implications and possible practical application of these findings are discussed.

Authors : Emre Yassitepe, Jilian N. Freitas, Oleksandr Voznyy, Lazaro Padilha, Edward Ted Sargent and Ana Flavia Nogueira
Affiliations : 1Department of Electrical and Computer Engineering, University of Toronto, 10 King’s College Rd., Toronto, ON, CANADA 2Institute of Chemistry, University of Campinas, Cidade Universitária Zeferino Vaz, Campinas, SP, BRAZIL 3Institute of Physics, University of Campinas, Cidade Universitária Zeferino Vaz, Campinas, SP, BRAZIL

Resume : CsPbX3 (X=Cl, Br, I) perovskite quantum dots (PQDs) are synthesized via a novel halide precursor allowing solely carboxylic acid capped dots. The PQDs show enhanced surface stability against degradation with successive purification steps. Here we will demonstrate the application of CsPbX3 PQDs in light emitting diodes and hybrid (polymer:PQD) solar cell applications. The partial detachment of ligands during purification allowed solution processing light emitting diode fabrication. All inorganic PQDs show high brightness and realized in RGB (Red, Green and Blue) light-emitting diodes with 0.32% external quantum efficiency at 510 nm. We form hybrid nanocomposites by blending conjugated polymers and PQDs in solutions. The mixtures show high colloidal stability and preserving the PQD properties. We will demonstrate the application of these hybrid nanocomposites in solar cells.

Authors : Cheol Hyun Bae, Ho Sik Lee, Jae Yong Yun, Woong Soon Kang, Seon Jin Kim
Affiliations : Division of Materials Science and Engineering, Hanyang University

Resume : Inconel 690 is widely used for steam generator(SG) tubes in nuclear power plants. Because SG tubes experience flow-induced vibration, fretting wear can occur between SG tubes and anti-vibration structures. Since the wear damage can reduce SG heat exchange efficiency in nuclear power plants by plugging the worn tube, investigation on the wear resistance of Inconel 690 SG tubes is necessary. During the operation of SG, Inconel 690 is oxidized due to high temperature and pressure of the secondary water. However, the effect of oxidation film on the wear behavior of Inconel 690 has not yet been studied, even though the oxidation film has important effects on the wear properties. Therefore, in this study, Inconel 690 tubes, oxidized under secondary water conditions, were used for fretting wear test. The results show that the spinel oxide, existent on the surface of Inconel 690, increases the room-temperature wear resistance, but decreases the high-temperature wear resistance.

Authors : Yuyi Feng1, Kwang-Dae Kim1, Clayton Netmitz2, Paul Kim3, Thomas Pfadler1, Melanie Gerigk4, Sebastian Polarz4, James A. Dorman5, Jonas Weickert1, Lukas Schmidt-Mende1
Affiliations : 1. Department of Physics, University of Konstanz, 78457, Germany 2. Department of Physics, University of North Carolina, Chapel Hill, NC-27516, USA 3. Chemical Engineering, Yale University, New Haven, CT-06520-0626, USA 4. Department of Chemistry, University of Konstanz, 78457, Germany 5. Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA-70803, USA

Resume : Free-standing nanowire or nanorod arrays are of great interest for applications in photovoltaic device, surface-enhanced Raman scattering (SERS), biosensing, plasmonics, thermal electronics, high density data storage, and photocatalysts. In photovoltaics nanorod arrays are of particular interest for organic and hybrid solar cells, whose near-optimal architecture is proposed to consist of arrays of nanostructures (approximately 200 nm long) providing huge interfaces, efficient light harvesting and one-dimensional charge transport pathways [1]. Silver, scaled down to nanowire arrays, is considered one of the most exciting nanomaterials for organic and hybrid solar cells, because of its extremely high electrical conductivity, tunable surface plasmon resonance in the UV-Vis region and strong light scattering effects [2]. However, in the past years, large scale fabrication of such nanostructures on ITO glass and other rigid substrates was challenging. Here we present large-area free-standing silver nanorod arrays on ITO glass and other substrates by anodic aluminium oxide template (AAO) - assisted pulsed electrochemical deposition. We use an in situ oxygen plasma cleaning process and a sputtered Ti layer to enhance the adhesion between the template and ITO glass. An ultrathin gold (2 nm) layer is deposited as a nucleation layer for the electrodeposition of silver. An unprecedented high level of uniformity and control of the nanorod diameter (38–76 nm), spacing (84–133 nm) and length (98–208 nm) has been achieved. In addition, the absorption spectra of free-standing silver nanowire arrays shows tunable plasmon resonance peaks. We are currently investigating the optical and electronic effects of the silver nanorod arrays in SERS, biosensing, electrode for photoelectric devices and others. [1] Weickert J, Dunbar R B, Hesse H C, Wiedemann W and Schmidt‐Mende L 2011 Nanostructured organic and hybrid solar cells Advanced Materials 23 1810-28 [2] Zhuo X, Zhu X, Li Q, Yang Z and Wang J 2015 Gold Nanobipyramid-Directed Growth of Length-Variable Silver Nanorods with Multipolar Plasmon Resonances ACS Nano 9 7523-35

Authors : Jae Ho Shim, Kyu Seung Lee, Hee Yeon Yang, Yohan Ko, Byung Joon Moon and Dong Ick Son*
Affiliations : Institute of Advanced Composite Materials, Korea Institute of Science and Technology, Eunhari san 101, Bongdong-eup, Wanju-gun, Jeonbuk 565-905, Korea

Resume : Inverted polymer solar cells have received a good deal of attention because of their compatibility with stability and large-scale roll-to-roll processing. In the inverted cell geometry, solution-processed metal-oxide films based on materials such as metal oxide nanoparticles are typically used as the electron-transporting layers. Here, We demonstrate enhanced charge collection in inverted Organic Photovoltaic solar cells (OPVs) using the surface modifier PEIE (Polyethyleneimine-ethoxylate), chemically functionalized ZnO/graphene core-shell type quantum dots (F-ZGQDs) monolayer as an electron transport layer(ETL). The mono-layered ZGQD plays the multi-functional role as surface modifier, photosensitizer and electron transport layer. We confirmed the internal structure of mono-layered F-ZGQDs by using the focused ion beam (FIB) milling technique. Additionally, we estimate the density of state (DOS) of F-ZGQDs using density functional theory (DFT). The inverted polymer solar cells with F-ZGQDs monolayer shows high power conversion efficiencies (∼10.3 %) due to effective interfacial properties and efficient charge transfer.

Authors : Kwang Jin Lee,a Yiming Xiao,a,b Jae Heun Woo,a,c Eun Sun Kim,a David Kreher,b André-Jean Attias,b Fabrice Mathevet,b Jean-Charles Ribierre,a Jeong Weon Wu,a* Pascal André,a,d*
Affiliations : a Department of Physics, CNRS-Ewha International Research Center (CERC), Ewha W. University (Seoul, South Korea) ; b Institut Parisien de Chimie Moléculaire, Chimie des Polymères, CNRS-UMR 8232, Université Pierre and Marie Curie (Paris, France) ; c Center for Length, Division of Physical Metrology, Korea Research Institute of Standards and Science (Daejeon, South Korea) ; d RIKEN (Wakoshi, Japan)

Resume : Charge transfer (CT) is an essential phenomenon relevant to numerous fields including biology, physics and chemistry.1-5 Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter semiconductor CT dynamics.6 With triphenylene:perylene diimide dyad supramolecular self-assemblies prepared on HMM substrates, we show that both charge separation and recombination characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalise the experimental data extending Marcus theory framework with dipole image interactions tuning the driving force. The number of metal-dielectric pairs alters the HMM interfacial effective dielectric constant and becomes a solid analogue to solvent polarizability. The model and further PH3T:PCBM data show that the phenomenon is general and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics and chemistry.

Authors : Kwang Jin Lee,a Yiming Xiao,a,b Sang Jun Kim,c Sang Youl Kim,c,d David Kreher,b André-Jean Attias,b Fabrice Mathevet,b Jean-Charles Ribierre,a Jeong Weon Wu,a* Pascal André,a,e*
Affiliations : a Department of Physics, CNRS-Ewha International Research Center (CERC), Ewha Womans University (Seoul South Korea) ; b Institut Parisien de Chimie Moléculaire, Chimie des Polymères, CNRS-UMR 8232, Université Pierre and Marie Curie (Paris, France) ; c Ellipso Technology Co. Ltd. (Suwon, South Korea) ; d Ajou University (Suwon, South Korea) ; e RIKEN (Wakoshi, Japan)

Resume : Plasmonic nanostructured substrates have received a growing attention because of their potentials to tune optoelectronic properties of materials located inside or in their vicinity.1-4 These photophysical characteristics include emission or absorption, and charge transfer (CT) has been widely neglected. CT is, however, an essential phenomenon relevant to numerous fields including biology, physics and chemistry.5-8 Here, we demonstrate that multi-layered plasmonic (MLP) substrates can alter semiconductor CT dynamics.9 With donor-acceptor dyad supramolecular self-assemblies prepared on top of MLP substrates, we show that both charge separation and recombination characteristic times can be tuned, resulting in longer-lived CT states. We use Marcus theory framework to rationalize the experimental data and describe how the driving force is affected by the separation between the organic semiconductor and the MLP substrates. The phenomenon is general and this work paves the way toward molecular and substrate engineering to control CT dynamics with potential applications in fields including optoelectronics and chemistry.

Affiliations : Total MS – Energie Nouvelles - 24 cours Michelet, La Défense 10 - 92069 PARIS LA DEFENSE Cedex, France. LPICM, CNRS, Ecole Polytechnique, Université Paris-Saclay, 91128 Palaiseau, France. Institut Photovoltaïque d’Ile-de-France (IPVF), 8 rue de la renaissance – F-92160 Antony, France ; R&D Center of Thin Film Technologies in Energetics, Ioffe Institute, 194054 Saint Petersburg, Russia ; LPICM, CNRS, Ecole Polytechnique, Université Paris-Saclay, 91128 Palaiseau, France. Institut Photovoltaïque d’Ile-de-France (IPVF), 8 rue de la renaissance – F-92160 Antony, France ; Total MS – Energie Nouvelles - 24 cours Michelet, La Défense 10 - 92069 PARIS LA DEFENSE Cedex, France. Institut Photovoltaïque d’Ile-de-France (IPVF), 8 rue de la renaissance – F-92160 Antony, France ; LPICM, CNRS, Ecole Polytechnique, Université Paris-Saclay, 91128 Palaiseau, France. Institut Photovoltaïque d’Ile-de-France (IPVF), 8 rue de la renaissance – F-92160 Antony, France ;

Resume : Al2O3 surface passivation of p-type c-Si has proved its effectiveness and industrial compatibility thanks to (spatial-ALD) Al2O3 / (PECVD) SiN:H stack, providing cell efficiency of 20.2% (PERC). We reduced Al2O3 thickness down to 2 nm in order to benefit from its high fixed charge density at Al2O3/c-Si interface, which has been shown to be thickness independent. Such a thin Al2O3 layer raises concerns regarding ALD growth mode and electrostatic impact of the capping layer. We have grown an ultrathin chemical silicon oxide (<1 nm) on top of the c-Si surface to avoid the usual Volmer–Weber growth mode during the first ten ALD cycles. To provide good chemical passivation, at least 5 nm of Al2O3 are required to release enough hydrogen during annealing, so missing hydrogen had to be brought by the capping layer. We replaced standard SiN:H by SiOC:H to avoid field effect passivation lessening due to a high density of positive fixed charges within the SiN:H layer. We established the beneficial effect on passivation of the interfacial chemical oxide thank to HR-TEM, photoluminescence, µ-PCD and corona discharge. We added exo-diffusion and SIMS characterizations to highlight the usefulness of replacing SiN:H by SiOC:H. Taking into account the ALD growth mode and the electrostatic impact of the capping layer, we kept SRV below 10 cm/s, while increasing theoretical ALD throughput by factor of 3.

Authors : Jinbong Seok[1][2], Jun-Ho Lee[3], Suyeon Cho[1], Byungdo Ji[2], Hyo Won Kim[3], Sung Wng Kim[1][2], Young Hee Lee[1][2], young-woo son[3], Heejun Yang[1][2]
Affiliations : [1]Center for Integrated Nanostructure Physics, Institute for Basic Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea; [2]Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea; [3]Korea Institute for Advanced Study, Seoul 130-722,Republic of Korea; [4]Samsung Advanced Institute of Technology, Suwon-si, Gyeonggi-do, 443-803, Korea;

Resume : Hydrogen is one of the most efficient and cleanest energy resources for the future. Recently, there have been extensive researches about hydrogen such as hydrogen evolution reaction (HER), hydrogen storage and hydrogen fuel cell. The Hydrogen evolution reaction (HER) is an important process as the first step of hydrogen energy system. Platinum (Pt) has been known to be the best catalyst for the HER. However, continuous efforts have been made to replace the Pt by cheaper materials due to the high cost and limited resources of Pt. Engineering surface atoms of layered transition metal dichalcogenides (TMDs) is a promising way to design catalysts for efficient electrochemical reaction, the HER. However, materials processing based on TMDs, such as vacancy creation, edge exposure, or mechanical strain for active HER, has resulted in insufficient atomic-precision lattice homogeneity over a wide area. Here, we report a durable and effective HER in a pristine metallic MoTe2 single crystal. The rate-determining step of the HER on the MoTe2, the hydrogen adsorption, unexpectedly enhances the HER. Moreover, an exceptional HER performance, with a Tafel slope of 22 mV per decade and an exchange current density of 1.0 mA/cm2, was realized by hybridizing the MoTe2 with platinum, thus paving the way for a hydrogen economy.

