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MATERIALS FOR ENERGY

B

Battery and energy storage devices

For sustainable economic growth and environment protection, energy generated from renewable sources has to be converted and stored by highly efficient and ecofriendly ways. Rechargeable batteries and supercapacitors are in the center of interest all over the world for the development of electrochemical energy storage system from the macroscale to the microscale.

Scope:

Electrochemical energy storage is a rapidly advancing field building on a continuous stream of innovative ideas. As renewable energy sources become increasingly prevalent the need for high energy-density, high- power storage devices with long cycle lives is greater than ever. The development of suitable materials for these devices begins with a complete understanding of the complex processes that govern energy storage and conversion spanning many orders of magnitude in length and time scales. The focus of this meeting is to bring together all aspects of batteries and electrochemical storage devices across multiple scales, from modelling and nanoscale characterization to full-scale battery construction and testing regimes. An interdisciplinary selection of speakers will cover this broad range of topics to develop an overview of the current research and challenges in the battery field. The intention is to bring together the international community working on the subjects and to enable effective interactions between research and engineering communities.  Although a Europe-bound event, participation is invited from all continents. It provides an excellent opportunity for scientists, engineers and manufactures to present recent technical progress and products, to establish new contacts in the appreciated networking events and to exchange scientific and technical information. The symposium is structured in nine different sections covering diagnostic techniques and systems design/components.

Hot topics to be covered by the symposium:

  • Lithium ion cells
  • Non lithium technologies
  • Flow-batteries
  • Supercapacitors
  • Battery systems
  • Automotive and mobile applications
  • Stationary battery system
  • Integrated systems
  • LCA electrochemical storage
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B1 : KUPECKI JAKUB
09:00
Authors : Jijeesh Ravi Nair, Martin Winter
Affiliations : Helmholtz Institute Münster, IEK-12, Forschungszentrum Jülich GmbH, Corrensstr. 46, 48149 Münster, Germany

Resume : Solid polymer electrolytes (SPEs) are introduced as a safe alternative to existing and widely used organic carbonate-based liquid electrolytes. In the field of lithium-ion battery (LiB), the liquid-state to solid-state transformation is expected to enhance safety, fast and reliable fabrication, and thermal stability. However, several constraints have restricted their entry into the production line such as low ionic conductivity, low cation transport properties and stringent processing conditions (use of organic solvents). Thus, the researchers have proposed several approaches including the in situ polymerization technique, which can be performed in a solvent-free environment. The thermally induced crosslinking process is a rapid and a hassle-free technique. Ionic conductivity can be fine-tuned by reducing the crystallinity, which in turn increases the amorphous character of the polymer matrix. Indeed, lithium ion conduction is directly linked to polymer chain mobility and increased amorphous nature can facilitate the ambient temperature ionic conductivity. Thus, SPE is produced using a thermally induced polymerisation process, which ensures the production of a thin, transparent and flexible membrane. The resulted membrane exhibits oxidation stability above 4.5V vs. Li/Li+, thermal stability above 150°C and cycles against LiFePO4 based cathodes in lithium metal cells for several hundreds of cycles. Thus, crosslinking is a fast and reliable option for the development of industrially up scalable polymer electrolytes for lithium metal batteries.

B.1.1
09:30
Authors : 1. Syed Kamran Sami 2. Saqib Siddiqui
Affiliations : 1. Department of Chemical Engineering Balochistan University of Information Technology, Engineering, and Management Sciences (BUITEMS) Quetta 87300, Pakistan 2. Department of Textile Engineering Balochistan University of Information Technology, Engineering, and Management Sciences (BUITEMS) Quetta 87300, Pakistan

Resume : In recent times flexible supercapacitors retaining high electrochemical performance and steadiness along with mechanical endurance has developed as a spring of attraction due to the exponential progress and innovations in energy storage devices. To meet the rampant increasing demand of energy storage device with small form factor, a unique, low cost and high performance supercapacitor with considerably higher capacitance and mechanical robustness is required to recognize their real life applications. Here in this reports, synthesis route of an electrode materials with low rigidity and high charge storage performance is reported using 1D-1D Hybrid structure of zinc oxide(ZnO) nanorods and conductive polymer smeared polyvinylidene fluoride–trifluoroethylene (P(VDF–TrFE)) electrospun nanofibers. The ZnO nanorods were uniformly grown on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) coated P(VDF-TrFE) nanofibers using hydrothermal growth to manufacture light weight, permeable electrodes for supercapacitor. The PEDOT: PSS coated P(VDF-TrFE) porous web of nanofibers act as framework with high surface area. The incorporation of ZnO nanorods further boost the specific capacitance by 59%. The symmetric device using the fabricated1D-1D hybrid electrodes reveals fairly high areal capacitance of 1.22mF/cm2 at a current density of 0.1 mA/cm2 with a power density of more than 1600 W/Kg. Moreover, the fabricated electrodes show exceptional flexibility and high endurance with 90% and 76% specific capacitance retention after 1000 and 5000 cycles respectively signifying the astonishing mechanical durability and long term stability. All the properties exhibited by the fabricated electrode make it convenient for making flexible energy storage devices with low form factor.

B.1.2
09:45
Authors : G. Hautier1, D. Di Stefano1, A. Miglio1, K. Robeyns1, Y. Filinchuk1, M. Lechartier2, A. Senyshyn3, H. Ishida4, S. Spannenberger5, D. Prutsch,6 S. Lunghammer,6 D. Rettenwander,6 M. Wilkening,6 B. Roling5, Y. Kato2
Affiliations : 1)Institute of Condensed Matter and Nanosciences (IMCN), Université catholique de Louvain, Chemin des étoiles 8, 1348 Louvain-la-Neuve, Belgium; 2)Battery AT, Advanced Technology 1, Toyota Motor Europe NV/SA, Hoge Wei 33A 1930 Zaventem, Belgium; 3)Heinz Maier-Leibnitz Zentrum, Technische Universität München, 85748 Garching, Germany; 4)Toray Research Center, Inc., 3-3-7 Sonoyama, Otsu, Shiga 520-8567, Japan; 5) Department of Chemistry, Philipps-Universität Marburg, 35032 Marburg, Germany; 6) Institute for Chemistry and Technology of Materials, Graz University of Technology, Stremayrgasse 9, A-8010 Graz, Austria

Resume : Solid-state materials with extremely high ionic diffusion are necessary to many technologies including all-solid-state Li-ion batteries. Despite the strong efforts made towards the search for crystal structures leading high lithium diffusion, very limited number of compounds showing superionic diffusion are known and clear materials design principles are greatly sought for. In this work, we demonstrate that LiTi2(PS4)3 exhibits the largest Li-ion diffusion coefficient ever measured in a solid. We use extensive characterisation (neutron, X-ray diffraction, impedance and NMR) as well as theoretical studies and rationalise the exceptional performances of this new superionic conductor through the concept of frustrated energy landscape. The absence of regular and undistorted lithium site to occupy leads to low energy barrier for diffusion as well as an exceptional pre-factor. Our work not only shines light on a new family of superionic conductors but offers a an avenue to discover new ones.

B.1.3
10:00
Authors : Vincenzo Baglio*, Cinthia Alegre, Concetta Busacca, Orazio Di Blasi, Esterina Modica, Vincenzo Antonucci, Antonino Salvatore Aricò, Alessandra Di Blasi
Affiliations : Istituto di Tecnologie Avanzate per l’Energia "Nicola Giordano" (CNR-ITAE), Messina (Italy)

Resume : High specific energy, low cost and the abundance and environmental friendliness of the metals employed are the main attractions of aqueous rechargeable metal-air batteries, such as Fe-air and Zn-air. However, the cycle life and power density of these metal-air batteries are limited by the performance of the bifunctional air electrode, which is responsible for the oxygen reduction reaction (taking place during the discharge of the battery) and for the oxygen evolution reaction (during the charge). The electrochemistry of oxygen is particularly challenging due to the known slow kinetics of the oxygen reduction reaction (ORR) and to the high potentials (>1.8 V vs. RHE) reached during the oxygen evolution reaction (OER), directly affecting the stability of the system. In the latest years, several electrocatalysts have been developed as bifunctional materials, including perovskites, layered metal oxides and transition metal-based catalysts. In this work, carbon nanofibers (CNF) synthesized by electrospinning are loaded with spinel-type cobalt oxide (Co3O4) and its modification with Ni or Fe (NiCo2O4, FeCo2O4). These samples are investigated as bi-functional catalysts for both the reduction of oxygen and the oxidation of water in an alkaline medium. Acknowledgements The research leading to these results has received funding from the “Accordo di Programma CNR-MiSE, Gruppo tematico Sistema Elettrico Nazionale – Progetto: Sistemi elettrochimici per l’accumulo di energia”.

B.1.4
10:15
Authors : Karol Pożyczka(a), D. Monikowska(b), M. Marzantowicz(a), E. Zygadło-Monikowska(b), F. Krok(a)
Affiliations : (a) Warsaw University of Technology, Faculty of Physics, Koszykowa 75, 00-662 Warsaw, Poland, (b) Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, Poland

Resume : In order to shift market demand from combustion-based cars to electric vehicles (EV), the latter have to be cheaper and offer comparable overall performance. Major bottlenecks of today’s EV are: charging rate, range on a single charge and impact of outside temperature. All those drawbacks are closely correlated with electrical properties of electrolytes used in EV. Therefore, in a search of better electrolytes, more effort must be put on proper measurement of a complete set of transport properties. In case of binary electrolytes those properties are: ionic conductivity, salt diffusion coefficient and cation transference number [1]. There are quite a few techniques to estimate such properties [1,2] but they are either complicated or susceptible to measurement errors. We have investigated electrolytes based on lithium alkyltrialkoxyborates salts [3] using simple and reliable electrochemical symmetric polarization procedure [4]. Analysis of the results was performed using approaches of Evans et al. [5], Watanabe et al. [6] or Ma et al. [1]. Comparison of results allowed to qualitatively single out the best performing sample and gave comprehensive overview of main factors affecting the electrical parameters of the electrolyte. Acknowledgements: NSC PL grant 2014/15/N/ST5/03909 [1] Y.Ma JES 142 (1995) 1859 [2] S.Zugmann EA 56 (2011) 3926 [3] E.Zygadło-Monikowska JPS 195/18 (2010) 6055 [4] K.Pożyczka EA 227 (2017) 127 [5] J.Evans Polymer 28 (1987) 2324 [6] M.Watanabe SSI 28–30 (1988) 911

B.1.5
10:30 COFFEE BREAK    
 
B2 : WEIL MARCEL
11:00
Authors : Wei-Ren Liu
Affiliations : Department of Chemical Engineering, Chung Yuan Christian University, Chung Li, Taiwan

Resume : A template-free solvothermal method is employed to successfully obtain ZnV2O4 spinel oxide and its electrochemical properties as anode material for sodium ion battery system are investigated for the first time. The structural, morphological, elemental composition, and electrochemical properties of the as-prepared ZnV2O4 are carried out. XRD reveals the presence of ZnO and VO2 impurities when synthesized for 1 day, while complete formation of ZnV2O4 was attained when the synthesis procedure is increased to 3 days. When cycled at 0.1 A∙g-1, it delivers an initial capacity of ~ 648 mAh∙g-1 at a potential window of 0.01-3.0V. Meanwhile, a reversible capacity of ~ 350 mAh∙g-1 is obtained when cycled at 0.2 A∙g-1 for 70 cycles which is significantly higher than the non-graphitic carbonaceous compounds which are commonly used as anode materials for sodium ion batteries. Furthermore, even after cycling at different current densities, 0.1 - 5 A∙g-1, ZnV2O4 is able to recover ~ 310 mAh∙g-1 when cycled back to 0.1 A∙g-1. These results indicate that potential applications of ZnV2O4 as anode material for sodium ion battery system.