Authors : MinJoong Kim, DongHoon Song, SeKwon Oh, EunAe Cho
Affiliations : Korea Advanced Institute of Science and Technology

Resume : Increasing demand for clean energy have triggered researches on alternative energy sources and devices to reduce use of fossil fuel. Hydrogen has been considered as one of the most promising energy source for future due to its high energy density and no air pollutant emission. Splitting water into hydrogen and oxygen is an environmentally friendly method for producing hydrogen gas. This technology can store excess electric energy in the form of chemical bonds of hydrogen, which can resolve an issue about surplus electric power of present renewable energy systems caused by irregular energy source such as airflow and sunlight. Water electrolysis reaction is divided into two half reactions; hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). High overpotential of both HER and OER is the most significant problems to hamper reaction rate and overall efficiency of water electrolysis, especially OER has much higher overpotential than HER. Therefore, recently major efforts have been devoted to exploring active catalysts for the OER in water electrolysis cell. Among many kinds of candidate materials for OER catalyst, cobalt (Co) and various Co based materials, including nanostructured Co3O4, CoSe2, Co based perovskites, CoP, CoB and Co/N-doped carbon, have drawn much attention for use in the alkaline water electrolysis system. These Co based catalysts have high OER activity in alkaline media comparable with precious metal based catalysts, such as IrO2 and RuO2. However, previous studies has focused mainly on the exploring desirable composites for low OER overpotential without careful mechanistic study. OER mechanism on Co based catalysts and descriptors for designing more efficient catalysts have been unclear yet. Herein, we report novel hybrid type catalysts, which composed of Co and molybdenum carbide (Mo2C), as efficient OER catalysts for alkaline water electrolysis, and evaluate the OER mechanism by investigating the effects of surface acidity of the catalysts on the OER activity in alkaline media. Mo2C has very similar electronic structure with platinum (Pt) group metal. So, it can be promising candidate as an efficient electrocatalyst for water electrolysis system. We synthesized Co-Mo2C hybrids using facile solution based process. Synthesized Co-Mo2C hybrids exhibit enhanced activity and durability compared with Co and ruthenium dioxide (RuO2) catalysts in alkaline media (0.1 and 1 M KOH). This result is ascribed to increase in surface acidity by formation of Co-Mo bimetallic surface on the Co-Mo2C hybrids. Increase in surface acidity leads to increase in hydroxide ion (OH-) adsorption on the catalyst surface, which can promote the OER kinetics in alkaline media.

Authors : N. Segercrantz, K. M. Yu, M. Ting, W. L. Sarney, S.P. Svensson, R. W. Martin, S. V. Novikov, C. T. Foxon, W.Walukiewicz
Affiliations : Department of Applied Physics, Aalto University, FI-00076 Aalto, Finland Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA; US Army Research Laboratory, 2800 Powder Mill Road, Adelphi MD, 20783 USA; US Army Research Laboratory, 2800 Powder Mill Road, Adelphi MD, 20783 USA; Department of Physics, SUPA, University of Strathclyde, Glasgow, G4 0NG, UK; School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD, UK; School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD, UK; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA;

Resume : GaN–based highly mismatched alloys have been proposed as materials suitable for photoelectrochemical (PEC) cells for solar water dissociation. A PEC photoelectrode suitable for spontaneous water splitting has to have a band gap small enough to efficiently absorb solar photons, and the band edges need to straddle the redox potentials of water. Here we report results of optical studies of GaNxSb1-x alloys over a wide composition range and show that the band structure of the alloys can be tailored for solar PEC applications. We have synthesized uniform GaNxSb1-x films with x ≤ 0.42 through an intermixing of MBE grown multilayer structures with a number of alternating layers of GaN and GaSb. All samples show a rapid decrease of the optical band gap with increasing Sb content. The results are explained by a modified band anticrossing model in which virtual crystal approximation is used to determine the band structure of the host crystal matrix. The modified model allows for accurate determination not only of the band gap but also of the valence and conduction band edge energies relative to the vacuum level. Since the observed band gap reduction results mostly from a large upward shift of the Sb-derived valence band edge the alloys offer a potential for matching of the band gap and the band offsets to the water redox potentials. Thus, we find that the GaN1-xSbx band edges straddle the water redox potentials for a composition as high as x = 0.2.

Authors : Katarzyna Grochowska1, Mariusz Szkoda2, Łukasz Mancewicz3, Jakub Karczewski3, Jacek Ryl4, Katarzyna Siuzdak1
Affiliations : 1 Centre for Plasma and Laser Engineering The Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Science Fiszera 14, 80-231 Gdansk, Poland; 2 Department of Chemistry and Technology of Functional Materials, Chemical Faculty, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland; 3 Faculty of Applied Physics and Mathematics, Gdansk University of Technology, Narutowicza 11/12, 80-233 Gdansk, Poland;4 Department of Electrochemistry, Corrosion and Material Engineering, Chemical Faculty, Gdansk University of Technology, Gdansk 80-233, Poland

Resume : In recent years, much research was carried out in the field of fabrication and characterization of titania nanotubes (TiO2 NTs) due to their unique properties, such as high specific surface area, non-toxicity, chemical stability and high photocatalytic activity. As a result, TiO2 nanotubes have been often applied for photocatalytic processes or in dye sensitized solar cells. It has been found that TiO2 modification with metal, non-metal atoms or metal oxides considerable enhances its photoactivity in the visible range. We propose modification of titania surface region by indium tin oxide (ITO) that is usually known as a semitransparent conductive oxide deposited onto the glass plate. The proposed modification was realized via magnetron sputtering technique where ITO plate was used as a target material and anodized titania served as a substrate. Afterwards, TiO2NT/ITO samples were calcined at 450°C for 2h. The ordered nanostructure and ITO clusters growth onto the nanotubes were proved by scanning electron microscopy. EDX and XPS analysis show that apart from titanium and oxygen, indium and tin atoms are present in the sample. On the basis of Tauc plot, it was found that for ITO-modified titania, the bandgap energy was shifted towards lower energy values. Obtained materials exhibit much higher activity under illumination registered as a photocurrent than pristine TiO2. Financial support from the National Science Center (2012/07/D/ST5/02269) is gratefully acknowledged.

Authors : Hin Chun Yau, Hannah Leese, Milo Shaffer
Affiliations : Department of Chemistry, Imperial College London, South Kensington Campus, London, SW7 2AZ, UK

Resume : Conducting elastomers are generally prepared by either depositing a network of nano-conductors (typically carbon nanotubes or silver nanowire) onto a flexible substrate or blending conductive nano-fillers with a polymer matrix. Although recent advancement in fabrication based on these two methods has already shown great improvement in both electrical and mechanical properties, innovative methods are still required to improve material homogeneity (nano-filler aggregation) and multiaxial conductivity (eliminating the insulating substrate). Single wall carbon nanotubes (SWNTs) are excellent nano-fillers due to their exceptional conductivity (metallic SWNTs) and relatively low bending modulus. Their high aspect ratio means percolation threshold could be reached at lower filler content, maintaining the softness of the flexible matrix. We performed a one-step reductive dissolution process to purify and dissolve SWNTs. The purified and charged SWNTs can then react with monomeric cyclic siloxane to produce homogeneous polydimethylsiloxane/SWNTs composites via anionic ring opening polymerisation. The purity of SWNTs and the reactivity with siloxane can be controlled by the degree of charging. In general, low charging ratio tends to purify SWNTs whereas high charging ratio gives higher reactivity with siloxane. Since the charged SWNTs are individualised due to Coulomb repulsion, uniform distribution of SWNTs within the composite can be achieved easily.

Authors : M. Viallon, A. Treizebre, Y. Pennec, G. Bedek, D. Dupont, M. Caillibotte, V.Thomy, V. Senez
Affiliations : Institute of Electronics, Microelectronics and Nanotechnology (IEMN), Villeneuve d'Ascq, France / Institu Supérieur de l'Electronique et du Numérique (ISEN), Lille, France ; Institute of Electronics, Microelectronics and Nanotechnology (IEMN), Villeneuve d'Ascq, France ; Institute of Electronics, Microelectronics and Nanotechnology (IEMN), Villeneuve d'Ascq, France ; Haute Ecole d'Ingénieur (HEI), Lille, France ; Haute Ecole d'Ingénieur (HEI), Lille, France ; Damart France, Roubaix, France ; Institute of Electronics, Microelectronics and Nanotechnology (IEMN), Villeneuve d'Ascq, France ; Institute of Electronics, Microelectronics and Nanotechnology (IEMN), Villeneuve d'Ascq, France / Institu Supérieur de l'Electronique et du Numérique (ISEN), Lille, France

Resume : Recently, photonic crystals (PC) have attracted much attention in application fields of optical reflectors and various implementations have been tested using either silicon or polysilicon. Our goal is to develop polymer based photonic membrane to control heat losses through radiative exchange in the MIR range for applications such as wearable textiles, building insulation or food packaging. We have fabricated silicon based PC, either ridges or holes, with dimensions about tens of microns. These structures have been simulated with a numerical model (FDTD) and characterized in the 5-15 µm range to evaluate the accuracy of the model. Various geometries have been studied to understand the effects of process variation on the functionality of the membrane. Then, we have processed polymer membranes (10 µm thick) with circular holes (few microns diameters) and various filling factor. Experiments and simulation have been undergone in order to study the influence of structures’ dimensions on their reflectivity. These membranes show narrow Fano’s type bands presenting high reflectiveness on narrow bandwidth. The efficiency of the various designs is compared by integrating the reflected energy on 5-15 µm spectrum divided by the energy produces by a black body in the same spectrum. This work permits to quantify actual efficiency of the polymer membranes and paves the way for the design of a smart responsive membrane modifying its reflectance in response to external stimuli (RH, T).

Authors : Prabu Moni, Westerley Chaves, Michaela Wilhelm, Kurosch Rezwan
Affiliations : University of Bremen, Advanced Ceramics, Am Biologischen Garten 2, IW3, Germany

Resume : The need to diminish greenhouse gas emissions opens the demand for discovery of very affordable and highly efficient materials with a unique structure for CO2 capture and energy storage (1-2). Recently, hybrid materials combining graphene or carbon nanotubes and inorganic-organic composites emerged as a new class of materials because of their unusual and superior properties including excellent thermal and chemical stability, high conductivity, outstanding oxidation and corrosion resistance, and tunable porosity (3). This study is focused on developing a highly conductive hybrid material with controllable surface characteristics and hierarchical structures using polysiloxanes as polymer backbone with graphene oxide (GO) as conductive nanofiller. Using emulsion based strategy with tetradecyltrimethylammonium bromide (TTAB) as surfactant we were able to create a monolithic structure made of polysiloxanes beads covered with reduced graphene oxide (rGO). From the AC impedance spectroscopic analysis, the electrical conductivity of SiOC ceramics increased with the incorporation of GO. In addition, the supercapacitor and CO2 adsorption behavior of the polysiloxane derived materials were tested. The CV curve shows the double layer capacitors with a high capacitance of 88 F/g at 2 mV s-1 in 0.5 M H2SO4 electrolyte solution and CO2 adsorption capacities up to 2 mmol/g, at 25 °C. Reference 1. Rutao Wang, Peiyu Wang, Xingbin Yan, Junwei Lang, Chao Peng, and Qunji Xue, ACS Appl. Mater. Interfaces 2012, 4, 5800−5806 2. Nilantha P. Wickramaratne, Jiantie Xu, Min Wang, Lin Zhu, Liming Dai, and Mietek Jaroniec, Chem. Mater. 2014, 26, 2820−2828 3. Luis Estevez, Rubal Dua, Nidhi Bhandari, Anirudh Ramanujapuram, Peng Wang and Emmanuel P. Giannelis, Energy Environ. Sci., 2013, 6, 1785–1790

Authors : Aoife K. Lucid, Jeremy P. Allen, Patrick R.L. Keating, Graeme W. Watson
Affiliations : School of Chemistry and CRANN, Trinity College Dublin, Dublin 2, Ireland

Resume : Ceria (CeO2) has received considerable interest as an electrolyte for intermediate temperature solid oxide fuel cells. [1] Unfortunately, within this temperature range (~600-800°C), ceria displays poor ionic conductivity, while at high temperatures and low oxygen partial pressures Ce(IV) can be reduced to Ce(III), due to facile oxygen vacancy formation, [2] which results in electronic conductivity. In an attempt to improve the ionic conductivity of ceria aliovalent doping is commonly employed, with trivalent species (e.g. Gd(III), Sm(III)) a particular focus due to their creation of charge compensating vacancies which forms an oxide ion diffusion pathway without the presence of Ce(III). Experimental evidence [3] has corroborated the increased ionic conductivity from trivalent dopants, however a detailed understanding on the effect of the dopant on the electronic structure of ceria and a full exploration of the range of trivalent dopants has been lacking. This study considers two aspects of trivalent doping using density functional theory simulations: (i) the formation of charge compensating vacancies and their role in oxide ion conductivity, and (ii) their effect on the reducibility of ceria. These aspects are explored for a range of p-, d- and f-block ions. [1] Brett et al., Chem. Soc. Rev., 37, 1568 (2008). [2] Scanlon et al., J. Phys. Chem. C, 113, 11095 (2009). [3] Fu et al., Int. J. Hydrogen Energy, 35, 745 (2010).