B.2.1
11:30
Authors : 1 L. Álvarez-Contreras2, J. Ledesma-García1, L. G. Arriaga3, N. Arjona3, and M. Guerra-Balcázar1*
Affiliations : 1 Facultad de Ingeniería, División de Investigación y Posgrado, Universidad Autónoma de Querétaro, Querétaro, C. P. 76010, México. 2 Centro de Investigación en Materiales Avanzados S. C., Complejo Industrial Chihuahua, Chihuahua, C. P. 31136, México. 3 Centro de Investigación y Desarrollo Tecnológico en Electroquímica S. C., Querétaro, C. P. 76703, México.

Resume : The use of electrochemical supercapacitors is a suitable option for energy storage systems and compared with batteries, exhibit a higher power capability, long life, and low maintenance cost. A Supercapacitor device has two storage mechanisms: the electrical double-layer (EDL) and the pseudocapacitance. In this work, PANI/MWNT and PANI/Graphene composites have been synthesized and evaluated as promising electrode materials in supercapacitors system. Chemically modified PANI/graphene and PANI/MWCNT composites were prepared by in-situ polymerization in acidic conditions. The physicochemical properties of composites were determined by scanning electron microscopy (SEM), X-ray diffraction, FT-IR, TGA, and Raman spectroscopy. Electrochemical properties of both materials have been characterized by cyclic voltammetry (CV) and galvanostatic charge-discharge technique. It was found that, for both cases, the graphene and multiwalled carbon nanotubes a uniform composite was formed with a high specific capacitance and good cycling stability

B.2.2
11:45
Authors : Giulia Piana, Francesca Coló, Federico Bella, Marisa Falco, Giuseppina Meligrana, Claudio Gerbaldi
Affiliations : GAME Lab, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino, Italy

Resume : In the recent years, large-scale energy storage systems are becoming extremely important to realize the load leveling of intermittent renewable energy sources, such as wind and solar, into the grid. Secondary (rechargeable) sodium-based batteries may represent the key enabling technology in this respect, because of high-energy density, low-cost, simple design, and easiness in maintenance. However, standard batteries use liquid electrolytes, which are based on toxic and volatile organic carbonate solvents, and their flammability clearly raises safety concerns. The most striking solution at present is switching on all solid-state designs exploiting polymer materials, films, ceramics, etc. [1] Here, we offer an overview of our recent developments on innovative polymer electrolytes for sodium-ion batteries. In our Labs, we develop different kind of polymer electrolytes by means of different techniques, including simple solvent casting [2] and UV-induced photopolymerization (UV-curing) [3,4], being simple, low-cost and easily scalable to an industrial level. The use of carbonates or ionic liquids as solvent could tailor our electrolytes properties for specific applications. All samples were thoroughly characterized from the physico-chemical and electrochemical viewpoints. They exhibited excellent ionic conductivity and wide electrochemical stability window, which ensure safe operation even at ambient conditions. Electrochemical performances in lab-scale devices were evaluated by means of cyclic voltammetry and galvanostatic charge/discharge cycling exploiting different electrode materials (prepared by water-based procedures and exploiting green compounds as binders). Research and development on Na-ion polymer batteries for moderate temperature application is at an early stage, only lab-scale cells were demonstrated so far. Nevertheless, with the appropriate choice and optimization of electrode/electrolyte materials, and successful combination thereof, the intriguing characteristics of the newly developed polymer electrolytes here presented postulate the possibility of their effective implementation in safe, durable and high energy density secondary Na-based solid-state devices conceived for green-grid storage and operating at ambient and/or sub-ambient temperatures. [1] J.-Y. Hwang, S.-T. Myung, and Y.-K. Sun, Chem. Soc. Rev. 46 (2017) 3529-3614. [2] F. Colò, F. Bella, Jijeesh R. Nair, M. Destro, and C. Gerbaldi, Electrochim. Acta 174 (2015) 185-190. [3] F. Bella, F. Colò, Jijeesh R. Nair, and C. Gerbaldi, ChemSusChem 8 (2015) 3668-3676. [4] F. Colò, F. Bella, Jijeesh R. Nair, and C. Gerbaldi, Electrochim. Acta 365 (2017) 293-302.

B.2.3
12:00
Authors : Caroline Gaya, Yinghui Yin, Amangeldi Torayev, Dominique Larcher, Christine Surcin, Matthieu Courty, Youcef Mammeri, Benoit Fleutot, Mathieu Morcrette, Alejandro A. Franco,
Affiliations : IRT Saint Exupéry, 3 rue Tarfaya, 31405 Toulouse, France; Laboratoire de Réactivité et Chimie des Solides (LRCS), CNRS UMR 7314, Université́ de Picardie Jules Verne, Hub de l’énergie, Rue Baudelocque, 80039 Amiens, France; Réseau sur le Stockage Electrochimique de l’Energie (RS2E), Fédération de Recherche CNRS 3459, Hub de l’énergie, Rue Baudelocque, 80039 Amiens, France; ALISTORE - European Research Institute, Fédération de Recherche CNRS 3104, Hub de l’énergie, Rue Baudelocque, 80039 Amiens, France; Laboratoire Amiénois de Mathématique Fondamentale et Appliquée (LAMFA), CNRS UMR 7352, Université́ de Picardie Jules Verne, Hub de l’énergie, Rue Baudelocque, 80039 Amiens, France; Institut Universitaire de France, 103 Boulevard Saint-Michel, 75005 Paris, France;

Resume : Since 1996 when Abraham et al. unveiled a rechargeable lithium-air battery,1 this technology has grasped the attention of many scientists. From theoretical point of view, they offer a real advantage for applications which require at the same time high gravimetric and volumetric energy densities. Practically, these batteries still need to be improved to match the theoretical expectations. Oxygen diffusion, electrode passivation and pore clogging have been recognized to be the main limiting factors. Then, developing the positive electrode where these three phenomena occur is of prior importance2. To enhance oxygen diffusion while lowering the impact of pore clogging we propose a bi-porous electrode configuration. In this communication, we firstly report our modeling study on theoretical bi-porous electrodes which enables us to sustain the development of our experimental design plan3. The tradeoffs between electrode composition, thickness and bi-porous ratio in order to improve the cell performances will be disclosed. Then, in order to implement our computational findings at experimental level, we describe the experimental fabrication process we used in order to create at lab scale such an electrode configuration. A strong focus on how the bi-porosity can be obtained and mastered will be provided. 1. Abraham, K. M. & Jiang, Z. A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery. J. Electrochem. Soc. 143, 1–5 (1996). 2. Xue, K.-H. H., Nguyen, T.-K. K. & Franco, A. A. Impact of the Cathode Microstructure on the Discharge Performance of Lithium Air Batteries: A Multiscale Model. J. Electrochem. Soc. 161, E3028–E3035 (2014). 3. Gaya, C., Yin, Y., Torayev, A., Mammeri, Y. & Alejandro, A. Investigation of bi-porous electrodes for lithium oxygen batteries. Electrochim. Acta Accepted, (2018).

B.2.4
12:15
Authors : Alessandro Stassi, Claudia D’Urso, Orazio Barbera, Nicola Briguglio, Esterina Modica, Vincenzo Antonucci, Antonino Salvatore Aricò, Vincenzo Baglio
Affiliations : Istituto di Tecnologie Avanzate per l’Energia "Nicola Giordano" (CNR-ITAE)

Resume : Metal-air batteries are receiving a significant interest due their high theoretical energy densities. Among them, iron-air batteries are considered the most economic and durable ones. Unlike zinc electrodes, the iron electrode does not suffer from shape change upon cycling and is also extremely tolerant to over-charge and over-discharge. Moreover, the iron-air battery does not suffer metal dendrite formation on repeated cycling, suggesting that the cycle lifetime of iron electrodes could, in theory, be longer, and an electrolyte flow system is not required to prevent dendrite formation since solid state reactions take place on the electrode surface. This simplifies the battery construction. Accordingly, the aim of this work is the design and fabrication of a simple iron-air battery, manufactured using computer numerical control (CNC) machining on PTFE. The prototype was used for characterizing iron (negative) electrodes and bifunctional oxygen (positive) electrodes prepared at CNR-ITAE laboratories. Acknowledgements The research leading to these results has received funding from the “Accordo di Programma CNR-MiSE, Gruppo tematico Sistema Elettrico Nazionale – Progetto: Sistemi elettrochimici per l’accumulo di energia”.

B.2.5
12:30 LUNCH BREAK    
 
B3 : JIJEESH RAVI NAIR
14:00
Authors : Marcel Weil, Jens Peters, Manuel Baumann
Affiliations : Institute for Technology Assessment and Systems Analysis, KIT, Karlsruhe (Germany); Helmholtz-Institute for Electrochemical Energy Storage, KIT, Ulm (Germany); Institute for Technology Assessment and Systems Analysis, KIT, Karlsruhe (Germany)

Resume : Batteries are considered as a key technology for the energy turnaround and a future grid with a high share in renewable energy source and related fluctuating energy provision. To ensure sustainability the environmental and economic consequences of such a technology should be known. Many Life Cycle Assessment (LCA) studies for Li-Ion batteries (LIB) can be found in literature, but they are based and rely on only on a few studies with primary data. Therefore there is an urgent need for primary Life Cycle inventory (LCI) data in order to ensure the reliability of battery LCA results. Eight different presently available battery technologies are analysed for four different stationary applications regarding their economic and ecological life cycle impacts. Notwithstanding the exhibited uncertainties, depending on the application field the ranking order of battery technologies differs significantly. In general it can be recognised, that in most cases LIB’s performs quite well, whereas lead acid batteries rather bad. But the gained LCA result for VRFB underlies great uncertainties, because it is based on outdated LCI data from 1999. But there are emerging batteries, which could replace present battery systems in the future and overcome the economic and ecological limitations of present energy storage systems. One interesting post-Li systems is Na-battery. A first LCA and cost analysis is published, and both studies show promising results in this early stage of technology development.