Authors : Julia Walton, Simon Hall
Affiliations : Complex Function Materials Group, School of Chemistry, Bristol University, Bristol Centre for Functional Nanomaterials

Resume : Organic conductors and charge-transfer complexes are of interest due to their wide range of physical properties, from semiconducting polyaromatic hydrocarbons (PAHs) such as rubrene to superconducting TTF-based Bechgaard salts. Charge-transfer complexes based on TCNQ acceptors and a PAH donor such as TCNQ-coronene exhibit semiconducting properties and are well-documented in literature; electron transfer can be tuned by variables such as temperature, pressure, stoichiometry composition and are hence of key interest in organic electronics due to the potential to ‘design’ highly conducting materials whilst preserving the low-cost and flexibility of organic materials. Crystals in polymorphic materials can exist in multiple packing arrangements. This is exemplified in PAHs by rubrene which is notable for holding the record for carrier mobility in organic conductors, however, certain polymorphs exhibit no measurable conductivity. Selection of particular polymorphs can hence be exploited to tailor physical properties in organic conductors. Whilst this is well-explored in PAHs, far less attention has been given to polymorphism in these charge transfer co-crystals. Recently, a new polymorph of coronene has been discovered via growth in a magnetic field. This work explores the application of external fields as a novel method of driving crystallisation towards selection of polymorphs that exhibit improved conductivity.

Authors : B. M. Jung, U. H. Choi, J. R. Choi, S. J. Kwon, S.-B. Lee
Affiliations : Composites Research Division, Korea Institute of Materials Science, Korea

Resume : Epoxy resins are important thermosetting polymers which have been used in composites as structural materials. They showed high thermal and chemical stability and good mechanical properties. However, there is no ionic conductivity in epoxy resin due to cross-linked structures of polymer chain restrict the transfer of small molecule like ion water, etc. There are some researches to fabricate ion conducting epoxy resin by the co-curing of epoxy resin and ionic liquid.[1,2] The mechanical properties and ionic conductivity are effected by morphology control of hybrid system. In this work, we used plastic crystal as electrolyte and crown-ether, and oligo-ethylene glycol as additive. Morphologies were controlled by change of volume ratio of epoxy resin/electrolytes and curing condition. The structure of cured epoxy resin was investigated by SEM. The cured polymer was shown about 10-6 S/cm of ion conductivity and 0.88 GPa of Young’s modulus. [1] B. G. Soares, A. a. Silva, J. Pereira, S. Livi, Macromol. Mater. Eng., 2014. [2] N. Shirshova, A. Bismarck, S. Carreyette, Q. P. V. Fontana, E. S. Greenhalgh, P. Jacobsson, P. Johansson, M. J. Marczewski, G. Kalinka, A. R. J. Kucernak, J. Scheers, M. S. P. Shaffer, J. H. G. Steinke, M. Wienrich, J. Mater. Chem. A, 2013, 1, 15300.

Authors : Soumi Chatterjee1,2, Ramaprasad Maiti1, Shyamal Kumar Saha2 and Dipankar Chakravorty1
Affiliations : 1MLS Professor’s Unit, Indian Association for the Cultivation of Science, 2A and 2B Raja S. C. Mullick Road, Kolkata 700032, India 2Department of Materials Science, Indian Association for the Cultivation of Science, 2A and 2B Raja S. C. Mullick Road, Kolkata 700032, India

Resume : Mesoporous silica SBA-15 was exploited to synthesize a nanocomposite in which a nanoglass of composition 35Li2O.65SiO2 could be incorporated within the nanochannels of diameter 5.5 nm of the template. A dc electrical conductivity of 10-4 S-cm-1 was measured for the nanoglass at room temperature with an activation energy of 0.1 eV. This arose due to oxygen ion vacancies caused by the presence of Si2+ and Si4+ species in the mesoporous silica at its interface with the nanoglass. A repulsive interaction between the defects and the lithium ions reduced the attractive electrostatic force between the non-bridging oxygen ions and the lithium ions. These nanocomposites are expected to have applications in lithium ion batteries for storage of renewable energy.

Authors : S. Polivtseva, A. Katerski, E. Kärber, I. Oja Acik, A. Mere, V. Mikli, M. Krunks
Affiliations : Department of Materials Science, Tallinn University of Technology, 19086 Tallinn, Ehitajate tee 5, Estonia.

Resume : SnS films as an alternative low cost chalcogenide absorber for thin film solar cells were grown by chemical spray pyrolysis. Acidic aqueous solutions consisted of tin chloride (SnCl2) and thiourea (SC(NH2)2) at molar ratios of 1:1 and 1:8 were deposited onto glass substrates at 200 °C in air. We studied the effects of post-deposition annealing treatments in nitrogen and vacuum at 450 °C for 60 min on properties of sprayed films. SnS films were examined by X-ray diffraction (XRD), Raman and UV-Vis spectroscopies, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). According to XRD and Raman studies, cubic SnS is the main crystalline phase of films independent of precursors’ molar ratio in the spray solution. 1:8 films annealed in nitrogen are composed of a mixture phases of Sn2S3 as the main and SnS as the minor phases. Annealing of 1:8 films in vacuum results in orthorhombic SnS phase, films show optical band gap of 1.4 eV. Thermal annealing of 1:1 films in vacuum leads to metallic Sn, while annealing in nitrogen results in films composed of a mixture of SnS and SnO2 phases. The formation of oxidized phases shows that oxygen containing phases are present additionally in the as-grown film. In this study we discuss the chemical reactions taking place during the thermal treatments, along with the optimal deposition conditions and optimal post-deposition treatment for fabrication of SnS single phase films.

Authors : Gustavo Baldissera, Clas Persson
Affiliations : Department of Materials Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm, Sweden; Department of Physics, University of Oslo, P.O. Box 1048 Blindern, NO-0316 Oslo, Norway and Department of Materials Science and Engineering, Royal Institute of Technology, SE-100 44 Stockholm, Sweden

Resume : Tungsten sulfides and selenides are materials with band gap energies are in a range of 1.2 to 2 eV, revealing a good match to solar energy materials [1]. Due to the potential for photovoltaic applications, we analyze the optical and electrical characteristics of the semiconductor compounds of tungsten chalcogenides WX2 and WX3 with X = S, Se, and Te. The different phases of the compounds are calculated within the density functional theory (DFT) using the generalized gradient approximation and a plane-wave basis set. The electronic structures of the phases are compared, and based on the investigation of the optical absorption and the density-of-states the most interesting compounds are further analyzed with a post-DFT approach [2]. [1] H. Jiang, J. Phys. Chem. C 116, 7664 (2012). [2] M. Dou, et al., Int. J. Hydrogen Energy 38, 16727 (2013).

Authors : Joop van Deelen, Felipe Bernal Arango, Marco Barink
Affiliations : TNO/Solliance

Resume : The design of thin film silicon based solar cells have received much attention. In general it has been found that the optical benefit of a periodic texture is often limited to specific wavelengths and more recently random or quasi random approaches have been proposed for improved light management. In this work, we focus on optical improvement for perovskite and CIGS cells. Modeling indicates that the reflection can be reduced to near zero levels when a non-random multiperiodic texture is used. Moreover, when the layers stack and textures are tuned with respect to eachother, excellent results can be obtained even with using a single period. This can be related to the combined optimization of the steepness of the texture and higher order refraction phenomena, which creates a net effect which appears as a broadband antireflection. Moreover, as the perovskite cell has a relative low reflection even with flat layers, we found nevertheless that the benefit of a texture can be significant, simply by higher incoupling of the light into the absorber layer. This also has its impact on possible perovskite/CIGS tandem cell stacks.

Authors : Dana Perniu, Cristina Bogatu, Alexandru Enesca, Anca Duta
Affiliations : Transilvania University of Brasov, The Center Renewable Energy Systems and Recycling, Brasov, Romania

Resume : The limitations of TiO2, known as photocatalyst for various pollutants, are related to the rapid rate of photogenerated electron-hole pairs and the light absorption in the UV domain hindering the processes up-scaling. The use of TiO2 deposited by cold spraying on flexible substrates and/or fabrics represents a twofold challenge of materials design: to enhance the TiO2 photoactivity and to formulate the ink. To improve the TiO2 photoactivity, the design strategy considers the Schotky diode concept, by developing TiO2/Ag heterostructures. The specific structure and composition of the developed materials corroborated with interface parameters influences the photodegradation ability of the system. In developing photocatalytic inks, fine control of the particles synthesis process and the dispersion rheological properties and stability were considered as optimization criteria. To obtain TiO2 - based photocatalytic dispersions, the particles were dispersed in aqueous and aqueous/alcoholic continuous medium and stabilized using surfactants (DTAB, PEG), polymers (polyvinylpyrrolidone, policrylamide) or capping agents (TODA). Based on transmittance spectra, the stability was discussed considering the stabilizer’s steric effect and the electrostatic repulsions between the particles. Methyleneblue photodegradation by TiO2 – based material deposited on fabrics from dispersion stabilized with TODA and DTAB provided removal efficiency higher than 75% under simulated solar radiation.

Authors : M. M. Kuklja+, S. N. Rashkeev+‡, R. Tsyshevsky+, Fenggong Wang+
Affiliations : +Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742, USA ‡ Qatar Environment & Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, P. O. Box 5825, Doha, Qatar

Resume : We present a new concept for design and use of interfaces formed by a metal oxide catalyst and energetic material for multiple energy applications. Electronic structure calculations are performed to explore mechanisms of energy absorption and release of the interfaces formed by energetic molecules (e.g., PETN, TNT) adsorbed on metal oxide surfaces (e.g., MgO, α-Al2O3, TiO2). We propose a photodecomposition mechanism, which is governed by interactions of energetic particles with structural and electronic defects (F0-centers) on metal oxide surfaces. We illustrate how the interfaces are designed to facilitate the low energy F0-center – energetic molecule transition, producing the excited triplet state, and F0-center – energetic molecule charge transfer, generating an anion radical. Irradiation by commonly used Nd: YAG lasers can initiate photodecomposition of both excited and charged energetic molecules. This photoinitiation is tailored to be triggered by a modest optical energy while the interface will release a large amount of thermal energy. The developed computational strategy to design new energetic materials, hybrid materials and multi-functional interfaces further clarify atomistic mechanisms of charge transfer on surface defects and energy conversion on interfaces thus providing a solid basis for fundamental understanding of decomposition chemistry of highly energetic materials, energy storage and conversion, photocatalysis, and molecular electronics.

Authors : Alexandra Siklitskaya, Jacek A. Majewski
Affiliations : University of Warsaw, Institute of Theoretical Physics L.Pasteura 5, 02-093 Warsaw, Poland

Resume : Carbon dioxide is one of the primary greenhouse gases implicated in global warming process. Alternative energy sources that make no contribution to CO2 emission are still in the development phase and not likely to replace current carbon-based energy sources during the few next decades. Therefore, sequestration process is of critical importance to maintain or even reduce the CO2 level in the atmosphere. To reach it one should gain understanding of possible microscale effects. In order to predict thermodynamic and transport properties of this system one should study the main components of the soils namely widely spread micaceous minerals like illite (K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O). In the present study the structural and thermodynamic properties of the illite - CO2 system were investigated with the Car-Parinello molecular dynamics( CPMD). We relaxed several structures and found the one with the lowest adsorption energy, further we determined possible CO2 capture reactions from total energies and free energies from CPMD. Molecular dynamics calculations with canonical ensemble (NVT) were performed. The stability of such systems was also predicted as a function of certain temperature.

Authors : Véronique Sproll, Gergely Nagy, Urs Gasser, Sandor Balog, Thomas J. Schmidt, Lorenz Gubler
Affiliations : Véronique Sproll, Electrochemistry Laboratory, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland; Gergely Nagy, Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland; Urs Gasser, Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland; Sandor Balog, Adolphe Merkle Institute,University of Fribourg, 1700 Fribourg, Switzerland; Thomas J. Schmidt, Electrochemistry Laboratory, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland, Laboratory of Physical Chemistry, ETH Zurich, 8093 Zürich, Switzerland; Lorenz Gubler, Electrochemistry Laboratory, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland

Resume : Over the last decades radiation grafting proved to be a versatile and flexible method for the preparation of proton exchange membranes (PEMs), which are a key component of polymer electrolyte fuel cells. Advantages of this method include the easy functionalization of base films such as ETFE, poly-(ethylene-alt-tetrafluoroethylene), offering a high level of performance adjustment via controllable preparation parameters (e.g. dose of the applied irradiation, reaction conditions, monomer or comonomer system, level of grafting and of crosslinking). Despite the experience gathered in this field, new approaches and detailed understanding of the generated structures is mandatory for the optimization of these membranes. To gain further insight into the impact of morphology of such membranes, two systems were synthesized using the same components (styrene monomer, subsequently sulfonated). Type A shows a low number density of grafts with a long chain length whereas type B ideally consists of a high number density of shorter grafted chains. For this discussion, the grafting level in both types is kept constant and grafting parameters had to be adjusted in a way to ensure comparable through-plane distribution profiles. To elucidate the -influence of the two pre-irradiation grafted copolymer designs, type A and B membranes were investigated in terms of through-plane homogeneity (EDX), graft-copolymer nanostructure (SANS, SAXS) and their ex-situ fuel cell relevant properties.