B.3.1
14:30
Authors : Jakob Asenbauer, Matthias Kuenzel, Tobias Eisenmann, Adele Birrozzi, Stefano Passerini, Dominic Bresser
Affiliations : Helmholtz Institute Ulm (HIU), 89081 Ulm, Germany Karlsruhe Institute of Technology (KIT), 76021 Karlsruhe, Germany

Resume : At present, graphite is the most employed Li-ion anode, yet its specific capacity is limited to 372 mAh g-1¬ and Li+ diffusion limitations prevent fast charging [1]. Alternative anodes, following either an alloying or conversion mechanism, usually show much higher capacities and superior rate capability, though severely suffering an extensive volume variation and relatively poor energy efficiency, respectively [2,3]. In an attempt to overcome these intrinsic challenges, a new material class has recently been proposed, conversion/alloying-materials (CAMs), combining these two mechanisms in one single compound [4]. Herein, we will report an in-depth evaluation of the energy efficiency and volume variation for a series of CAMs. For the energy efficiency, a particular focus was set on the impact of an increasing alloying contribution and capacity limited cycling, while the volume variation was studied by complementary in and ex situ techniques to identify the main driving forces and obtain a detailed understanding of the occurring phenomena. Our findings provide – to the best of our knowledge – the first insight into these two highly important parameters and reveal the advantageous synergistic effect of CAMs. References [1] Y. Yamada et al., Langmuir. 25 (2009) 12766–12770. [2] M.N. Obrovac, V.L. Chevrier, Chem. Rev. 114 (2014) 11444–11502. [3] J. Cabana et al., Adv. Mater. 22 (2010) E170–E192. [4] D. Bresser et al., Energy Environ. Sci. 9 (2016) 3348–3367.

B.3.2
14:45
Authors : Tobias Eisenmann (a b), Gabriele Giuli (c), Angela Trapananti (c), Jakob Asenbauer (a b), Franziska Mueller (a b), Stefano Passerini (a b), Dominic Bresser (a b)
Affiliations : a) Helmholtz Institute Ulm (HIU), 89081 Ulm, Germany b) Karlsruhe Institute of Technology (KIT), 76021 Karlsruhe, Germany c) School of Science and Technology, University of Camerino, 62032 Camerino, Italy

Resume : For the continuation of the great success story of Li-ion batteries, there is a strong need for further improvement concerning their energy and power density [1]. As these two characteristics are eventually governed by the cell chemistry, large efforts are undertaken to replace, e.g., graphite on the anode side by high capacity materials storing Li+ classically via conversion or alloying. Recently, a new class of materials has been introduced, combining both conversion and alloying in one active material (CAMs) [2]. Transition metal (TM) doped ZnO (ZnxTM1-xO), as a classic example, offers capacities exceeding 950 mAh g 1 and excellent rate performance, but the precise impact of the TM dopant remained to be clarified [2]. Herein, we report a detailed study comparing Fe- and Co-doped ZnO by means of in/ex situ X-ray absorption spectroscopy, X-ray diffraction and electrochemical methods [3]. The results reveal that the aliovalent Fe doping (Fe3+ vs Co2+) induces cationic vacancies, which enable lithium insertion into the wurtzite lattice at higher potentials, and, as a result, the subsequent conversion step is kinetically favored. To the best of our knowledge, such lithium insertion into wurtzite ZnO has not been reported so far and the findings may pave the way for the development of advanced CAMs. References [1] B. Scrosati, J. Garche, J. Power Sources. 195 (2010) 2419. [2] D. Bresser et al., Energy Environ. Sci. 9 (2016) 3348. [3] G. Giuli et al., Materials. 11 (2018) 49.

B.3.3
15:00
Authors : Guan-Min Huang, Tsung-Chun Tsai, Chun-Wei Huang, Wen-Wei Wu
Affiliations : Department of Materials Science and Engineering, National Chiao Tung University, No.1001, University Rd., East Dist., Hsinchu City 300, Taiwan

Resume : As we know, batteries and supercapacitors have become the widespread energy storage systems nowadays. To meet the ever-growing demand for high-efficiency energy storage, a novel device, hybrid supercapacitor, is developed by integrating these specific advantages from both. Here, we established a nano hybrid supercapacitor and investigated the lithium storage mechanisms via in situ transmission electron microscopy (TEM). Using our unique in situ experimental setup that employs colloidal electrolyte, we elucidate two different mechanisms during operation, including the electrochemical reaction (battery-type) and ions intercalation (supercapacitor-type) of the electrode material, Co3O4/CNTs. The transition metal oxides would undergo chemical phase transformations while the porous CNTs absorbed lithium ions physically. Additionally, the structure and composition of the electrodes material were also characterized by high-resolution TEM, electron diffraction, energy dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS). With these results, it can provide direct evidence of lithium storage behaviors and help to enhance the application of hybrid supercapacitors.

B.3.4
15:15
Authors : A.K. Ola Hekselman, Andrew D. Ballantyne, David J. Payne
Affiliations : Department of Materials, Imperial College London, South Kensington Campus, London, SW7 2AZ, UK

Resume : Lead-acid battery (LAB) is the most popular power supply for automotive industry and even with an increasing development of Li-ion technology, LABs are still present in state-of-the-art hybrid and fully electric vehicles due to their position as ‘the’ energy storage device for the 12 V internal electronics.[1] The global usage of lead has been continuously increasing since the 1960s, with over 85 % of the market accounting for the production of LABs. Despite the widespread and new emerging applications, such as energy storage systems for smart grid, a major challenge facing the lead-acid technology is its toxicity and the environmental impact of lead. To address these issues, we are developing a low-energy, low-temperature and an environmentally friendly alternative to the traditional pyro- and hydrometallurgical processes, which are currently dominating the recycling of LABs. The proposed process involves the dissolution of Pb-containing battery waste into deep eutectic solvents (DES), followed by an electrochemical recovery of metallic lead.[2] In our work, cyclic voltammetry and chronoamperometry were used to determine the electrodeposition behavior and mechanism, while ICP-OES and EXAFS provided insight into speciation of lead in DESs, and SEM and XPS were used to characterize the lead electrodeposits. [1] P. T. Moseley, D. A. J. Rand and J. Garche in 21 - Lead–acid batteries for future automobiles: Status and prospects, Elsevier, Amsterdam, 2017, pp. 601-618. [2] A. D. Ballantyne, J. P. Hallett, D. J. Riley, N. Shah and D. J. Payne, Royal Society Open Science 2018, 5.

B.3.5
15:30 COFFEE BREAK    
 
B4 : WEI-REN LIU
16:00
Authors : Jakub Kupecki
Affiliations : Department of High Temperature Electrochemical Processes (HiTEP), Institute of Power Engineering, Poland National Fuel Cell Research Center, University of California, Irvine, US

Resume : Solid oxide electrolysis (SOE) enables highly efficient production of hydrogen using intermittent renewable energy. The gas obtained from the electrochemical reaction can be used directly or injected into the grid (P2H - power-to-hydrogen), used as a substrate in Sabatier reaction (P2G - power-to-gas), directed to Fisher-Tropsch synthesis (P2L - power-to-liquid) or consumed in the Haber-Bosch process for production of ammonia (P2A - power-to-ammonia). No matter which process is chosen, the operating principles of solid oxide electrolyzers remain the same. Versatility of the SOE stacks makes them perfect candidates for advanced systems which allow utilization of excess electricity which would be otherwise curtailed. Several limitations and challenges are however identified in operation of solid oxide electrolyzers. Moreover, the performance of the stack depends on number of parameters and capturing of these correlations remains non-trivial. Solution comes in a form of advanced modeling techniques which aid in understanding the relation of operating conditions, specification of the materials, geometry and design of the cells and stacks on the system-level performance. The work discusses the advanced approaches in modeling and simulation which are applied to variant analyses of standalone SOEC and SOE stacks, including both stationary and non-stationary operation.

B.4.1
16:30
Authors : Taylor D. Sparks, Shadi Al Khateeb
Affiliations : University of Utah; Al-Balqa Applied University

Resume : To improve battery performance a high cathode surface area is needed to maximize the electrode electrolyte contact area. For this purpose and for the first time, conductor and binder free porous FeS2 films through the entire thickness were deposited by spray pyrolysis. 1M of Fe(NO3)3*9H2O, FeCl3, and NH2CSNH2 were utilized as the precursors. Film deposition was performed at 400C in open atmosphere. The deposited films were sulfurized at 500C for 4 hrs with H2S gas or in sealed quartz ampoules with sulfur flakes. The best crystallized films were obtained using FeCl3 and NH2CSNH2 precursors followed by sulfurization in the sealed ampoules. The films where characterized with XRD, SEM, EDS and EIS. The films were cycled at C/10 and C/20 and gave comparable capacities compared to the literature finding for FeS2 powders mixed with conductor and binder additions.

B.4.2
16:45
Authors : 1Youssef Dabaki, 1ChokriKhaldi, 3NouredineFenineche, 4Omar ElKedim, 1, 2Mohamed Tliha ,1JilaniLamloumi
Affiliations : 1 University of Tunis, Laboratory of Mechanics, Materials and Processes, Group of Metal Hydrides, ENSIT, Tunisia 2Department of Physics, University Faculty, Umm-Alqura University, Al-Qunfudah, Saudi Arabia. 3 FEMTO-ST, MN2S, UTBM, Site de Sévenans, 90010 Belfort Cedex, France. 4 IRTES-LERMPS/FR FCLAB, UTBM, Site de Sévenans, 90010 Belfort Cedex, France.

Resume : The energy industry of today must evolve toward a direction cheaper, cleaner and more efficient. It is expected that hydrogen plays an important role in a future energy economy based on sources and carriers own and respectful of the environment. Many efforts have been made to develop solutions based on hydrogen; however, the hydrogen itself is not a source of energy, just a vector of energy and, as in the case of the electrical energy, it must be generated in one way or another with the use of another source of energy. If the hydrogen is generated, it can supply power to the internal combustion engines and the gas fireplace is of the steam of pure water. The use of hydrogen can generate 3 to 4 times more energy per mass compared to conventional sources. Nevertheless, the hydrogen must be stored. The storage in the liquid state requires heavy tanks and at high pressure cooled at extremely low temperatures. This consumes at least 20% of the stored energy. A possible solution to this problem is to store hydrogen in the solid state, forming relatively easily the hydride. The storage of hydrogen by metals and alloys is an effective way to obtain a strong volumetric capacity in hydrogen. In this mode, the hydrogen is stored in a solid form and the density of hydrogen can be greater than that of the liquid hydrogen. The hydrogen can also be absorbed and desorbed in a reversible fashion to high rates. Ni - MH batteries have superior properties which are low maintenance, high power, long cycle life, good thermal performance and configurable design. Hydrogen storage alloys play a major role in the life of a Ni - MH battery and determine the electrochemical properties of the battery. LaNi5, belonging to the CaCu5 crystal structure type, satisfy many of the properties. The most important property of LaNi5 is fast hydrogen kinetics [1-3]. Recently, CaNi5, belonging to same crystal type, has taken some attention due to its low cost, higher hydrogen storage capacity, good kinetic properties [4-6]. In the present work, Ca, Ni and Mn have been crushed mechanically with the composition CaNi5-xMnx (or x= 0.5and 1) during 10, 20, 30, 40, 50 and 60 hours. The results obtained should provide more detailed data on the influence of the substitution of Mn and electrochemical properties of the hydrogen storage in the CaNi5-xMnx (or x= 0.5 and 1) alloy. The hydrogen storage capacity for electrode was measured electrochemically ranging from 100 to120 mAh/g, respectively, for 0.5 and 1. Keywords: Ni-MH batteries, hydrogen storage materials, CaNi5-based alloy, mechanical milling, electrochemical properties. References: [1] Tliha M, Khaldi C, Mathlouthi H, Lamloumi J, Percheron-Guegan A (2007) Electrochemicalinvestigation of the iron-containing and no iron-containing AB5-type negative electrodes. JAlloysCompd 440:323–327. [1] Khaldi C, Mathlouthi H, Lamloumi J, Percheron-Guegan A (2004) Electrochemical study of cobalt-free AB5–type hydrogen storage alloys. Int J hydrogen energy 29:307–311. [3] Y. Dabaki, S. Boussami, C. Khaldi, H. Takenouti, O. ElKedim, N. Fenineche, J. Lamloumi, The effect of ZnO addition on the electrochemical properties of the LaNi3.55Mn0.4Al0.3Co0.2Fe0.55 electrode used in nickel metal-hydride batteries, Journal of Solid State Electrochemistry, 21, 1157-1164, (2017). [4] G.D. Sandrock, J.J. Murray, M.L. Post, J.B. Taylor, Mater. Res. Bull, 17, 887, (1982). [5] J.O. Jensen, T.S. Møller, N.J. Bjerrum, Journal of Alloys and Compounds, 330–332, 2002, 215–218.

B.4.3
17:00
Authors : Heftsi Ragones, Yosi Kamir, Svetlana Menkin, Diana Golodnitsky
Affiliations : Heftsi Ragones, Yosi Kamir, Svetlana Menkin - School of Chemistry, Tel-Aviv University Diana Golodnitsky- School of Chemistry, Wolfson Applied Materials Research Center Tel-Aviv University, Tel-Aviv, 69978, Israel

Resume : The increasing demand for multifunctional portable/wearable electronic devices, including wireless sensors and implantable medical devices is continuously growing. Such devices need rechargeable batteries with dimensions on the scale of 1–10 mm3 (few to tens mm2 footprint area of substrate) including all the components and all the associated packing. Thus, in the past decade, along with the developments in battery materials, the focus has been shifting more and more towards innovative fabrication processes, unconventional configurations, and designs with multi-functional components. 3D printing technologies enable a well-controlled creation of functional materials with three-dimensional architectures, representing a promising approach for fabrication of next-generation electrochemical energy storage (EES) devices with high performance due to a higher electrode/electrolyte interfacial area. In this work, we demonstrate a novel design and a novel approach of 3D printing of batteries of different shapes and size by using filaments composed of active electrode materials bound with polymers. The electrodes were printed by fused-filament fabrication (FFF) method. We demonstrated a reversible electrochemical cycling of 3D printed lithium iron phosphate (LFP) and lithium titanate (LTO) composite polymer electrodes vs. lithium metal anode with high performance and capacity in cells containing both conventional non-aqueous and ionic-liquid electrolytes.

B.4.4
17:15
Authors : Kuan-Zong Fung[1,2], Shu-Yi Tsai [1,2], Li-Fu Chang [3], Bo-Yuan Huang [1], Mei-Han Chen [1]
Affiliations : 1. Department of Materials Science and Engineering, National Cheng Kung University, Tainan, TAIWAN 2. Hierarchical Green-Energy Materials Research Center, National Cheng Kung University, 70101 Tainan, TAIWAN 3. Research Center for Energy Technology and Strategy (RCETS), National Cheng Kung University, Tainan, TAIWAN

Resume : Functional oxides are known to show interesting electrical properties by introduction of desired defect structures. Electrode performance in Li batteries is also highly dependent on its defect reaction through synthesis and/or charging-discharging cycles. In this study, the behavior of Li-rich layered oxide cathode and Li4Ti5O12 (LTO) are investigated and illustrated based on their defect reactions. For examples, the as-received zero-stain anode oxide Li4Ti5O12 shows conductivity as low as 10-9 S/cm and then causes high interface polarization and low rate capability. With proper processing under low pO2, the electron conduction and electrochemical properties of LTO was significantly improved. Such property enhancement may be well illustrated by defect reaction under low pO2 environment. In other words, lattice oxygen near surface of LTO tends to be removed under very low pO2. Consequently, positively charged oxygen vacancy is formed and then charge-compensated by the creation of two negatively charged electrons. These electrons are eventually associated with tetravalent Ti ions. The fast electron pathway is established by the coexistence of Ti+3 and Ti+4 in Ti cation sublattice. Furthermore, Li-rich layer-structured cathode formulated as xLi2MnO3-(1-x)LiMO2(M = Mn, Ni, Co, etc.) during 1st charging process was found to exhibit oxygen oxidation, vacancy formation. In the following discharging, the manganese reduction (or activation) occurred. As a result, a reversible capacity as high as 250 mAh/g was observed (Fig. 1(a)). Such redox reactions may be illustrated by defect chemistry. In other words, during 1st charging, electrons and oxygen was extracted from lattice oxygen with the formation of oxygen vacancies. In the next discharging process, electrons was accepted by cathode oxides accompanied by valence changing of Mn+4 to Mn+3. It is known that typical electrochemical reactions are highly dependent up movement of electrons and ions. With understanding of defect reaction during materials processing and charging/discharging, advanced electrode materials with much improved electrochemical and/or stability may be developed.

B.4.5
 
POSTER SESSION 1 : VINCENZO BAGLIO
17:30
Authors : Seon-Jin Lee, Kyoung-Tae Kim, Ji-Woong Shin, Mi-Ra Shin, Jin-Ju Bae, Ryu Jin, Min-Gyeom Kim, Han Jeong heum, Young Hwan Lee, Tae Whan Hong, Jong-Tae Son*
Affiliations : Department of Nano-Polymer Science & Engineering, Korea National University of Transportation Chungju, Chungbuk 380-702, Republic of Korea; Department of advanced Materials Engineering, Korea National University of Transportation Chungju, Chungbuk 380-702, Republic of Korea

Resume : Li[Li1/3–2x/3MxMn2/3– x /3]O2(M = Ni, Co, or/and Cr) are currently receiving significant attention for use as modern cathode materials for LIBs, owing to their high capacity of over 200 mAhg-1 when charged to 4.5 V or higher. Because of the rapidly fading capacity and the poor rate-capability of Li[Li1/3–2x/3MxMn2/3–x/3]O2 materials, extensive efforts have been made in recent years to improve their rate-capability. In this work, LixNi0.35Mn0.65O2 with graphene was prepared by sol-gel method. XRD(x-ray diffraction) and SEM(scanning electron microscope) were used to characterize their structure and microstructure. The rate-capability and cycle stability at 55 ℃ were enhanced due to the electrical conductivity.

B.B.1
17:30
Authors : Manoj Mayaji Ovhal, Jae-Wook Kang*
Affiliations : Graduate School of Flexible and Printable Electronics, Chonbuk National University

Resume : Flexible, transparent energy storage systems have evoked huge research attention due to compatibility in innovative wearable electronics and displays. However, it remains a great challenge to fabricate flexible, transparent conductive electrodes (TCEs) with high energy storage capability of conducting materials while retaining its transparency. Herein, the cost-effective method was employed to fabricate electrodes by using a thin layer of conjugated polyelectrolyte and nickel hydroxide on metal nanowire as a current collector, which were embedded into UV-cured polymer films. The flexible hybrid electrodes were exhibit excellent transparency (T550 nm = 92%) and high conductivity (sheet resistance 38 ± 5 Ω). The symmetrical all-solid-state supercapacitors were assembled using gel-electrolyte, which results in a maximum areal capacitance of 3.2 mF cm-2 (at the scan rate of 100 mV s-2). These devices show excellent mechanical stability with highest reported capacitance values so far. Collectively, the simple, cheap and controllable method for fabrication of flexible and transparent supercapacitor, advance the technology feasible next-generation wearable electronics.

B.B.2
17:30
Authors : Manoj Mayaji Ovhal, Jae-Wook Kang*
Affiliations : Graduate School of Flexible and Printable Electronics, Chonbuk National University

Resume : Flexible, transparent energy storage systems have evoked huge research attention due to compatibility in innovative wearable electronics and displays. However, it remains a great challenge to fabricate flexible, transparent conductive electrodes (TCEs) with high energy storage capability of conducting materials while retaining its transparency. Herein, the cost-effective method was employed to fabricate electrodes by using a thin layer of conjugated polyelectrolyte and nickel hydroxide on metal nanowire as a current collector, which were embedded into UV-cured polymer films. The flexible hybrid electrodes were exhibit excellent transparency (T550 nm = 92%) and high conductivity (sheet resistance 38 ± 5 Ω). The symmetrical all-solid-state supercapacitors were assembled using gel-electrolyte, which results in a maximum areal capacitance of 3.2 mF cm-2 (at the scan rate of 100 mV s-2). These devices show excellent mechanical stability with highest reported capacitance values so far. Collectively, the simple, cheap and controllable method for fabrication of flexible and transparent supercapacitor, advance the technology feasible next-generation wearable electronics.