Authors : D. Taharchaouche1, F. Mechachti1, A.Djebaili1*, J.P. Chopart2, B. Frederic2
Affiliations : 1 Laboratory of chemistry and environmental chemistry L.C.C.E - University of Batna- Algeria 2 Laboratory of Mechanical Stress-Transfer Dynamics at Interfaces – LACMDTI URCA,BP 1039, 51687 University of Reims Cedex2, France

Resume : To explain the isomerization reaction mechanism of substitued polyacetylenes, we used an HF (ab-intio) and DFT (B3LYP) 6-31G and 3-21G** methods. The various (rotations, conversions, rearrangemnts) and the different intermediates (transition state) were investigated. The results were as following: * The studied bonds in the fragments (C10H12, C10H6F6, C10H6Cl6) showed an important stability, justified by the low HOMO-LUMO energetic gap observed. However, the stability of many conformations showed that, the trans form was the more stable than the cis form. * The different reactions profiles, reveled that the size and the nature of the dopant (substituant) play a major role in the evolution of the activation energy. * The calculated activation energy values indicated that the rates constants were in the order: kC10H12 >>kC10H6F6>> kC10H6Cl6. * Reaction intermediates during Cis-Trans transition showed that the geometrical parameters (angles and diedres angles) were amongst the most changed parameters, this was observed in the cases of substituted and unsubstitued PA.

Authors : Sahn Nahm, HaiBo Xu, Young-Jin Ko, Tae-Gon Lee, Su-Jin Park, Myoung-Sub Noh
Affiliations : Department of Materials Science and Engineering, Korea University, 1-5 Ga, Anam-Dong, Seongbuk-Gu, Seoul 136-701, Korea

Resume : (Na1-xKx)NbO3 (NKN) platelets synthesized at 600oC for 12 h have an Amm2 orthorhombic structure that is a stable NKN structure at room temperature. However, the structure of NKN platelets synthesized at 500oC for 1 h is a mixture of R3m rhombohedral and Amm2 orthorhombic structures. Formation of the rhombohedral structure is attributed to the presence of the OH- and H2O defects in the NKN platelet. The piezoelectric strain constant (d33) of the NKN platelets synthesized at 600oC for 12 h is 100 pmV-1 but the NKN platelets synthesized at 500oC for 1 h show a smaller d33 of 50 pmV-1 due to the presence of these defects. Piezoelectric energy harvesters (PEHs) are fabricated using composites consisting of NKN platelets and polydimethylsiloxane. A large output voltage of 20 V and output current of 3.0 μA are obtained by bending the PEH with NKN platelets synthesized at 600oC for 6.0 h with a strain of 2.13% and an average strain rate of 3.79 %s-1. Moreover, this PEH shows a high output electrical energy of 3.0 μW at an external load of 5.1 MΩ. In addition, an output voltage of 5.0 V and current of 400 nA are also obtained by softly tapping this PEH by hand.

Authors : K. Taïbi 1, N. Haddadou 1, N. Boutal 1, M. Trari 2
Affiliations : 1- Crystallography-Thermodynamics Laboratory, Faculty of Chemistry, USTHB, P.O.Box 32, El Alia, 16111, Algiers, Algeria; 2- Laboratory of storage and Valorization of Renewable Energies, Faculty of Chemistry, USTHB, P.O.Box 32, El Alia, 16111, Algiers, Algeria **Corresponding authot. Tel: (+213) 556847477; E-mail:

Resume : A large number of perovskite (ABO3) materials exhibit a ferroelectric behaviour. A special attention has been given to the complex perovskite (AA’BB’O3) compounds with disorder cations leading to a new class of ferroelectric called relaxor. Materials having such characteristics are very interesting in the field of applications in electronics (1, 2) and in photocatalysis (3). The usual ferroelectric materials are lead-based ceramics and derived compounds which present disadvantage due to the toxicity and volatility of PbO during the manufacturing process. To protect the environment, researches are oriented towards lead-free materials. In the other hand, photocatalysis studies and particularly the photocatalytic hydrogen production represents a very promising contribution to a clean and renewable energy system. In this way, we present the ferroelectric properties of some lead-free perovskites compounds and their behaviour as photocatalyst. The concerned compositions are belonging to the systems BaTiO3-BaZrO3-A2O3 systems (A= rare earth or trivalent cations). As an example: - Typical relaxor behaviour and diffuse phase transition were observed in Ba0.975Eu0.017(Ti0.75 Zr0.25)O3, composition. The different characteristics of these ceramics present a real interest for environment applications. These compositions show a relaxor effect with unfortunately transition temperature below room temperature. Nevertheless, the photoelectrochemical investigation show an optical gap of 2.25 eV obtained from the diffuse reflectance spectrum. The energetic diagram clearly assesses the photoactivity of this perovskite. 95% of chromate (10-4 M) is reduced after 6 h of exposition to sunlight. - Ferroelectric relaxor with a phase transition close to room temperature was obtained for Ba0.785Bi0.127Y0.017TiO3, This composition is very interesting for electronic applications and can replace lead-based ferroelectric ceramics to prevent the environmental pollutions during the preparation step. In the other hand, Ba0.725Bi0.120Y0.033TiO3 (optical gap = 2.43 e.V) has been tested successfully for H2 production upon visible light when combined to the Delafossite CuFeO2 as sensitizer. An evolution rate of 24 micromol mn-1 and a quantum yield of 0.4% under polychromatic light were obtained. References 1. L.E. Cross, Ferroelectrics, 151, 305-3.., 1994 2. K. Uchino, Ferroelectrics, 151, 321-3.., 1994 3. Y. Yang, Y. Suna, Y. Jiang, C*hemistry and physics,96, 234-239, 2006

Authors : Chengbin Wang, Cuilan Ren, Wei Zhang
Affiliations : Shanghai Institute of Applied Physics

Resume : Helium diffusion and clustering in nickel are studied by molecular dynamics simulations. Extensive atomistic simulations are performed using a modified analytic embedded-atom model. We find that the rate of helium clustering increases with increasing temperature, and interstitial helium clusters can create nickel interstitials when they reach sufficient size and temperature is higher than 600 K. Finally, the mobility of helium clusters is also investigated using trajectory time decomposition method. The diffusion properties of He clusters with 1–3 helium atoms are found to obey the Arrhenius relationship over the whole temperature range considered while He clusters with 4 helium atoms show an non-Arrhenius relationship at higher temperatures.

Authors : Jian Peng* (corresponding author,, Xianhua Cheng, Yaobo Hu, Guangsheng Huang, Deqiang Kong, Fusheng Pan
Affiliations : Jian Peng*: State Key Laboratory of Mechanical Transmission, College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China. Chongqing Academy of Science and Technology, Chongqing 401123, China; Xianhua Cheng; Yaobo Hu; Guangsheng Huang; Deqiang Kong: State Key Laboratory of Mechanical Transmission, College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China; Fusheng Pan: State Key Laboratory of Mechanical Transmission, College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China. Chongqing Academy of Science and Technology, Chongqing 401123, China

Resume : In order to improve the weight reduce potential of magnesium alloy in wind power equipment, green car and other fields related to energy and energy saving, a new melt treatment methods were developed to purify the alloy and to improve its mechanical properties. The Mg-8Al-0.7Zn-0.25Mn-1.0Y/1.6Ce-0.1Sr alloys melt with an extra holding treatment at temperature of 650℃ were used for die casting, the microstructure and mechanical properties of the products of the two kinds of alloys were investigated by optical microscopy, scanning electron microscopy, X-ray diffractometer and tensile test. The results show that the low-temperature holding treatment can reduce the content of Fe in magnesium alloys effectively and result in a bigger average grain size of the alloy as die-casting state. The average value of ultimate tensile strength, yield strength and elongation of the alloy contain Ce can be improved from 151.4 MPa, 121.6 MPa and 0.709% to 222.7 MPa, 143.8 MPa and 4.064%. And the electrical and thermal conductivity are improved significantly to attribute to the decrease of Fe impurity. This allows the alloy to be used in a wider range of energy fields.

Authors : M. Qamar,a M. Abdalwadoud,b A. Khan,a M. N. Siddiqui,b B. Merzougui,c
Affiliations : a Center of Excellence in Nanotechnology (CENT), King Fahd University of Petroleum and Minerals, Dhahran 31261, Kingdom of Saudi Arabia. b Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Kingdom of Saudi Arabia. c Qatar Environment & Energy Research Institute, Qatar Foundation, Doha 5825, Qatar.

Resume : Although photocatalysis offers one of the most promising processes to be utilized in solar energy conversion, it suffers with unavailability of stable catalysts that can absorb the photons across the UV-visible region and efficiently generate electron-hole pairs with longer life time. Recently, reduced or oxygen-deficient form of TiO2 has been found to be active under visible light. However, facile route to prepare such photocatalyst remains to be explored. Here, we report a single-pot and low temperature solvothermal method to synthesize highly oxygen-deficient TiO2 and its heterostructure with reduced graphene oxide (RGO) in the absence of any additional reducing agent. Microscopic images showed the formation of TiO2 nanocubes with <20 nm in size. Moreover, these nanocubes were primarily consisted of Ti3+, and capable of absorbing a broad solar spectrum (ultraviolet-visible region). Photoelectrochemical oxidation of water was investigated in the presence of synthesized TiO2 and TiO2/RGO under visible (λ > 420 nm) and UV-visible (λ > 300 – 600 nm) radiation, and the performance was compared with those of anatase TiO2 and nitrogen-doped TiO2.

Authors : Hoon Kee Park, Ho Won Jang
Affiliations : Department of Materials Science and Engineering, Seoul National University, Seoul 151-744, Korea.

Resume : Water splitting has attracted increasing attention for clean energy generation and efficient energy storage. Due to relatively high overpotential than hydrogen evolution reaction(HER), the oxygen evolution reaction(OER) is a key reaction in water splitting. To overcome this problem, current studies are focused on development of efficient, abundant and inexpensive OER catalyst. Although Nickel/iron(NiFe)-based compounds have been known as active OER catalysts for decades, NiFe-based materials such as NiFe LDH receiving attention recently. Here we report an approach to improve efficiency of water splitting electrodes based on flexible NiFe-based foil. Anodic oxidation method is applied to enhance the oxygen evolution activity of NiFe alloy foil. The anodized NiFe alloy foil exhibit significant higher activity than the corresponding Ni foam in base conditions. The anodic oxidation method generate NiFe oxide and hydroxide layers on NiFe alloy surface, act as electrocatalyst. Spontaneously, the anodic oxidation method widen the specific surface area of water splitting electrodes. Increased reaction sites and catalytic behavior of NiFe hydroxide is the reason of improved water splitting property. This work demonstrates the promising electrocatalysts of NiFe based materials for the oxygen evolution reaction.

Authors : Jianyong Zhang
Affiliations : School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, 510275, China

Resume : Porous materials have gained considerable interest in fundamental and practical research due to their potential application in gas storage, separation and others. Dynamic covalent or coordination bonds are a class of bonds that can be broken and reformed reversibly under mild reaction conditions. For example, imine bond, formed via the reversible condensation of an amine and an aldehyde, displays ideal dynamic covalent bond characteristics. Using dynamic covalent/coordination chemistry, complex discrete molecular architectures and extended frameworks have been constructed from relatively simple molecular precursors. However, much less is understood about gel porous materials based on dynamic covalent bonding or metal-organic coordination, despite their numerous potential applications as absorbents, sensors, catalytic and responsive materials. Recently we develop this catalogue of gel/aerogel materials that are based on dynamic imine [1-3] or metal-organic coordination bonding [4-7]. Their structure, porosity and formation mechanism have been investigated. The gels show unique hierarchical porosity consisting of interconnected microporous nanoparticles. Their potential applications in gas sorption and others have been demonstrated. For example, some imine aerogels show high CO2/N2 selectivity. The rich diversity of building units makes it possible to develop a wide range of novel functional materials directed by dynamic covalent/coordination bonding. 1. J. Zhang*, L. Liu, H. Liu, M. Lin, S. Li, G. Ouyang, L. Chen and C. Y. Su, J. Mater. Chem. A, 2015, 3, 10990-10998. 2. H. Liu, J. Feng, J. Zhang,* P. W. Miller,* L. Chen, and C. Y. Su,* Chem. Sci., 2015, 6, 2292-2296. 3. W. Luo, Y. Zhu, J. Zhang,* J. He, Z. Chi, P. W. Miller, L. Chen and C. Y. Su, Chem. Commun., 2014, 50, 11942-11945. 4. J. Zhang* and C. Y. Su, Coord. Chem. Rev., 2013, 257, 1373-1408. 5. S. C. Wei, M. Pan, K. Li, S. Wang, J. Zhang* and C. Y. Su*, Adv. Mater., 2014, 26, 2072-2077. 6. L. Li, S. Xiang, S. Cao, J. Zhang,* G. Ouyang, L. Chen and C. Y. Su*, Nature Commun., 2013, 4, 1774. 7. S. C. Wei, M. Pan, Y. Z. Fan, H. Liu, J. Zhang* and C. Y. Su*, Chem. Eur. J., 2015, 21, 7418-7427.