B.B.3
17:30
Authors : Longtao Ma, Chunyi Zhi
Affiliations : Department of Materials Science and Engineering, City University of Hong Kong

Resume : The exploitation of a high-efficient, low-cost and stable non-noble metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersing Fe-Nx species on a two dimensional (2D) highly-graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an over-potential of 390 mV at 10 mA·cm-2 for OER) in alkaline medium. Furthermore, an elastic polyacrylamide (PAM) hydrogel based electrolyte with the capability to remain great elasticity even under highly corrosive alkaline environment, is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery performs a low charge-discharge voltage gap (0.78 V at 5 mA·cm-2) and large power density (118 mW·cm-2). It could be compressed up to 54% strain and bended up to 90o without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on porous support for bi-functional oxygen catalyst as cathode integrating specially designed elastic electrolyte are feasible strategies for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

B.B.4
17:30
Authors : Yoonjae Lee(a), Myung Hyun Lee(a), Namtae Kim(a), Byeong Il Lee(a), Haemin Yang(a), Jae Jeong Kim(a), Kee-Kahb Koo(b), Young Gyu Kim(a)*
Affiliations : (a) School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Seoul, 08826, Korea; (b) Department of Chemical and Biomolecular Engineering, Sogang University, Seoul 04107, Korea

Resume : Three-dimensional architecture of electronic chips has attracted much attention because higher density electronic devices are needed for various applications. Through-Silicon Via (TSV) or microvia, one of the techniques to achieve the high density architecture, is vertical interconnect between chips providing the shortest path. Although there are several advantages of these techniques such as low power consumption, and high signal transmission, realizing TSV or microvia has some problems to be solved. Especially, defect-free filling of Cu is an important issue. We have been particularly interested in the development of levelers, organic additives for Cu electrodeposition, for the defect-free Cu electrodeposition. Among them, a triethylene glycol (TEG)-based leveler containing the two quaternary ammoniums at both ends has been synthesized and reported in our previous reports. In this presentation, we are going to introduce several derivatives of the TEG-based levelers synthesized in our lab and experimental results of their relationships between electrochemical properties and structures. All the synthesized levelers were confirmed to have the convection-dependent adsorption characteristics, which is the distinct property of the levelers. However, they showed different suppression effects depending on the length and polarity of the backbone structures.

B.B.5
17:30
Authors : Shengmei Chen, J Antonio Zapien
Affiliations : Department of Materials and Science Engineering, City University of Hong Kong, Kowloon, Hong Kong 999077.

Resume : Rational design of cost-effective, nonprecious metal-based catalysts with desirable oxygen reduction reaction (ORR) performance by simple and economic synthesis route is a great challenge for future fuel cell and metal air batteries commercialization. Herein, the light-weight 3D Co-N-doped hollow carbon spheres (Co-NHCs) has been fabricated via a facile emulsion approach followed by carbonization. The prepared 0.1-Co-NHCs catalyst with suitable Co doping content exhibits favorable ORR catalytic activity (onset potential of 0.99 V and half-wave potential of 0.81 V vs. RHE), comparable to that of the commercial Pt-C (onset potential of 1.02 V and half-wave potential of 0.83 V vs. RHE) and rivals that of Pt-C with better cycling stability. The excellent performance of the catalyst is attributed to the synergetic effect of Co and N doping with high total ratio of active sites, high surface area and good conductivity of the material. More impressively, the assembled rechargeable zinc–air batteries base on the 0.1-Co-NHCs catalyst outperforms those afforded by commercial Pt-C. The progress represented by this reported work is of great importance in the development of outstanding non-noble metal based electrocatalytst for the fuel cell and metal air battery industry.

B.B.6
17:30
Authors : G. Napoli, L. Andaloro, S. Micari, G. Dispenza, V. Antonucci
Affiliations : National Research Council of Italy (CNR) -Institute of Advanced Energy Technologies (ITAE)

Resume : Gradual electrification is widely considered as a feasible strategy for reducing the oil dependency and CO2 emissions of road transportation. In chase of these aims increasing importance has been attributed to Electric Vehicles (EVs). Although the European Commission has strongly supported sustainable mobility initiatives in recent years, with the purpose of decarbonizing road transport and mitigating urban air pollution, results are below expectations. The main support factor to achieve the goals is the spread of EVs but no change will be possible without an infrastructures network that supports its use contributing to maximize the positive impacts. In this paper a methodology to provide optimal locations of electric vehicle infrastructures in a highway network is proposed. The aim is to calculate the required number of charging stations and to set their position using the demand (the flow of EVs) and the supply (the road network). The algorithm is applied in a high dimension case, considering the Italian highway network. The objective is to establish a plan for charging infrastructure to enable long distance trips. Charging demand is estimated based on traffic flows between origins and destinations. The results are organized in terms of charging stations number for each Italian region by varying the scenario according to the power and depict a map which includes the positioning and sizing. In addition, the model has been applied to analyze expected trends in the coming years.

B.B.7
17:30
Authors : L. Andaloro, G. Napoli, G. Dispenza, F. Sergi, A. P. F. Andaloro, S. Di Novo, V. Antonucci
Affiliations : National Research Council of Italy – Institute of Advanced Energy Technologies Salita S. Lucia sopra Contesse, 5, 98126 Messina, Italy

Resume : As suggested by European regulations several initiatives in transport field are taking place in order to introduce low/zero environmental impact vehicles. Many investments have been made in the electric vehicles (BEVs-Batteries Electric Vehicles) field although these still present limits related to low range and long charging times. FCHEVs (Fuel Cell Hybrid Electric Vehicles) are considered promising, as they are able to take advantage of both the batteries and the FCs at the same time. In addition the hydrogen-based transport solutions are coherent with transition from fossil fuels to renewable energies, since several H2 production processes, including electrolysis, support increase of renewable sources. The hybridization between FC and batteries can be minimum (APU) or maximum (TOTAL FC). In the medium level, called RANGE EXTENDER, FC works as on board batteries charger; the principal advantage of this configuration is increase of range (with respect to BEV). This configuration has been chosen by CNR ITAE in order to carry out the prototype of a minibus within the “i-NEXT” project (funded by Italian Ministry of Education, University and Research). The hybrid powertrain is based on a FC system (Power: 20 kW) connected in parallel to the lithium batteries (Nominal Power: 30 kW; Peak Power: 120 kW; Energy: 70 kWh). In order to evaluate the total range of autonomy, starting from 100% of SOC and full H2 tanks, in this work tests drive in only batteries mode and in hybrid mode will be presented.

B.B.8
17:30
Authors : G. Dispenza, F. Sergi, G. Napoli, N. Randazzo, V. Antonucci, L. Andaloro
Affiliations : National Council of Research – Institute of Advanced Energy Technologies (CNR-ITAE) “Nicola Giordano”, Salita S. Lucia sopra Contesse, 5, Messina, Italy

Resume : Both the production and the use of hydrogen are topics that attract highest attention in transport sector, responsible for about 30% of world energy-related greenhouse gases (GHG) emissions, while the practical aspects of a hydrogen economy, are rarely addressed. In this work the cost of hydrogen was studied through the design, realization and validation of a solar-powered hydrogen fueling station in smart cities applications. CNR-ITAE together with other industrial partners has developed, under the Italian research project called i-NEXT (innovation for greeN Energy and eXchange in Transportation), the on-site hydrogen production plant. The plant is fed by a microgrid able to receive energy from solar radiation by a 100 kWp rooftop photovoltaic plant and connected with a battery energy storage system of 300 kWh (composed by 16 sodium nickel chloride high temperature batteries) in this way the plant is able to deliver hydrogen and electricity for an electric and hydrogen vehicles fleet. This work compares, through three different case studies coming from a first test campaign, the real cost of hydrogen obtained by using the electricity coming from the main grid (thermoelectric power plants), by using energy from photovoltaic plant and finally by the integration of the battery energy storage system that supports and offsets energy from photovoltaics plant.

B.B.9
17:30
Authors : Juergen Kahr(1), Wolfram Kohs(2), Daniela Fontana(3), Atanaska Trifonova, Corina Täubert(1)
Affiliations : (1) AIT Austrian Institute of Technology GmbH, Center for Low-Emission Transport, Electric Drive Technologies, Giefinggasse 2, 1210 Vienna, Austria, juergen.kahr@ait.ac.at (2) AVL List GmbH, 8020 Graz, Austria (3) Lithops srl, Strada del Portone 61, 10137 Torino, Italy, daniela.fontana@lithops.it

Resume : Advanced lithium ion batteries represent a quite promising alternative to the state-of-the-art technologies especially due to their higher energy density. Extensive work on the next generation 5V Li-ion is currently ongoing – on both active materials and electrolyte. However, the electrolyte stability at more positive potentials remains still a challenge particularly since it strongly influences the cell safety. Several approaches were investigated – e.g. salt concentration, new solvent systems, additives for improving the stability of both electrolyte and SEI layer formation. In this context assessing safety concerning cell processes became of increased interest and here mass spectroscopy (MS) has been proven to be a reliable tool for monitoring volatile species originating from electrolyte decomposition or interactions between cell components and the electrolyte. We investigated the gases evolved during galvanostatic cycling experiments by means of operando GCMS. Here we present gas species arising from the electrochemical decomposition of the LiPF6 / organic carbonate- based electrolyte such as CO2 and HF. The impact of electrolyte additives on the quality of the SEI-film will also be discussed. The author gratefully acknowledges the FFG (Austrian Research Promotion Agency) for funding this research within project No. 858298.

B.B.10
17:30
Authors : Kang-qiang He b, Samson Ho-Sum Cheng b, Chen Liu a*, Cheng-lin Chen a, Cheng-zhu Liao c, Jiao-ning Tang a, Robert K.Y. Li b*
Affiliations : a College of Materials science and Engineering, Shenzhen University, Shenzhen 518055, PR China b Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China c Department of Materials Science and Engineering, South University of Science and Technology of China, Shenzhen 518055, China

Resume : Incorporating garnet-type ceramics into polymer electrolyte for all-solid-state lithium batteries has attracted a great attention since an obvious enhancement of the electrochemical performance can be attained. However, the issues like unsatisfying ionic conductivity and interface stability are still remaining unsolved. Herein, we report a novel composite solid electrolyte with excellent electrochemical properties and cycling performances, which is composed of garnet-type Li6.4La3Zr1.4Nb0.6O12 (LLZNO) and polyethylene oxide (PEO), the optimal composite electrolyte exhibits a maximum ionic conductivity of 5.23×10-5 S cm-1 at room temperature as well as an enlarged electrochemical window of 4.7V. The LLZNO nanoparticles, incorporated into PEO matrix, have great contributions on ionic conductivity, electrochemical stability and interfacial resistance. Besides, the all-solid-state LIBs (LiFePO4/SPE/Li) using the designed composite electrolytes display an amazing capacity of 169.5 mAh g-1 (0.5C, 60oC) that is close to the theoretical capacity of LiFePO4 and present 79.48% capacity retention after 350 cycles. It is concluded that the addition of LLZNO nanoparticles tremendously enhance the electrochemical properties of composite electrolyte leading to superb cycling results for solid-state LIBs.

B.B.11
17:30
Authors : Kang-Qiang He, Samson Ho-Sum Cheng, Hui-Wen Yang, Chen Liu, Chengzhu Liao, Jiaoning Tang, Robin L.W. Ma, C.Y. Chung, Robert K.Y. Li
Affiliations : a College of Materials science and Engineering, Shenzhen University, Shenzhen 518055, PR China b Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China c Department of Materials Science and Engineering, South University of Science and Technology of China, Shenzhen 518055, China d Department of Mechanical and Aerospace Engineering, Hong Kong University of Science and Technology, Hong Kong, China

Resume : In contrast to conventional lithium ion batteries (LIBs) with organic liquid electrolytes that have flammability, leakage and electrochemical instability issues, the all-solid-state lithium batteries based on solid polymer electrolytes (SPEs) have attracted much attention owing to their easy processing, flexibility and safety. Here, we report a novel composite solid electrolyte with excellent electrochemical properties and cycling performances, which is made by co-addition of garnet-type Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and ethylene carbonate(EC) in polyethylene oxide (PEO) based polymer electrolyte, the optimal composite electrolyte exhibits a maximum ionic conductivity of 1.5×10-4 S cm-1 at room temperature as well as an enlarged electrochemical window of 4.7V. Incorporating appropriate amount of LLZTO nanoparticles and EC into PEO matrix were found to have remarkable contributions to Li ionic conductivity, electrochemical stability, interfacial resistance and mechanical properties of the SPE. Besides, the all-solid-state LIBs (LiFePO4/SPE/Li) using the designed composite electrolytes display an amazing capacity of 169.5 mAh g-1 (0.5C, 60oC), that is close to the theoretical capacity of LiFePO4, and about 85% capacity retention after 300 cycles. It is concluded that the co-addition of LLZTO nanoparticles and EC tremendously enhance the electrochemical properties of composite electrolyte leading to superb cycling results for solid-state LIBs.

B.B.12
17:30
Authors : Kang-qiang He a,b, Cheng-lin Chen a, Rong Fan a, Chen Liu a*, Cheng-zhu Liao c, Robert K.Y. Li b, Jiao-ning Tang a*
Affiliations : a College of Materials science and Engineering, Shenzhen University, Shenzhen 518055, PR China b Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong, China c Department of Materials Science and Engineering, South University of Science and Technology of China, Shenzhen 518055, China

Resume : All-solid-state batteries have long been desired for the next generation power source because of their excellent performance of electrochemical stability and safety. The abundant sodium resources and low cost make sodium ion batteries (SIBs) attractive for electrochemical energy storage devices. However, the large interfacial resistance and low ionic conductivity retard their practical applications. Till now, few of the ongoing studies focus on solid polymer electrolytes (SPEs) for SIBs. Compared with nanoparticle fillers, nanowire fillers with high aspect ratio in polymer electrolyte can further suppress the degree of crystallinity of the polymer chains. Inspired by this, in this work, a fully solid composite electrolyte is designed using PEO as polymer substrate and incorporated with homogeneously dispersed TiO2 nanowire fillers for the first time. The ionic conductivity of composite electrolyte increases to 3.11×10-4 S cm-1 at 60°C by adding 6wt% of TiO2. In addition, the solid-state SIBs (Na3V2(PO4)3-CNT/SPE/Na ) based on composite electrolytes exhibit excellent cycling performance with attractive capacities of 91.8 mAh g-1 and 72.7 mAh g-1 at current rates of 1C and 10C at 80°C, respectively. It should be noted that the composite electrolyte designed solid-state SIBs even can operate at 50°C and the rate of 1C with a 68 mAh g-1 capacity, while the pure PEO based battery can not work in the same conditions.The excellent cycling as well as rate performance are further demonstrated in the present study.

B.B.13
17:30
Authors : Kyungeun Baek, Jun Gyeong Lee, Aming Cha, Jiseok Lee,* Kwangjin An,* Seok Ju Kang*
Affiliations : School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Korea

Resume : Closed Li–O2 batteries consisting of electrolytes derived from molten salt have emerged as attractive energy-storage cells because of their unique oxygen-supply mechanism to form a stable Li2O discharge product without requiring an oxygen-gas reservoir. However, the formation of stable Li2O discharge product increases the overpotential during the charging process, which compromises the cell performance because of the resulting parasitic reaction. In this study, we demonstrated a potent approach to reversibly operate an oxygen-gas-reservoir-free Li–O2 battery by using chemically impregnated nickel oxide (NiO) nanoparticles as a catalyst on the carbon electrode. The efficient bottom-up process for decorating NiO on a carbon material in binary molten electrolyte enables not only to significantly reduce the loading level of the catalyst but also to enhance the electrochemical performance with preventing the detrimental parasitic reaction in the oxygen-gas-reservoir-free Li-O2 cell. In particular, using the in situ gas analysis with electrochemical measurements, the 20 wt% NiO added to the carbon cathode is sufficient to reduce the charging potential without generation of parasitic gas evolution.

B.B.14
17:30
Authors : Koichi Hamamoto, Naoki Hamao, Yuki Yamaguchi and Yoshinobu Fujishiro
Affiliations : National Institute of Advanced Industrial Science and Technology (AIST), Inorganic Functional Materials Research Institute, 2266-98, Shimo-shidami, Moriyama-ku, Nagoya 463-8560, JAPAN

Resume : Oxide-based all solid-state batteries have received much attention as a safety power source for large-scale systems. In addition, the solid electrolyte makes it possible to achieve flexible cell structures such as a bipolar battery stack configuration. However, in an oxide-based all solid-state battery, it is difficult to achieve the same electrochemical performance as a battery using an organic liquid electrolyte. Many of the problems are related to the electrode/electrolyte interface. One of the causes of the electrochemical performance adverse effect is the small interfacial area between the electrode and the electrolyte. The solid electrolyte does not penetrate into the porous electrode like an organic electrolytic solution. Therefore, a new manufacturing technique for constructing a preferable electrode/electrolyte interface is required. In this research, we attempted to fabricate a thin corrugated LATP-based (Li1 x yAlxTi2-xSiyP3-yO12) ceramic electrolyte sheet which is able to make a large electrode/electrolyte interface area for three dimensional structured all solid-state battery. The corrugated electrolyte sheet was prepared by combining a conventional sheet forming technique and press forming using a micropatterning mold. We obtained a corrugated electrolyte sheet with a maximum size of 4 x 4 cm. The minimum thickness and pitch of the corrugated electrolyte were 25 μm and 100 μm, respectively. In addition, half-cells were fabricated using corrugated electrolyte sheet and its electrochemical properties were evaluated. It became clear that this property greatly depends on the morphology of the corrugated electrolyte sheet. Acknowledgements This research was partially supported by the Center of Innovation Program from Japan Science and Technology Agency, (JST−ALCA-SPRING) and Council for Science, Technology and Innovation, Cross-ministerial Strategic Innovation Promotion Program (SIP).

B.B.15
17:30
Authors : Gawang-Yong, Byung-Ki Na
Affiliations : Chungbuk National University, Korea

Resume : Theoretical capacities of silicon is about 4,000mAh/g and is higher than carbon-based materials. When silicon reacts with lithium ion, the reaction brings to big volume changes of 400%, which causes mechanical stress. For that reason, some disadvantages are caused such as destroying the electrode, separating from collector electrode, forming an unstable interface layer between active material and electrolyte. Carbon coated silicon oxide with hierarchical pores was prepared to form buffers which released the volume change. After generating SiO2/ZnO composite, carbon was coated with PVC. After preparing carbon coated SiO2/ZnO composite, ZnO was dissolved by acid treatment. Acid treated materials have hierarchical pore structures. C-SiO2/ZnO composite was synthesized with carbon via sol-gel method and decomposition of PVC. Zn(NO3)2∙H2O, C2H5OH, H2O and TEOS were stirred at 60℃ to form Zn containing SiO2 by sol-gel synthesis. It was dried at 80℃ and heated at 650℃ under air. It was mixed with PVC and thermally decomposed at 900℃ under Ar to form carbon-coated SiO2/ZnO composite. It was put into the acid solution to dissolve out ZnO. Finally carbon-coated SiO2 with hierarchical pore structure was prepared. Because of the effect of amorphous SiO2 and carbon, XRD pattern shows broad and higher peaks. TG-DTA showed that water and residual organic materials were eliminated at 200℃ and SiO2 was formed crystalline structure at about 800℃. BET surface area was increased dramatically by removing ZnO in the case of Zn:Si:C=1:1:8. C-Si02/ZnO-01 (Zn:Si:C=1:1:8) appeared best cycling performance at 50 cycles, but the capacity was increased up to 10 cycles. To enhance electrochemical performances of C-SiO2/ZnO composites, optimized ratio of the materials is needed.

B.B.16
17:30
Authors : C. D’Urso, N.Briguglio, V. Baglio, V. Antonucci, A.S. Aricò
Affiliations : CNR-ITAE, Via salita Santa Lucia sopra Contesse, 5 – 98125 Messina (Italy)

Resume : ZEBRA (Zero Emission Battery Research Activities) high temperature batteries are made of sodium-nickel chloride cells. These cells operate at about 270 ° C-350 ° C and are enclosed in a thermal container. ZEBRA batteries are solid-state because they contain Na-β "-alumina as a solid electrolyte. Beta alumina is a two-dimensional conductor of sodium ions. The total electrochemical reaction is as follows: 2 Na NiCl2 = 2 NaCl Ni The two main subgroups of beta alumina are β-Al2O3 and β"-Al2O3 that differ in stoichiometry and sequence of oxygen ions through the conduction plane. Because of its higher conductivity, β "-Al2O3 is the most suitable phase for battery applications. The activities were directed to the chemism of cathodic matter through the use of multiple redox pairs to improve both the capacity and the reaction kinetics or the power of the device. The advantage of this approach lies in the ability to operate under conditions that entail a significant change in nominal characteristics. Depending on the required characteristics (high kinetic or high energy density), the most appropriate redox pair can be spontaneously activated in relation to its redox potential and the electric charge buffering characteristics. The mechanism of operation is based on the different redox potential and on the different reaction kinetics of the various redox pairs. Redox systems with high potential are less reactive but produce an increase in energy density. On the contrary, redox systems with high kinetics can respond well to the intermittence of renewable sources and can also be used in grid balancing services. The development of nanomaterials with a high surface area represents a further strategy that allows a relatively inert redox pair but with optimal capacity to provide high energy density, to be able to guarantee high kinetics as well. This in relation to the fact that the interface is more extensive and the greater the number of reaction sites when the material is nanosized and the surface area high. Acknowledgements The research leading to these results has received funding from the “Accordo di Programma CNR-MiSE, Gruppo tematico Sistema Elettrico Nazionale – Progetto: Sistemi elettrochimici per l’accumulo di energia”.