Authors : Mohammad Wahiduzzaman(a), Benjamin J. Sikora(a), Sujing Wang(b), Christian Serre(b), Guillaume Maurin(a)
Affiliations : (a) Institut Charles Gerhardt Montpellier, UMR 5253 CNRS, Université Montpellier, Montpellier, France (b) Institut Lavoisier Versailles, UMR 8180 CNRS, Université Versailles Saint Quentin en Yvelines, France.

Resume : Metal-organic frameworks and other nanoporous hybrid materials have widespread applications in energy and environmental applications, but the pathway from laboratory synthesis to practical implications is substantially challenging. More specifically, these framework materials often present an arduous challenge for structure determination due to their relatively poor crystallinity, low symmetry and large unit cell volumes that make the indexation of their powder X-ray patterns very complex and thus requires more efficient tools for step-wise modeling, screening and characterization. Inspired by the concept of molecular building units, we developed a software for such structure solution based on a revisited version of the AASBU (Automated Assembly of Structure Building Units) method. As a first step, this computational tool has been thoroughly validated on a series of experimentally-known MOF structures. The software has been further able to successfully predict some recently synthesized novel Zr-based MOFs characterized by the SBU present in the widely-studied UiO-66(Zr) MOF. As the software is under active development, we are confident that in the near future we will present a mature version of the software to the scientific community which will allow the determination and in silico prediction of novel structures that are created by more advanced and complex organic, inorganic and hybrid clusters.

Authors : M. Torréns (a), F.A. Garcés (a), B. Rodríguez-García (a), J.R. Galán-Mascarós (a) (b)
Affiliations : (a) Institute of Chemical Research of Catalonia (ICIQ), Avenida Països Catalans 16, E-43007 Tarragona, Spain. (b) Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluis Companys 23, E-08010 Barcelona, Spain

Resume : Electrolytic high purity hydrogen production is still underuse (less than 4% of the global H2 production) because of its high price point when compared with steam reforming. Despite being a very sustainable method for H2 production, novel electrolytic technologies need to be develop to reach competitiveness in the world market. It is well accepted that the sluggish water oxidation kinetics is the limiting step in this process. To solve this drawback, many water oxidation catalysts (WOC) have been studied. One of the most promising candidates for the development of novel hydrolyzer technologies are the coordination polymers of the Prussian blue (PB) family [1]. These materials exhibit excellent stability, and processability, being active in a wide pH range. However, high current densities are still the major challenge because an appropriate electrode support for these novel WOC has not been identify yet. Here we present the development of stable high-surface area electrodes decorated with the Co-Fe PB for sustained and low-cost anodes in an electrolyzer architecture. The study of immobilization methods of the PB on substrates with high surface area, and the respectively characterization of the modified surface by ESEM, FTIR and XRD will be discussed. Finally, the electrochemical analysis of the surfaces, and the correlations between components, processing, catalytic activity and high stability will be highlighted. [1] Pintado, S. et al., J. Am. Chem. Soc, 135(36)( 2013)13270

Authors : Håkan Wilhelm Hugosson, Amina Mirsakiyeva.
Affiliations : KTH Royal Institute of Technology, Stockholm, Sweden.

Resume : The thermoelectric conjugated polymer poly(3,4-ethylenedioxythiophene), or PEDOT, contains a carbon backbone consisting of alternating short and long carbon bonds. Therefore there are two isomeric states: aromatic and quinoid. Charge injection or the presence of charged doping agents leads to the formation of localized charge in the conjugated polymer - a so-called polaron. This polaron induces a localized structural distortion (a shift from the aromatic form towards the quinoid) in the conjugated carbon backbone. Self-localized polarons in conjugated carbon systems have been found using semi-empirical or HF-theory, but formerly never using DFT with local or gradient corrected functionals (e.g. LDA/BLYP). Self-localization has been seen using DFT and long range hybrid functionals with partial exact exchange included. Using modern ab initio molecular dynamics methods based on DFT we have studied PEDOT and its charge carrying polarons. The localization of the polaron is now studied in the time-averaged changes in bond-distances and also in snap-shots of the frontier orbitals for long oligomers (12 monomers).

Authors : L. Popovici, A.M.I. Trefilov, V. Garleanu, A. Tiliakos, I. Stamatin
Affiliations : University of Bucharest, Faculty of Physics, 3Nano-SAE Research Centre, Bucharest-Magurele, Romania

Resume : We design a novel gas diffusion layer (GDL)/catalyst/membrane assembly using carbon xerogels as an alternative to the carbon paper which traditionally sustains the MEA assembly in proton exchange membrane Fuel Cells (PEMFCs). Xerogel synthesis reports a variation on the classical method for carbon xerogel synthesis, where the xerogel cross-linking process is performed in a centrifugal field, resulting in monolithic cylindrical configurations. We synthesize resorcinol-formaldehyde-GO (RFGO) xerogels by sol-gel polycondensation of resorcinol with formaldehyde in the presence of GO as the acidic catalyst in centrifugal fields of various magnitudes (125G/75G/37.5G) – the final pyrolysis stage of the method reduces GO into graphene. Platinum-ink, serving as FC catalyst, is directly sprayed on the carbonized xerogel cylinder and incorporated in the FC assembly by hot-pressing against a Nafion membrane. The integrated PEM fuel cell presents a maximum current density between 400 and 700 mA for the given catalyst loading ─ 0.6 mg/cm².

Authors : Javier Vazquez-Galvan, [a]* Cristina Flox [a] and Joan Ramon Morante [a,b]
Affiliations : [a] Department of Advanced Materials for Energy Catalonia Institute for Energy Research Jardins de les Dones de Negre, 1, 08930 Sant Adria de Besos, Barcelona . [b] Departament d’Electronica, Facultat de Fisica, Universitat de Barcelona, Spain. *Corresponding author

Resume : Vanadium redox flow battery offers not only a great promise to provide a robust and constant energy storage system, but also several advantages such as scalability, long cycle life, high efficiency, power and energy are independent. Despite all of its merits, VFBs have reached only a limited market presence after the continuous development the last 30 years. The improvements VFB performances require a better reversible kinetics with minimum side reactions (i.e hydrogen evolution) for a commercial outbreak. Our approach has been applied Rutile-TiO2 hydrogen-treated electrocatalyst for high performance all-vanadium redox flow batteries (VFRB) as a simple and eco-friendly strategy well-suited for large-scale applications. TiO2 hydrogen-treated shell in a graphite felt core (GF@TiO2:H) was prepared by a combination of hydrothermal synthesis followed by thermal treatments. Comparatively to commercial electrodes, rutile TiO2-based nanorods decorating graphite felt samples perform an abrupt inhibition of hydrogen-evolution reaction, which is a critical barrier for operating at high charge/discharge rate for long term cycling in VFRB. Moreover, significant improvements in charge and electron transfer processes towards V3+/V2+ redox reaction is achieved using GF@TiO2:H electrodes due to the enhancement in the electron donor properties of the TiO2 after hydrogen annealing, as a consequence of oxygen vacancies formation in the lattice structure. Keys performance indicators of VFRB have been increased not only in terms of high capability rates (200 mAcm-2) but also the electrolyte-utilization ratio achieved (82%), corresponding the best value reported up to date. A specific discharge capacity of around 31 WhL-1 with a 61% of energy efficiency was observed after more than 120 cycles. Taking into account all improvements mentioned above, it is a cost-effective way to boost this technology into the market.

Authors : N. Zanfoni, P. Simon, R. Chassagnon, S. Bourgeois, V. Potin, L. Imhoff, B. Domenichini
Affiliations : Laboratoire Interdisciplinaire Carnot de Bourgogne (ICB) - UMR 6303 CNRS - Univ. Bourgogne Franche-Comté - 9 av. Alain Savary - 21078 Dijon Cedex - France

Resume : In recent years, ceria based oxides have been widely used as catalysts or as electrolyte material for fuel cells. Moreover, it has been observed that interaction between noble metal such as Pt with ceria enhances its catalytic activity by improving the reducibility of the surface. Recently, DFT calculations have predicted that atomically dispersed platinum is stabilized in specific oxidation state Pt2+ at the surface of CeO2 {100} type nanofacets. This study was made in the context of recent approach which may make possible the observation of single Pt atoms in surface nanopockets through high resolution scanning transmission electron microscopy. Pt-CeO2 thin films were obtained by direct liquid injection CVD with a synthesis approach which allows direct observations of the layers on carbon coated Cu TEM grids. This approach does not require any prior preparation of the samples, which may damage or modify their structure and chemical state. In this way, the real chemical state and morphology of the deposits are preserved and quantification of very low Pt content is possible. TEM results show that the layers are composed of very well crystallized ceria particles with a homogeneous grain size (~10 nm). However, EELS measurements have revealed that the carbon membrane is consumed during deposition, even though its morphology is conserved after deposition. Finally, a very low Pt content (~1%) is revealed with cationic Pt localized at the extreme surface of the CeO2 particles.

Authors : E.C. Serban1, A.E. Balan1, A. Cucu1, Alexandra M. I. Trefilov1, Mihaela Necula2, Sonia Mihai2, Cursaru Diana Luciana2 and Ioan STAMATIN1
Affiliations : 1University of Bucharest, Physics Department, 3 Nano-SAE Research Centre, Bucharest, Romania 2Petroleum-Gas University of Ploiesti, 39 Bucuresti Blv, 100680, Ploiesti, Romania

Resume : Currently, UFCs (Urea Fuel Cells) became a promising alternative for new energy conversion and generation. The advantages of the urea fuel cell compared to the hydrogen fuel cell are that the fuel is non-toxic, non-flammable and easy to transport without pressurization. The fuel can also be recovered from waste water. Electro-decompostion of urea in the presence of a Ni catalyst is considered an effective approach for hydrogen production. In this work, three different catalysts based on Ni metallic were synthesized, characterized and used as anodic catalyst in urea fuel cells. The physico-chemical properties of electro-catalysts were investigated by SEM, FT-IR, TGA, DSC and CV. Electrochemical measurements showed that the Ni is an alternative catalyst material for applications in waste water remediation, hydrogen production and fuel cells.

Authors : Chamorro(1), P. Boulet(1), S. Migot(1), P. Miska(1), T.S. Shyju, P. Kuppusami(2),(3), J.F. Pierson(1)
Affiliations : (1) CNRS, Institut Jean Lamour, Université de Lorraine, UMR7198, Nancy F-54011, France (2) Centre for Nanoscience and Nanotechnology, Sathyabama University, Chennai-600119,India (3) Centre of Excellence for Energy Research, Sathyabama University, Chennai-600119, India

Resume : The a II-VI semiconductor ZnS has been studied due to its unique optical properties and could be a promising candidate for p-type semiconductor materials. If the luminescence properties of Cu-doped ZnSare well known, the reports of Zn1-XCuXS films exhibiting a p-type behavior are scarce. In this work, Zn1-XCuXS thin films were synthetized by RF magnetron sputtering using ceramic ZnS and metallic Cu targets. The Cu target power was changed in order to vary the Cu content in the films while other experimental parameters remain constant. (0002)-oriented hexagonal ZnS films are obtained for all the conditions. XRD results suggest the Cu insertion in Zn atomic positions of the ZnS crystal lattice decreases the a and c lattice parameters and therefore the ZnS volume. Films with Cu contents above 6% show changes in the microstructural, optical and electronic properties of the films. Following the intensity of the (0002) ZnS diffraction peak, when decreasing the Cu content shows a striking loss in the preferential orientation growth is found also related with a loss in the ZnS crystal quality. The energy bandgap measured by optical absorption decreases with the Cu content.Moreover, an absorption in the near infrared region appears probably due to a plasmon resonance linked to an increase in the carrier concentration. The electrical measurements reveal that the films are conductive with a p-type behavior above a Cu concentration of 6%.

Authors : Sinan Akkaya (, Serdar Özbay (, Kürşat Kazmanlı (, Mustafa Ürgen (
Affiliations : Istanbul Technical University, Metallurgical and Materials Engineering Department, Istanbul/TURKEY

Resume : Ti1-xAlxN coatings with different compositions were deposited on steel and copper substrates in a cathodic arc physical vapor deposition system. To achieve the different coating compositions evaporation targets with different Ti and Al contents were used. Additional adjustments to the coating structure were realized by utilizing different modes of substrate bias, namely the DC mode, where a constant potential of -75 volts was applied to substrate, and a pulsed bias mode, where a unipolar pulse of 24 kHz and an amplitude of -1k volts was applied. After the deposition process, samples were subjected to a heat treatment in a high vacuum furnace. Samples were characterized optically, using a UV-Vis-NIR spectrophotometer both as deposited and heat treated states. Thermal emittance of the samples was measured using an emissometer. XRD measurements were also carried out to determine the changes to the structure and phase distribution induced by the heat treatment, separating TiN and AlN phases. The reflectance of the coatings in the 220-1500 nm range depends primarily on the Al/Ti ratio with higher Al content coatings showing lower reflectance. Additionally, coatings produced using pulsed high voltage bias exhibit lower reflectance values compared to the coatings deposited with DC bias and otherwise identical parameters. As a general behavior observed for all coatings, high vacuum heat treatment led to the decrease of reflectance and emissivity of the coatings. Keywords: TiAlN, Cathodic Arc, Physical Vapor Deposition, Optical Properties, Thermal Emissivity, Selective Solar Absorbers

Catalysis II (Parallel with Poster II) : Georg Madsen
Authors : S. Giusepponi and M. Celino
Affiliations : ENEA, C.R. Casaccia, Via Anguillarese 301, 00123 Rome, Italy

Resume : Magnesium hydride is a very promising material for solid-state hydrogen storage. However,some drawbacks have to be overcome to use it in real applications. The use of catalysts is a viable solution to lower the desorption temperature and increase the overall kinetics. An accurate model has been developed to study the mechanism of action of the catalyst and how it interacts with the interface MgH2 - Mg, through which H atoms diffuse. The accurate evaluation of the work of adhesion and defect energy formation, versus the distance from the interface are linked to the atomic-scale structural distortion induced by the catalyst. Moreover, molecular dynamics simulations at several temperature provide a clear description of the desorption mechanism and an estimate of the desorption temperature.

Authors : Hyunah Kim, Jimin Park, Ki Tae Nam, Kisuk Kang
Affiliations : Hyunah Kim, Ki Tae Nam, Kisuk Kang; Department of Materials Science and Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea. Jimin Park; Center for Biomaterials, Korea Institute of Science and Technology, 5, Hwarang-ro 14-gil, Seongbuk-gu, Seoul 136-791, Republic of Korea.

Resume : Nowadays global warming and energy crisis has accelerated to develop renewable energy. Splitting water into hydrogen and oxygen molecules is an environmentally-friendly solar-to-energy conversion method which could produce hydrogen energy. However, the oxygen evolution reaction has been regarded as a bottleneck in overall water splitting reaction. The noble-metal catalyst shows remarkable catalytic activity, but their high cost gives limitation for realization of overall water-splitting systems. Therefore, developing cost-effective, abundant, and efficient water splitting catalysts under neutral condition is necessary. Although extensive studies have focused on the metal-oxide catalysts, the effect of metal coordination on the catalytic ability remains still elusive. Here we select four cobalt-based phosphate catalysts with various cobalt- and phosphate-group coordination as a platform to better understand the catalytic activity of cobalt-based materials. Although they exhibit various catalytic activities and stabilities during water oxidation, Na2CoP2O7 with distorted cobalt tetrahedral geometry shows high activity under neutral conditions, along with high structural stability. First-principles calculations suggest that the surface reorganization by the pyrophosphate ligand induces a highly distorted tetrahedral geometry, where water molecules can favourably bind, resulting in a low overpotential. In conclusion, we observed the importance of local cobalt coordination in the catalysis and suggest the possible effect of polyanions on the water oxidation chemistry.

Authors : Ivan Kondov (1), Patrick Faubert (2), Holger Reinecke (2), Claas Müller (2)
Affiliations : (1) Steinbuch Centre for Computing, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany; (2) Universtiy of Freiburg, Department of Microsystems Engineering – IMTEK, Laboratory for Process Technology, Georges-Köhler-Allee 103, 79110 Freiburg, Germany

Resume : Oxygen reduction reaction (ORR) is the electrochemical cathode process in polymer electrolyte fuel cells and Li-air batteries. Important for the construction of sustainable fuel cells is to identify candidates for novel ORR catalysts that not only satisfy the requirements for catalytic activity and durability under the cell operation conditions, but are also free of precious metals and rare elements. Recent development of alkaline polymer electrolytes opens up possibilities to use Ni alloys as an alternative cathode catalyst. One possibility to increase the poor catalytic activity of pure fcc Ni is modification with small amounts of Cr. In this study, we investigate different modifications of nickel catalyst with chromium combining density functional theory with established electrochemical models, and employing atomistic structure models of different sizes derived from available characterization data. We find that catalytic activity and stability of nickel surfaces can be enhanced via doping and decoration of the active Ni surface with chromium and chromium oxides. Based on the results we discuss the factors contributing to activity enhancement and to stabilization of ORR intermediates and suggest that specific modifications may increase catalyst performance considerably. Furthermore, we suggest a design strategy for improving the catalyst performance on the device level by coupling the atomistic model to a kinetic Monte Carlo simulation and a mass/charge transport model in fuel cell.

Authors : Gareth Hartley, Natalia Martsinovich
Affiliations : University of Sheffield

Resume : Photocatalytic water splitting is potentially a very attractive route to producing hydrogen fuel using the energy of sunlight. To this end, a large number of photocatalysts are being studied, but their efficiencies remain low. Graphitic carbon nitride (g-C3N4) is in many ways an ideal photocatalyst material: its structure and electronic properties can be tuned, it is non-toxic and cheap to synthesize. However, it is inefficient due to poor light-harvesting properties and low charge mobilities. Modifications to the g-C3N4 structure could greatly improve its optical and electronic properties and therefore its water splitting efficiency. Computational materials design is essential here: many candidate structures can be screened computationally before they are made, to direct experimental efforts to the structures with desirable properties. We use calculations to predict the effect of modifying the idealised g-C3N4 structure by replacing the three-coordinated nitrogen linker atom with a range of heteroatoms (phosphorus, boron) and aromatic groups (benzene, triazine and substituted benzenes). Electronic properties of the modified carbon nitride structures are studied using density-functional theory (DFT) calculations, focussing on the valence and conduction band positions and band gap energies. Both two-dimensional (2D) sheets and three-dimensional (3D) multilayer structures are explored. Our studies suggest that 3D g-C3N4 can catalyse only the hydrogen reduction half-reaction, in line with experimental reports. However, 2D sheets of g-C3N4 have suitable valence and conduction band for splitting water. Two new structures are found with smaller band gaps and better band positions than g-C3N4 for water splitting: benzene and s-triazine linked structures. The boron-doped structure is also interesting: it has the smallest band gap and is expected to absorb red light. Therefore, it may be useful as a component for photocatalytic Z-schemes. Thus, our computational study identifies boron-doped and benzene- and triazene-containing carbon nitrides as new promising materials for experimental studies.

Authors : Jerome Canivet, Jonathan Bonnefoy, David Farrusseng, Matthew B. Chambers, Caroline Mellot-Draznieks, Marc Fontecave
Affiliations : CNRS-IRCELYON, Villeurbanne, France; CNRS-C2P2, Villeurbanne, France; Collège de France, Paris, France

Resume : Metal-Organic-Frameworks appear to be appealing platforms for immobilization of single-site organometallic catalysts. The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Through post-synthetic ligand exchange methodology, we successfully proceeded to the heterogenization of this molecular catalyst via the synthesis of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and more selective for formate. Through the study of the behaviour of MOF systems having a controlled Rh loading, competitive catalytic reaction occurring inside the Cp*Rh@UiO-67 framework are postulated. Finally, a combined computational-experimetnal methodology allowed unravelling the band-gap as a new descriptor of the chemical compostion of the hybrid material, to assess ultimately the covalent incorporation of the organometallic catalyst within the framework.

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General : Sandip Bhattacharya
Authors : Gus L. W. Hart, Lance J. Nelson, Conrad W. Rosenbrock, Fei Zhou, Vidvuds Ozolins
Affiliations : Dept. of Physics and Astronomy, Brigham Young Univ., Provo UT 84602 USA; Dept. of Physics, Brigham Young Univ. Idaho, Rexburg ID 83460 USA; Physics Division, Lawrence Livermore Natl. Lab., Livermore CA 94550; Dept of Mat. Sci. and Engineering, University of California, Los Angeles CA 90095 USA

Resume : When building physical models (truncated expansions, force-fields, etc.), one often employs the widely accepted intuition that the physics is determined by a few dominant terms. This reductionist paradigm is provides no recipe for how one develops intuition for identifying the dominant terms. A "Bayesian compressive sensing" technique provides simple, general, and computationally efficient solution to the challenge of picking out the relevant terms. Combined with the high-throughput first principles approach to materials, BCS makes it possible to automatically build models for binary alloy models without human monitoring. Furthermore, the method can automatically adjust to generate the simplest model (fewest terms) that meets a specific accuracy requirement. Beyond the alloy applications, our BCS code can readily be applied to other model building problems. One merely needs a basis representation and training data to build a model in just a few seconds.

Authors : Yanwen Zhang1*, G. Malcolm Stocks,1 Ke Jin1,2, Chenyang Lu3, Hongbin Bei1, Brian C. Sales,1 Lumin Wang3, Laurent K. Beland1, Roger E. Stoller1, German D. Samolyuk1, Magdalena Caro4, Alfredo Caro4, and William J. Weber,1,2
Affiliations : 1 Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA 2, University of Tennessee, Knoxville, TN 37996, USA 3 University of Michigan, Ann Arbor, MI 48109-2104, USA 4 Los Alamos National Laboratory, Los Alamos, NM 87545, USA

Resume : The development of metallic alloys is arguably one of the oldest sciences, dating back at least 3,000 years. Most research and applications have been focused on alloys with one principal element, to which the addition of alloying elements in low concentrations leads to various performance improvements and changes in radiation resistance. In sharp contrast to traditional alloys, recent success in the synthesis of single-phase concentrated solid solution alloys (SP–CSAs) has opened up new frontiers in materials research. In these alloys, a random arrangement of multiple elemental species on a regular lattice (fcc or bcc) results in unique site-to-site lattice distortions and local disordered chemical environments. Intense radiation in nuclear fission and fusion energy power systems, nuclear waste forms, high-energy accelerators and space exploration transfers energy to the electrons and atoms that make up the material, and thereby produces defects that ultimately compromise material strength and lifetime. A grand challenge in materials research is to understand complex electronic correlations and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Since SP–CSAs possess unique links between intrinsic material properties (can be altered by alloy complexity), energy dissipation and various defect dynamic processes; they are ideal systems to fill knowledge gaps between electronic-/atomic-level interactions and radiation resistance mechanisms. In our work, we show that chemical disorder and compositional complexity in SP–CSAs have an enormous impact on defect dynamics through substantial modification of energy dissipation pathways. Based on a closely integrated computational and experimental study using a novel set of Ni-based SP-CSAs, we have explicitly demonstrated that increasing chemical disorder can lead to a substantial reduction in the electron mean free path and electrical and thermal conductivity. These reductions have a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Considerable enhancement in radiation resistance with increasing chemical complexity from pure nickel to binary, and to more complex quaternary solid solutions, is observed under ion irradiation. Contrary to conventional alloys with low solute concentration but multiple phases, energy dissipation and defect evolution at the level of electrons and atoms in SP–CSA systems with extreme compositional disorder is an unexplored frontier in materials science. The integrated experimental/modeling effort provides new insights into defect dynamics at the level of atoms and electrons, and an innovative path forward towards solving a long-standing challenge in structural materials. Understanding how material properties can be tailored by alloy complexity and their influence on defect dynamics may pave the way for new design principles of radiation–tolerant structural alloys for advanced energy systems, as well as for new defect engineering paradigms benefiting broader science and technology. Work supported by the Energy Dissipation to Defect Evolution Center (EDDE), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science.

Authors : Christopher Tholander, Agnė Žukauskaitė, Ferenc Tasnádi, Jens Birch, Igor Abrikosov, Lars Hultman, Björn Alling
Affiliations : Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden;Fraunhofer Institute for Applied Solid State Physics, Tullastr. 72, 79108 Freiburg, Germany, Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden;Theoretical Physics, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden;Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden; Theoretical Physics, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden;Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden;Thin Film Physics Division, Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden, Max-Plank-Institute für Eisenforschung GmbH, Max-Plank-Strasse 1, 40237 Düsseldorf, Germany;

Resume : Physical vapor deposition, such as reactive magnetron sputtering, allows for synthesis of metastable alloys, inaccessible through growth methods operating close to thermodynamic equilibrium. Thus, a huge chemical space is opened for property optimization. Sc0.5Al0.5N is an example of such an alloy, where the piezoelectric response is increased by more than 400% in comparison to AlN. This makes ScAlN an excellent candidate for use in micromechanical systems which are key components in modern electronic devices, such as radio frequency signal processing. Using an approach of theoretical prediction and experimental verification, we study the mechanisms behind phase formation and the piezoelectric increase in metastable nitrides. We show that the effect of high piezoelectric constants is general for the III-A nitrides (AlN, GaN, InN) alloyed with III-B nitrides (ScN, YN) [1,2]. Based on our determined criteria, we scan the periodic table for quaternary AlN-based alloys and map out new possible candidates suitable for metastable piezoelectric thin films, in particular, Tix/2Mgx/2Al1-xN, Zrx/2Mgx/2Al1-xN, and Hfx/2Mgx/2Al1-xN, and establish the energy difference EB3-EBk as a descriptor that can be used to find additional piezoelectric alloys in high-throughput studies [3]. [1] C. Tholander, I.A. Abrikosov, L. Hultman, and F. Tasnádi, Phys. Rev. B 87, 094107 (2013). [2] C. Tholander, J. Birch, F. Tasnádi, L. Hultman, J. Palisaitis, P.O.Å. Persson, J. Jensen, P. Sandström, B. Alling, and A. Zukauskaite, Acta Mater. 105, 199 (2016). [3] C. Tholander, F. Tasnádi, I.A. Abrikosov, L. Hultman, J. Birch, and B. Alling, Phys. Rev. B 92, 174119 (2015).