B.B.17
17:30
B.B.18
17:30
Authors : Vijay Shankar Rangasamy *, Savitha Thayumanasundaram, Jean-Pierre Locquet
Affiliations : Functional Nanosystems Group, Department of Physics and Astronomy, KU Leuven, Belgium

Resume : Recently, polymer electrolytes are gaining much attention due to their non-volatility, possibility to reduce decomposition at the electrodes, flexibility, and improved safety. Polyelectrolytes are polymer systems in which one of the conducting species (anion or cation) is chemically bonded to the polymer backbone. In the present study, Nafion has been used as the polymer network which was ion exchanged with 2M LiOH (Nafion-Li). During the reaction, the proton in the sulfonic acid group (–SO3H) of Nafion is exchanged with Li to provide lithium ion conduction. To further enhance the electrochemical properties, a pyrrolidinium based ionic liquid was added due to its high ionic conductivity and wide electrochemical stability window. The conductivity of Nafion-Li polymer electrolyte is found to be in the order of 10-10 S/cm which increases to 10-5 S/cm with the addition of ionic liquid. Cyclic voltammetry measured in the voltage range of -0.4 V to 2 V shows a lithium deposition peak and a lithium stripping peak, confirming a reversible redox reaction in the prepared polymer electrolytes. Galvanostatic charge-discharge studies of the optimized polymer electrolytes was performed by assembling coin type half cells with LiFePO4 as the cathode and lithium as the anode in the voltage range 2.5 to 4.2 V. The first charge and discharge capacity of the doped “Nafion-Li” polymer electrolyte were 160 and 150 mAh/g, respectively. In-situ impedance spectroscopy and rate capability of the assembled cells were also studied.

B.B.19
17:30
Authors : S. Didry1, C. Tafoual1, C. Autret1, B. Montigny2, J. Santos-Peña2
Affiliations : 1 - Research Group Materials, Microelectronics, Acoustics, Nanotechnologies (GREMAN) UMR 7341 Tours University /CNRS, CEA, ENIVL Faculty of Sciences and Techniques, Parc de Grandmont, 37200 Tours, France 2 - Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l’Energie (EA 6299), Tours University, Parc de Grandmont, F-37200, France

Resume : Sodium ion technology is one of the most powerful alternatives to other energy storage technologies currently marketed or in a development stage. Compared to classical system as the lead-acid battery, Na-ion technology surpass in energy, specific properties and environmental friendliness. In comparison with the other Li-based technologies (Li-ion, Li-S, Li-Air), Na-ion lowers the device prices for a similar value of autonomy. However, the size of Na+ and its lower redox potential (+0.3V higher than for lithium) are still defying a suitable Na-ion batteries (NIB) technology. Therefore, there is increasing interest in coupling adequate positive and negative electrodes for maximizing the final device energy [1]. Despite the chemical and electrochemical resemblances of Li and Na, a number of negative electrodes for LIB shows very limited or none activity against sodium. For instance, graphite can intercalate 1/70 mole of sodium instead of 1/6 mole of lithium. Due to this limitation there is a wide research on positive electrodes in order to obtain high voltage systems. Current research in sodium-ion positive electrodes is focused on few families of inorganic compounds, namely transition metal layered oxides with O3, P2 and P3 crystal structures [2]. In this work we investigate P2-type electrodes based on NaxLiyM1-yO2 (M=Mn, Ni, Fe, Cr…) electrodes. The presence of partial Li substitution in the transition metal layer may assist the structural stability upon cycling. The active materials were synthesized using a sol-gel or solid state method, and characterized by XRD, SEM, TEM and BET techniques. Cyclic voltammetry and galvanostatic tests were performed using a two-electrodes cell using the metal oxide as working electrode and metallic sodium as pseudo- reference and counter electrode. Electrochemical impedance spectroscopy studies were performed using a three-electrodes cell using the metal oxide as working electrode and metallic sodium as counter and reference electrodes. [1] B.L. Ellis, L. F. Nazar, Current Opinion in Solid State and Materials Science 16 (2012) 168 [2] M.D. Slater, D. Kim, E. Lee, C.S. Johnson, Adv. Funct. Mater. 23, 947–958, 2013.

B.B.20
17:30
Authors : Kwangjin Park1, Dongwook Han2
Affiliations : 1Department of Mechanical Engineering, Gachon university, 1342 Sungnamdaero, Sujeong-Gu, Sungnam Si, Gyeonggi-do, [13120], Republic of Korea 2Deptartment of Materials Science and Engineering, Hallym University, 1, Hallymdaehak-gil, Chuncheon-si, Gangwon-do, [24252], Republic of Korea

Resume : We investigated that the recycling of protective layer for Ni rich layered oxide material for Li ion batteries. To decrease the electrochemical performance according to leaving of cathode powder in air was confirmed by various analysis due to formation of lithium residuals. The surface of protective layer was covered by the lithium residuals and that lead to cancel the coating effect. The residual lithium was decreased and the cell performance was recovered by applying the recycling process in this work. After the recycling process, the performance became similar to that immediately after the initial coating, and the coating layer showed a resurgence, which was confirmed by SEM and TEM images. The initial capacity for the initial coated Ni rich NCM and the sample after recycling was 209 mAh/g and 206 mAh/g at 1C, respectively. The cycle retention for the initial coated NCM and the sample after recycling was 93.4% and 92.6% after 50th cycles at 1C. It is concluded that the coating layer and the electrochemical performance was recovered by recycling process.

B.B.21
17:30
Authors : Jungho Song, Jongok Won†
Affiliations : Sejong University, Seoul, Gwangjin-gu, Seoul, Korea

Resume : As the importance of renewable energy has increased, Redox Flow battery (RFB) has received attention. As a secondary battery capable of storing a large amount of energy, RFB has attracted much attention as a long life, excellent stability, and a mass energy storage system(ESS). One of the components of RFB, ion exchange membrane, is a very important material that determines the performance of a battery. In Vanadium Redox Flow Battery, which is activated by reduction and oxidation of redox active species (Vanadium) in the organic electrolyte solution, the anion exchange membrane should be able to block the transport of the vanadium, allow the charge carrier, and have excellent ionic conductivity and thermal and chemical stability. Thus, a new IPN (Interpenetrated Polymer Network) anion exchange membrane was prepared by polymerizing [3- (methacryloylamino)propyl] trimethylammonium chloride (MAPTAC) with natural Urushiol that has high thermal and chemical stability. Due to addition of MAPTAC, ion conductivity was increased to 5.5*10-1 S/cm which is higer than that of pristine Celgard 2400. The porous Celgard 2400 was coated with Urushiol / MAPTAC and crosslinked at 95°C for 48 hours. The ion conductivity and vanadium permeability of the membrane were investigated and the performance of vanadium acetylacetonate based non-aqueous vanadium redox flow battery with Urushi/MAPTAC IPN anion exchange membrane was evaluated.

B.B.22
17:30
Authors : Jiyoon Jung, Jongok Won,Seung Sang Hwang†
Affiliations : Sejong University, Seoul, Gwangjin-gu, Seoul, Korea; Materials Architecturing Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul, Korea,

Resume : As energy use increases, there is a need for an energy storage system (ESS) for the storage of the renewable energy generation. Non-aqueous vanadium redox flow battery (VRFB) has attracted attention as an ESS due to its long cycle life and low pollution. One important component in VRFB is a membrane which separates the anode and cathode electrolytes and it maintains the electrical balance of the electrolyte during the charge-discharge process. Therefore, membrane for VRFB should have high ionic conductivity and low vanadium permeability. A new composite membrane for VRFB was prepared by coating Imidazolium-based ionic polysilsesquioxane (PSQ) on surfaces of the porous Celgard support which has a high ionic conductivity and excellent mechanical strength. PSQ has a ladder structure with double-stranded structure of Si-O-Si backbone, which has an excellent heat resistance and mechanical strength. New composite membrane showed a high ionic conductivity which is consistent with that of the pristine Celgard and the vanadium permeability decreased three order of magnitude of the pristine Celgard. VRFB cell performance test was performed, and the energy efficiency (EE) of the new membrane was 55% and the coulombic efficiency (CE) was 76% at 3mA/cm2, which was 16% and 21% higher than that of pristine Celgard, respectively. This result implies that a coated membrane on a porous support with an ionic PSQ is a promising anion conductive membrane for VRFB applications.

B.B.23
17:30
Authors : Kuan-Zong Fung [1,2], Shu-Yi Tsai [1,2], Li-Fu Chang [1], Bo-Yuan Huang[1],
Affiliations : 1. Department of Materials Science and Engineering, National Cheng Kung University, 70101 Tainan, TAIWAN; 2. Hierarchical Green-Energy Materials Research Center, National Cheng Kung University, 70101 Tainan, TAIWAN

Resume : Layered Composites formulated as xLi2MnO3-(1-x)LiMO2(M = Mn, Ni, Co, etc.) receive much attention due to their surprisingly high reversible capacity for Li-ion battery applications. For better understanding of such high-capacity layered cathode, a systematic study on powder morphology, crystal structures and reaction mechanisms of Li1.2Mn0.54Ni0.13Co0.13O2 during electrochemical charge/discharge cycles were conducted. For example, the capacity of Li-rich layered cathode powder was strongly affected by its particle size. To obtain various particle sizes of cathode powder, different powder synthesis routes have been adopted. From sol-gel process, particle size of Li1.2Mn0.54Ni0.13Co0.13O2 powder synthesized by solid-state reaction method gives particle size as coarse as 1.0μm. As a result shown in Fig.1, the initial discharge capacity of sol-gel processed Li-rich cathode was 250 mAh/g. After 40 cycles, the discharge capacity from the same cathode still shows a capacity as high as 205 mAh/g. However, for cathode powder obtained from solid-state reaction, its initial capacity was only 190 mAh/g that is 24% lower than that of sol-gel processed cathode. After 40 cycles, the capacity degraded to 137 mAh/g. The enhanced capacity of sol-gel processed Li-rich cathode is attributed to its enormous surface area and short Li diffusion distance provided for electrochemical reaction to take place. Although Li-rich layer-structured cathode capacity as high as 250 mAh/g at low rate, its electrochemical properties such as capacity loss at first cycle, rate capability and capacity fading still need to be examined and characterized. In this study, Li[Li0.2Mn0.54Ni0.13Co0.13]O2 were investigated. The TEM structural analysis shows that the evidence of spinel phase after cycling. It is believed that the transition from layered structure to spinel structure may also induce a large lattice distortion resulting in lattice breakdown and capacity fading. In additions, the phase transition may be caused by the redox reaction of transition metal ions through charging/discharging tests.

B.B.24
17:30
Authors : Savitha Thayumanasundaram*, Vijay Shankar Rangasamy, Jean-Pierre Locquet
Affiliations : Functional Nanosystems, KU Leuven, Celestijnenlaan 200D, Leuven, 3001-Belgium

Resume : Ionic liquids have been gaining attention as potential battery electrolytes mainly due to their high room temperature conductivity. In this study, we explore a heterogeneous doping model comprising ionic liquid doped polymer electrolytes. Polymer blends of Poly(vinyl alcohol) (PVA) and Poly(acrylic acid) (PAA) in different ratios were studied from which the blend composition of 25 mol% PAA - 75 mol% PVA polymer membrane was optimized based on thermal and mechanical properties. Electrolytes with 30, 50 and 70 mol% of 0.2 m LiTFSI-PYRTFSI added to the 75PVA:25PAA system were studied. The ionic liquid with pyrrolidinium cation was used because of its wide electrochemical stability window (5 V). A maximum ionic conductivity of 1 mS cm–1 is observed at 90 °C for the membrane with 70 mol% IL. Cyclic voltammetry of the 70 mol% IL doped polymer membrane shows peaks corresponding to the lithium stripping (+0.25 V vs. Li+/Li) and deposition (−0.3 V vs. Li+/Li) processes indicating the occurrence of a highly reversible redox process. Electrochemical characterization of the polymer/IL electrolyte was tested by assembling coin type half cells with Li4/3Ti5/3O4 (LTO) as the working electrode and lithium as the reference/counter electrode. The specific capacity of the first cycle is found to be 155 and 162 mAh/g for charge and discharge steps, respectively. Galvlanostatic charge-discharge study at different C-rates is also performed to analyze the rate capability of the assembled cell.