Authors : Mikael Kuisma, Angelica Lundin, Kasper Moth-Poulsen, Per Hyldgaard, Paul Erhart
Affiliations : Department of Chalmers University of Technology, Gothenburg, Sweden; Department of Chemistry and Chemical Engineering, Gothenburg, Sweden; Department of Chemistry and Chemical Engineering, Gothenburg, Sweden; Department of Microtechnology and Nanoscience, Chalmers University of Technology, Gothenburg, Sweden; Department of Chalmers University of Technology, Gothenburg, Sweden

Resume : Molecular photoswitches capable of storing solar energy are interesting candidates for future renewable energy applications. In this context, substituted norbornadiene-quadricyclane systems have received renewed interest thanks to recent advances in their synthesis. Their properties can be tailored by introduction of functional side groups resulting in a very large number of potential compounds. Since this parameters space is practically impossible to navigate exclusively experimentally, we have followed a computational design approach to identify candidate compounds and delineate optimal design strategies. Specifically, using quantum mechanical calculations we carried out a systematic screening of critical optical (solar spectrum match) and thermal (storage energy density) properties of a matrix of more than 70 compounds and more than 800 structures. The substituents were chosen to be synthetically accessible thus providing realistic candidates for future experimental realization. It is shown that it is possible to design molecules that can reach the theoretical maximal solar power conversion efficiency. This, however, requires a strong red-shift of the absorption spectrum, which causes detrimental absorption by the higher-lying photo-isomer (quadricyclane) as well as a significantly reduced thermal stability. In addition, the respective compounds are typically based on two substituents and have a correspondingly large molecular mass, leading to storage densities below 400 kJ/kg. By contrast, single-substituted systems achieve a good compromise between efficiency and storage density reaching values in excess of 600 kJ/kg for the latter, while avoiding competing absorption by the photo-isomer. Based on these results we identified promising candidates along with general guiding principles for the future development of molecular solar thermal storage systems.

10:00 Coffee break    
Authors : Dr. Anne F. de Baas
Affiliations : European Commission

Resume : The talks will present 1) EU Policy activities, 2) EU Calls and 3) EU projects with materials modelling with application in the energy area. The EC has as objective to achieve Materials by Design as part of the Industry2020 visions. To develop this policy, the European Materials Modelling Council, has been founded which is uniting all stakeholders. The EMMC generates every two years a Road Map endorsed by manufacturers, software owners, translators and modellers as input to the EU H202 LEIT NMBP programmes and this process and how to participate will be presented. This wide stakeholder organisation also develops standards for vocabulary, model classification, workflow presentations and metadata and it will be explained how to participate to the development thereof. A specific area dedicated to materials modelling is now part of H2020.The principal aim of the WP 2014-2015 part was to stimulate the use of existing materials modelling software by the European manufacturing industry. The EC LEIT NMBP WP 2015 included a call for Business Decision Support Systems based on materials modelling and the background and results will be presented (if public by then). Calls based on WP 2016 and 2017 will include a networking topic and a Modelling Market Place topic. FP7 and ongoing H20202 projects dealing with the topics of the session will be presented Applications of these modelling activities will cover the energy domain (battery materials, photo-voltaic materials, thermoelectric materials, fuel cell materials and power electronics).

Authors : Dr Michael Parkes, Prof. Nicholas M Harrison
Affiliations : Department of Chemistry, Imperial College London, London SW7 2AZ, UK

Resume : It is at the anode triple phase boundary between Ni, YSZ and fuel molecules that the reactions on which the efficiency and ageing of the fuel cell depend. Despite a significant body of research, the structure of the YSZ electrolyte surface has not been characterized at an atomic level and so the nature of the surface reaction sites is not known. In this study a systematic approach to the defect thermodynamics of YSZ is used to establish both the atomistic geometry of the Y and Ovac sites and an heuristic that facilitates the prediction of low energy structructues in more complex environments such as the surface and the TPB. This is used to construct an initial model of the interface between YSZ and the reactive gasses and to speculate about the nature of the reaction sites active in the oxygen reduction reaction and the carbon contamination reaction.

Authors : Ragnar Strandbakke(1), Einar Vøllestad(1), David Wragg(3), Sabrina Sartori(2), Raphael Prato(1), Jose M. Serra (4), Cecilia Solis (4), Truls Norby(1)
Affiliations : 1: Department of Chemistry, University of Oslo, FERMiO, Gaustadalléen 21, NO-0349 Oslo, Norway. 2: Department of Physics, University of Oslo, FERMiO, Gaustadalléen 21, NO-0316 Oslo, Norway. 3: Department of Chemistry, University of Oslo, P.O. Box 1033, 0315 Oslo, Norway. 4: Instituto de Tecnolog´ıa Qu´ımica, Avenida de los Naranjos s/n, 46022 Valencia, Spain

Resume : The double perovskite BaGd0.8La0.2Co2O6-δ (BGLC) shows excellent performance as oxygen electrode for Proton Ceramic Fuel Cells (PCFCs) and electrolyzer cells (PCEC), with polarization resistances in wet oxygen of 0.04 and 10 Ωcm2 at 650 and 350 ⁰C, respectively [1]. Compared with other reported PCFC cathodes [2], BGLC performs better both at high and low temperature. The high performance of BGLC is rationalized by a suggested partial proton conductivity at intermediate temperatures, and significant hydration is shown by thermogravimetry up to 400 ⁰C. To lower the A-site basicity and increase the chemical stability of BGLC in steam under PCEC operation, we substitute some La for Ba and a stable composition at 1.5 bar steam is reached with 50 % substitution of Ba. We investigate polarization resistance on symmetrical button cells, conductivity, and hydration vs x in Ba1 xGd0.8La0.2+xCo2O6-δ, with x = 0-0.5. Structural properties vs temperature and x in dry and hydrated samples are investigated by use of synchrotron and neutron powder diffraction and high temperature XRD. DC conductivity of BGLC vs x and temperature reaches a maximum of 1600 Scm 1. References [1] R. Strandbakke, V.A. Cherepanov, A.Y. Zuev, D.S. Tsvetkov, C. Argirusis, G. Sourkouni, S. Prünte, T. Norby, Solid State Ionics 278 (2015) 120. [2] J. Dailly, S. Fourcade, A. Largeteau, F. Mauvy, J.C. Grenier, M. Marrony, Electrochimica Acta 55 (2010) (20) 5847.

Authors : K. Uchiyama1, T. Kariya2,3, T. Sato1, M. Yamaguchi1, T. Inoue1, T. Kumagai1, H. Tanaka2, T. Hirono3, T. Kuse3, K. Yanagimoto3, H. Funakubo2
Affiliations : 1.National Institute of Technology, Tsuruoka College, 2. Department of Innovative and Engineered Materials, Tokyo Institute of Technology, 3. Research and Development Center, Sanyo Special Steel Co., Ltd.,

Resume : A Solid Oxide Fuel Cell (SOFC) is considered to be one of the electricity generation systems because of its high efficiency and fewer environmental loads during its operations. However, the present SOFC requires high operating temperatures of 800-1000 °C, which results in higher device cost. Therefore lowering the operating temperatures below 600 °C is indispensable to enhance the SOFC application fields. In the conventional SOFC, oxygen-ionic-conductor is used as an electrolyte; however, it needs high operating temperatures over 1000 °C to obtain sufficient ionic conductivity. Therefore, we have proposed a new SOFC structure with a proton-conductive oxide thin films de-posited on a Pt-plated porous stainless-steel (PSS) substrate as an electrolyte. The proton conductors show high conductivity at 400-600 °C. In this study, we will report the high quality deposition of these perovskites, such as Y-doped BaCeO3(BCYO) and SrZrO3(SZYO), and their application to SOFCs.

Authors : S. I. Simak
Affiliations : Materials Modelling Laboratory, IFM, Linköping University, Sweden

Resume : Ceria is an important material in many environmentally benign applications. In particular, it is a promising electrolyte in intermediate temperature solid oxide fuel cells (IT-SOFC). The characteristic high oxygen mobility is crucial to such applications. The optimization of this mobility has attracted many studies. Attempts at improving the ionic conductivity usually revolve around choosing the correct kind and concentration of dopants. We have approached the problem from a different direction: how does the conductivity depend on the lattice parameter? To justify this approach one can consider that most external parameters carry with them a volume change. The effect of volume change on the ionic conductivity in ceria has been studied in the framework of the density functional theory. We show that properly controlling external conditions one can treat the lattice constant of ceria as an adjustable parameter and change the topology of the energy landscape for the oxygen ion transport. We reveal the existence of a narrow range of lattice parameters, which lead to such a topology that the ionic conductivity in ceria is essentially enhanced. The tuning of the lattice parameter is possible via proper external conditions, such as oxygen pressure, concentartion of dopants and the choice of a substrate. This finding opens avenues for the future design of fast ionic conductors.

12:00 Lunch break    
TCO and PV : Wolfram Jaegermann
Authors : Geoffroy Hautier
Affiliations : Université catholique de Louvain

Resume : High-throughput computing has been emerging as a very powerful way to search for new materials. By building databases of thousands of computed materials properties, one can search for the few compounds with the exceptional properties for a given application. I will illustrate how this approach can be used to search for materials with specific opto-electronic properties (transparency, carrier mobility, conductivity) targeting two important applications: transparent conducting oxides and thermoelectric materials. I will especially focus on recent computational findings confirmed experimentally and stress the opportunities and challenges in computationally-driven materials design. In the last part of my talk, I will present how the data generated through high-throughput computing can be widely spread and introduce the Materials Project: a large publicly available database of computed materials properties (

Authors : Alireza Faghaninia, Michael T. Sullivan, Derreko I. Becker-Ricketts, Cynthia S. Lo
Affiliations : Department of Energy, Environmental & Chemical Engineering, Washington University in St. Louis

Resume : Accurate ab initio electronic transport models can facilitate high throughput calculations and screening of semiconductor materials for energy applications. Previous attempts at screening new transparent conducting oxide (TCO) materials have focused on their average effective mass, due to the simplicity and speed of such calculations. This calculation is often simplified by being based solely on the shape of the band extrema. Although the approximate effective mass certainly gives a valuable prediction of material performance, it lacks sufficient complexity for accurate calculation of electronic properties, especially in degenerate semiconductors. In particular, electron-phonon interactions, which limit the mobility, particularly at room temperature, are ignored. Here we employ an ab initio transport Model in the Boltzmann Transport (aMoBT) framework, which accurately predicts the electrical mobility and conductivity of both n-type and p-type semiconductors. We screen more than 70 promising TCOs that were pre-screened using the average effective mass, and rank them based on their conductivity, as limited by ionized impurity scattering and electron-phonon scattering mechanisms. We now report the most promising candidates from each of the n- and p-type semiconductors, and assert the utility of aMoBT, as incorporated into an automated atomistic calculation framework, in designing new materials for solar cell applications.

Authors : M. Vila, G. Mallia, N. M. Harrison
Affiliations : M. Vila (Imperial College London); G. Mallia (Imperial College London); N. M. Harrison (Imperial College London)

Resume : Investigation of materials by computer simulation has become a powerful tool over the last decades as a means to understand and predict the behaviour of matter. Recently, NiO has been used as a promising hole transport layer in organic photovoltaics. Understanding the formation of excitons is therefore of fundamental and technological interest. Nevertheless, a predictive theory of excitonic states remains elusive due to the difficulties inherent in modelling the strong electronic correlations. Here, Hartree Fock, DFT, hybrd-exchange and TDDFT calculation are employed – as implemented in the CRYSTAL code – to study the ground and the excited states of the strongly correlated NiO. Specially interest will be focused on the evaluation of the energy levels of excitons as well as their localization in the lattice and the induced polarisation of the electron density.

Authors : Masoomeh Ghasemi, Suzana G. Fries, Martin Stankovski, Jonas Johansson
Affiliations : 1. Solid State Physics, Lund University, Box 118, SE-22100 Lund, Sweden; 2. ICAMS, Interdisciplinary Centre for Advanced Materials Simulation, Ruhr-Universität Bochum Universitätsstraße 150 44801 Bochum, Germany; 3. LU Open, Lund University, Box 117, SE-22100 Lund, Sweden; 4. Solid State Physics, Lund University, Lund, Sweden

Resume : III-IV semiconductor nanowires are promising building blocks of future electronic and optoelectronic devices. The nanowires are often doped with foreign impurity atoms to tune their electronic properties. In addition to this, native defects such as vacancies, interstitials and anti-sites may also form unintentionally. Moreover, during the growth of Au-seeded nanowires, Au impurities may also incorporate in the semiconductor. The aim of the current project is to study the energetics and concentrations of variety of native defects and foreign impurity atoms in the GaAs nanowires. We are calculating the formation energy of different point defects in GaAs including the Zn dopant, Au impurities and vacancies in different charged states through Density Functional Theory (DFT) calculations. Then, based on the relative stability of the defects, we will set up a thermodynamic model for the GaAs compound using a methodology which combines phase diagram and thermochemical experimental and first-principles information, so called CALPHAD method [1]. As a result of the current study, the existing thermodynamic model of the GaAs phase which does not take the impurity and native defect concentrations into account will be optimized. This model can eventually be used for modelling the growth of Zn-doped and Au-seeded GaAs nanowires [2]. [1] H.L. Lukas et. al., Computational thermodynamics: The Calphad method. Cambridge University Press 2007. [2] Yang et. al., J. Cryst. Growth, 414 (2015), 181.

Authors : Alexandra Szemjonov 1, Frédéric Labat 1, Ilaria Ciofini 1, Sandrine Ithurria 2, Silvia Pedetti 2, Nicolas Lequeux 2, Benoit Dubertret 2, Thierry Pauporté 1
Affiliations : 1 Chimie ParisTech, PSL Research University, CNRS, Institut de Recherche de Chimie Paris (IRCP), 11 Rue Pierre et Marie Curie, F-75005 Paris, France; 2 Laboratoire de Physique et d’Etude des Matériaux, UMR 8213 du CNRS, ESPCI, 10 rue Vauquelin, 75231 Paris, France

Resume : A deep understanding of structure-property links is essential for the design of quantum dot solar cells (QDSCs), where interfacial recombination is a major source of current loss. However, the accurate characterization of semiconductor interfaces is so far challenging both from the experimental and theoretical point of view, especially in case of lattice-mismatched compounds. In this study, we combine theoretical and experimental methods to address this challenge. As an interesting alternative to spherical QDs, quasi 2D CdSe nanoplatelets (NPLs) of different thicknesses were linked to ZnO nanorods by SH- ligands. These systems were characterized by SEM, Raman and UV-VIS spectroscopy. The results confirm the presence of NPLs on the substrate, and suggest significant structural changes upon the interface formation between them. The latter was confirmed by a theoretical analysis using a highly efficient periodic density functional theory-based computational method. We also calculated the vibrational and electronic properties of this system, and the electron injection efficiency from the NPL towards the ZnO surface. This charge injection, in line with the working principle of QDSCs, turned out to be favored, but only partial. The proposed combined experimental/theoretical approach should be applicable for other lattice-mismatched semiconductor heterostructures in a wide range of optoelectronic devices to help rationalize their operating principles and thus design new systems.

15:30 Coffee break    
Authors : Fadwa El Mellouhi1, El Tayeb Bentria1, Asma Marzouk1, Akinlolu Akande2, Sergey Rashkeev1, Mohamed El-Amine Madjet1, Golib Berdiyorov1, Carlo Motta3, Stefano Sanvito3 Sabre Kais1 and Fahhad Alharbi1
Affiliations : 1Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University Qatar Foundation, Doha, Qatar 2School of Science,Institute of Technology, Sligo, Ireland 3School of Physics and CRANN, Trinity College Dublin, Ireland

Resume : In the past four years, the solar cell field has experienced an unprecedented meteoritic emergence of a new family of solar cell technologies; namely, perovskites solar cells (PSC) using (CH3NH3)PbI3 as absorber. [1] However, two main challenges prevent deploying PSC technology: the presence of the toxic element lead (Pb) and their structural instability. I will discuss our design strategy to increase the efficiency of hybrid halide perovskites which consists of understanding[2] designing then screening alternative stable, nontoxic, lead-free materials. Our efforts to design lead free family of hybrid materials demonstrate that hybrid materials containing organic cations might require careful considerations among them the size of the cell used during the screening process. Our strategy will be presented as well as some resulting promising compounds. Acknowledgement: Computational resources are provided by research computing at Texas A&M University at Qatar and the Swiss Super Computing Center(CSCS). This work is supported by the Qatar National Research Fund (QNRF) through the National Priorities Research Program (NPRP 8-090-2-047) References: [1] M. Peplow, “The perovskite revolution [news],” Spectrum, IEEE, vol. 51, no. 7, pp. 16–17, 2014. [2] C. Motta, F. El Mellouhi, S. Kais, N. Tabet, F. Alharbi, and S. Sanvito, Revealing the role of organic cations in hybrid halide perovskites CH3NH3PbI3, Nature Communications 6, Article number:7026 (2015) (doi:10.1038/ncomms8026)

Authors : David A. Keller, Koushik Majhi, Kevin J. Rietwyk, Adam Ginsburg, Hannah-Noa Barad, Zhi Yan, Yaniv Bouhadana, Eli Rosh-Hodesh, Assaf Y. Anderson, Arie Zaban
Affiliations : Bar Ilan University, Ramat Gan, Israel

Resume : A promising family of photovoltaic solar cells, based solely on metal oxide thin films, has recently been gaining interest. To improve the inadequate electrical properties of the pure metal oxide materials, various metal oxides are mixed, to create new composite materials that may exhibit enhanced properties. The new materials are then examined as light absorbing layers in photovoltaic cells, stacked between other metal oxide layers in multi-layered structure. The structure is consisting of different metal oxide layers: transparent conductive layer, electron transport layer, absorber layer and hole transport layer. Because of the multi-layered structure, it is difficult to resolve the operating mechanism of these solar cells. To meet this need, a home-built high-throughput incident photon to current efficiency (IPCE) measuring system was constructed. Using the new system and other high-throughput optical, electrical and structural scanning systems, we thoroughly studied the operating mechanisms of several all-oxide samples, including composite materials of Fe2O3, Co3O4, Bi2O3, TiO2 and others. In many of the cells we found evidence for two distinct processes with different operating mechanisms. The two mechanisms may work in parallel, compete, or even counter each other. As for their origin, the two mechanisms may result from photovoltaic activity of two different layers, or alternatively from activity of two separate bandgaps within the same material. Once the different mechanisms are understood, it is possible to enhance or to suppress one of them. This will allow for further improvement of the all-oxide cells’ photovoltaic performance.

Authors : Antonio Capretti, Arnon Lesage, Wim Sinke and Tom Gregorkiewicz
Affiliations : Van der Waals-Zeeman Institute, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands; Van der Waals-Zeeman Institute, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands; ECN Solar Energy, Petten, The Netherlands; Van der Waals-Zeeman Institute, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands;

Resume : In all practical photovoltaic cells, a major source of power conversion losses is the thermalization of carriers produced by the absorption of ultraviolet / blue light. The energy of photons in excess of the bandgap produces heat instead of electrical power. Artificial nanoscale materials, also known as metamaterials, are a potential platform to tackle this loss, because they can combine high spectral selectivity and quantum-confinement effects. Here we design and fabricate a metamaterial which can be incorporated on a traditional solar cell as an ‘add-on’ down-converter for solar radiation. This metamaterial provides absorption of photons from blue to ultraviolet, and emission via red / near-infrared photoluminescence. The light emission centers are Si nanocrystals, which are capable of efficient photoluminescence due to quantum confinement and enhancement through carrier multiplication processes. The metamaterial is obtained by combining semiconductor and dielectric nanostructures based on silicon, supporting electromagnetic resonances. We experimentally observe that the metamaterial photoluminescence is considerably boosted (> 200% time) by the enhancement of the Si-NCs absorption cross-section. Moreover, we investigate the opportunity to increase the emission rate and the probability of carrier multiplication. These results will facilitate the full control of optical transitions in an all-Si active metamaterial for energy applications.

Authors : Rakibul Islam, Roch Chan-Yu-King, Anthony N.Papathanassiou, Corinne Binet, Carole Gors, Jean-François Brun and Frederick Roussel
Affiliations : University of Lille- Sciences and Technologies, Unité Matériaux et Transformations(UMET) –UMR CNRS 8207, UFR de Physique, Bat P5, 59655 Villeneuve d’Ascq, France; University of Science and Arts of Oklahoma, Chickasha, OK 73018, USA; University of Athens, Physics Department, Solid State Physics section, Panepistimiopolis, GR15784 Zogarfos, Athens, Greece; University of Lille- Sciences and Technologies, Unité Matériaux et Transformations(UMET) –UMR CNRS 8207, UFR de Physique, Bat P5, 59655 Villeneuve d’Ascq, France; University of Lille- Sciences and Technologies, Unité Matériaux et Transformations(UMET) –UMR CNRS 8207, UFR de Physique, Bat P5, 59655 Villeneuve d’Ascq, France; University of Lille- Sciences and Technologies, Unité Matériaux et Transformations(UMET) –UMR CNRS 8207, UFR de Physique, Bat P5, 59655 Villeneuve d’Ascq, France; University of Lille- Sciences and Technologies, Unité Matériaux et Transformations(UMET) –UMR CNRS 8207, UFR de Physique, Bat P5, 59655 Villeneuve d’Ascq, France

Resume : We report an evidence of interfacial charge trapping mechanism in chemically synthesized polyaniline (PANI)/reduced graphene oxide (RGO) nanocomposites. The relative imaginary permittivity of the nanocomposites is carried out through broadband dielectric spectroscopy. Dielectric analyses indicate that the direct current (dc) conductivity (σ) decreases with increased RGO fraction and a Debye-like relaxation process which is analyzed within the framework of the Kohlrausch-William-Watts (KWW) model is observed at a frequency of ca. 5 kHz with increased RGO fraction in the nanocomposites. This relaxation can be explained by an electrical charge trapping mechanism which takes place at PANI/RGO interfaces. In addition, the dielectric relaxation dynamics and dc conductivity of the nanocomposites are studied as a function of temperature. The dielectric relaxation processes are interpreted according to Sillars approach and the results are consistent with the presence of conducting prolate spheroids (RGO) embedded into polymeric matrix (PANI). FE-SEM and TEM images confirm the multilayered nanostructural features of the composite and the numerous interactions between the RGO platelets and PANI aromatic rings through π-π stackings are evidenced by Raman spectroscopy and WAXRD studies. Such nanocomposite materials exhibiting charge trapping capabilities may find promising applications in supercapacitor or gate memory devices.

Authors : F.Alnjiman, S. Diliberto, P.Miska, J.F. Pierson
Affiliations : Institut Jean Lamour, Université de Lorraine, UMR CNR 7198, Nancy, France

Resume : AlxGayIn1-x-yN III-nitrides semiconductor alloys have been widely studied for optoelectronic applications. Those alloys are interesting for solar cells absorbing layers. Nevertheless, the indium alloys suffer from the possible lack of indium in a close future. In this context, other alloys such as nitrides II and IV of the Zn-IV-N2 type have recently been proposed in which the IV element can be Sn, Ge or Si. These materials would present similar or superior properties while composed of abundant (then cheap) and non-toxic elements. Studies on ZnSnN2 are scarcer and the properties of this material are not well known. This work presents the development of ZnSnN2 thin films by reactive co-sputtering using zinc and tin metallic targets. The stoichiometry of the films was controlled by optimizing operating parameters such asthe target voltage, the nitrogen partial pressure or the total pressure.By modifying the growth parameters, we are able to obtain crystalline films.Advanced characterization techniques such as Mössbauer spectroscopy are used to get information about the chemical environment of tin.No contribution of metallic tin is observed. Fourier transform infrared spectroscopy and Raman spectrometry also reveal ZnSnN2 vibration modes. The opticalband gap has been deduced from UV-Visible spectroscopy measurements. Reference: [1] P. C. Quayle, J. He, J. Shan and K. Kash, MRS Communications, 3(03), 135-138 (2013).

Authors : Mariam Barawi*, Roberto Giannuzzi, Giulia Veramonti and Michele Manca.
Affiliations : Istituto Italiano di Tecnologia - Center for Biomolecular Nanotechnologies, via Barsanti snc, 73010, Arnesano (Lecce), Italy

Resume : Nowadays the idea to accomplish efficiencies buildings in which would possible combine green energy resources and efficiencies walls and windows to save the consumption is growing interest by scientific community. Photovoltachromic devices integrate photovoltaic and electrochromic functionalities allowing both their separate or conjugate use1. The recent development in the field of doped oxide nanocrystals may allow to develop a new class of transparent devices able to shield the infrared heat load carried by sunlight. Their optical features may be finely tuned by changing the nature of the nanomaterials engaged in the dynamic shift of the plasmonic scattering with specific parts of the solar spectrum. In this work, high-quality mesoporous electrodes based on Nb doped TiO2 nanocrystals made by colloidal synthesis2 has been studied and used to fabricated smart windows devices. This material present the possibility to be used in self-powered “plasmochromic” devices which are simultaneously capable of generating electric energy as a photovoltaic system, as well as controlling the energy fluxes by means of a smart variation of their optical transmittance. The effect of electrochemical charging on the optical features of the Nb doped TiO2-NCs mesoporous films has been systematically investigated by making them to work as anodes in a set of lab-scale EC cells filled with three different batches of electrolytes, respectively based on lithium iodide and 2-dimethyl-3-propylimidazolium iodide in propylencarbonate. Several devices has been fabricated and preliminary results shows a modulation of the NIR of around 90% and on the solar transmittance greater than 30%, accompanied with negligible reduction of the luminous transmittance, has been demonstrated in an optimized device. 1. Granqvist, C. G. Electrochromics for smart windows: Oxide-based thin films and devices. Thin Solid Films 564, 1–38 (2014). 2. De Trizio, L. et al. Nb-Doped Colloidal TiO2 Nanocrystals with Tunable Infrared Absorption. Chem. Mater. 25, 3383–3390 (2013).


No abstract for this day

Symposium organizers
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