B.B.25
17:30
Authors : Kuan-Zong Fung [1,2], Shu-Yi Tsai [1,2], M. R. Lin [1], Isabel Sobrados [3], Maria. L. Calzada [3], Jesús Sanz [3], Ricardo Jiménez [3]
Affiliations : 1. Department of Materials Science and Engineering, National Cheng Kung University, 70101 Tainan, TAIWAN; 2. Hierarchical Green-Energy Materials Research Center, National Cheng Kung University, 70101 Tainan, TAIWAN; 3. Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC. C / Sor Juana Inés de la Cruz 3 , 28049, Cantoblanco, Madrid, Spain

Resume : Li ion batteries using inorganic solid electrolytes have received great attention recently due to its better safety feature. For instance, NASICON-structured Li1.3Al0.3Ti1.7(PO4)3 (LATP) is found to exhibit high ionic conductivity with adequate stability. The high interface polarization between solid electrolyte and cathode has been a major concern in all state Li ion batteries.. To reduce the interface polarization at electrode/electrolyte interface, composite electrode design consisting of solid electrolyte and electrode has been demonstrated. To obtain a good composite based on solid electrolyte/ and cathode powder mixture, a containing solid electrolyte and cathode, a cofiring process at high temperature is commonly used. Therefore, it is necessary to investigation the possible reaction in a composite cathode in order to suppress the interface reaction and exhibit desired electrochemical performance. In this study, the objective is to investigate the cathode/electrolyte reactions as a function of cofiring temperature, cathode structure and chemical compositions. LATP powder was obtained from solid state reaction using adequate amount of Li2CO3, TiO2, Al2O3, and NH4H2PO4 as raw materials. Li1.3Al0.3Ti1.7(PO4)3 with NASICON structure was obtained when calcined at 900ºC for 6 h. Cathodes with different crystal structures, such as olivine, and layerer structures, are selected. LATP is directly mixed with cathode powders and then heated at various temperatures. It is expected that the structural stability, morphology, and electrical/electrochemical properties of cathode will be affected by the reaction between solid electrolyte and cathode at high temperature. For instance, LATP tends to have reaction with layered oxide cathode. As a result, the conductivity of composite cathode will be reduced. The capacity of cathode will be suppressed as well. On the other hand, olivine-structured LiFePO4 and LATP having similar polyanion framew ork may show minimum reaction in comparison to layered oxides. Thus, the cathode reaction with LATP solid electrolyte will be investigated after annealing at different temperature. XRD, Electrochemical Impedance Spectroscopy (EIS), and cell testing will be performed to investigate the variation on structural, electrical and electrochemical properties

B.B.26
17:30
Authors : A.P. Nowak1, M. Sprynsky2, K. Trzciński1, M. Szkoda1, A. Lisowska-Oleksiak1
Affiliations : 1) Gdansk University of Technology, Faculty of Chemistry, Narutowicza 11/12, 80-233, Gdansk, Poland 2) Nicolaus Copernicus University, Facuty of Chemistry, Gagarina 11, 87-100 Torun, Poland

Resume : Recently the silicon oxide nanostructures were tested as and alternative anode material for lithium batteries [1-3]. Silica is one of the most popular material on Earth with high theoretical capacity of about 1965 mAh/g known to undergo faradaic processes in the presence of lithium ions at sufficiently high cathodic potential. The mechanism is given on the basis of HRTEM and SAED and XPS data as follows [2,3]: 5 SiO2 + 4 Li+ + 4e- = 2 Li2Si2O5 + Si (1) Si + xLi+ + xe- = LixSi (2) The reactions (1) and (2) are all reversible. Mechanism with irreversible silicate formation and lithium oxide creation is also possible: SiO2 +4 Li+ + 4e- = 2 Li2O + Si (3) 2 SiO2 + 4 Li+ + 4e- = Li4SiO4 + Si (4) The above electrochemical reactions of SiO2 can be a source of high theoretical capacity, significantly higher than capacity of LiC6. Here we show the influence of thermal treatment of the studied electrode material on the electrochemical properties of the electrode material. [1] A. Lisowska-Oleksiak, A.P. Nowak, B. Wicikowska, RSC Adv., 4 (2014) 40439. [2] N. Yan, F. Wang, H. Zhong, Y. Li, Y. Wang, L. Hu and Q. Chen, Scientific Reports, 3 (2013)1568. [3] Q. Sun, B. Zhang, Z.-W. Fu, Appl. Surf. Sci., 254 (2008) 3774.

B.B.27
17:30
Authors : A.P. Nowak, M. Wrotny, K. Trzciński, M. Szkoda, A. Lisowska-Oleksiak
Affiliations : Gdansk University of Technology, Faculty of Chemistry, Narutowicza 11/12, 80-233, Gdansk, Poland

Resume : The necessity of minimising the emission of carbon dioxide results in constant development of research on renewable energy sources, such as lithium-ion batteries. This is particularly visible in the increasingly popular hybrid cars, plug-in hybrid cars or electric cars, prices of which significantly decreased recently. For that reason, much attention is being paid to research on the new generation of high-energy lithium batteries, operating parameters of which would make powering zero-emission electric motors. Nowadays graphite is used as an electrode material. However, graphite electrode is not suitable for the next-generation lithium ion batteries that is smart electrical grid systems and electric vehicles1. Silicon and silica are expected to replace graphite electrode in the next-generation lithium-ion batteries2,3. Here we show diatomic earth as an anode material of Si@SiOx type for lithium-ion batteries. [1] K.M. Abraham, Prospects and limits of energy storage in batteries, J. Phys. Chem. Lett., 6 (2015) 830-844 [2] R. Teki, M. K. Datta, R. Krishnan, T. C. Parker, T.-M. Lu, P. N. Kumta, N Koratkar, Nanostructured Silicon Anodes for Lithium Ion Rechargeable Batteries, Small, 5 (2009) 2236-2242 [3] A. Lisowska-Oleksiak, A.P. Nowak, B. Wicikowska, Polish Patant Application, P.413911, 2014

B.B.28
17:30
Authors : N. Briguglio, C. D’Urso, , V. Baglio, V. Antonucci, A.S. Aricò
Affiliations : CNR-ITAE

Resume : ZEBRA batteries (Zero Emission Battery Research Activities) for their high energy and power density are one of the possible solutions to electrical storage for stationary applications. These systems are based on nickel chloride-sodium cells operating at high temperatures (about 270°–350 °C), and rely on a ceramic β”-alumina tube or planar membrane as solid electrolyte. In this work, recent results generated from 3 cm2 button cells, including base line cell performance, cell design and chemistry will be presented. The activity was directed to the realization of two new planar configuration of a beta sodium battery, that means the study of a planar sealing between the metal and the ceramic components. This battery, as many other electrochemical storage technologies, may play an important role for the transmission and distribution of electricity, because it can satisfy, in a very flexible way, many different needs (voltage and frequency control, self consumption of stochastic renewable energy, peak shaving etc.). For this purpose the storage system has to be characterized not only by a suitable energy capacity, but by quick response and high power performance too. A planar configuration could optimize the battery in terms not only of energy density (already satisfactory for this kind of batteries), but also of power density (still to be improved). The planar configuration could also provide a better stack design and thermal regulation. This battery utilizes a ceramic material as the ionic membrane between the anodic and cathodic semi cells and so it has to operate at 300°C. The current form of the β”-alumina membrane is “glass shaped” in order to contain the reagents, so the possible planar shape has to include a sealing system able to contain the reagents, which are in liquid status at the high temperature of the battery and they are also highly chemical reactive, especially the liquid sodium. In particular the research activity was previously directed to the study of the components of the seal between the metal bodies of the semi cells and the ceramic beta alumina and afterwards to a new configuration of the sealing system. The studied materials were insulating paints, ceramic pastes and glass seals and they were tested in order to assess their chemical stability in presence of sodium and their mechanical stability during thermal cycling. The research activity was addressed to define the right geometry of the ceramic support of the β”-alumina. Another purpose was to define a mechanical seals between the ceramics support and metallic body of the two, anodic and cathodic, electrodic compartments. A new activity was started to realize a new configuration in which also the body of battery was realized in ceramic material (α-Alumina), which allows a greater wettability in the anodic compartment. During the experimentation the seal materials were chosen, the activity was directed to evaluate the performances of a planar mono cell to thermal cycles, simulating the charge and discharge temperature profiles, typical of the operating battery. The mono cell was realized with a new sealing system, composed by a new geometry of a ceramic ring to contain the beta alumina membrane and to guarantee the mechanical stability. In both planar configurations of the cell made, it has been noticed that this type of design reduces the volume of the cathodic and anodic semi cell; in this way, not only the energy density is increased but also the power density is improved. Furthermore, the planar design would improve the stack geometry and its thermal distribution. The problems faced in this work were the material resistance to the chemical attack of liquid sodium at high temperature, the mechanical resistance and the compensation of the different thermal expansion coefficient between the solid electrolyte (β-alumina) and the metallic body. The first button cell consisted of two battery cases (stainless steel) for cathode and anode sides, a Nichel network cathode current collector, a stainless steel anode current collector, an α-alumina (99.5% purity) fixture and a planar composite yttria-stabilized zirconia (YSZ)/ BASE (3 cm2 active area) disc. The second buttom cell consisted of battery cases (α-Alumina) for cathode and anode sides, a steel plate held by a spring as a current collector both at the anode and at the cathode (the use of springs makes it possible to better exploit cathodic and anodic active materials), an α-alumina (99.5% purity) fixture and a planar composite yttria-stabilized zirconia (YSZ)/ BASE (3 cm2 active area) disc. It is using an inexpensive stacked design to improve performance at lower temperatures, leading to a less expensive overall storage technology. The new design greatly simplifies the manufacturing process, providing a subsequent pathway to the production of scalable, modular batteries at half the cost of the existing tubular designs.

B.B.29
17:30
Authors : Maria Anna Cusenza*, Sonia Longo, Francesco Guarino, Maurizio Cellura
Affiliations : Department of Energy, Information Engineering and Mathematical Models, Università degli Studi di Palermo, Italy

Resume : The increasing use of renewable energy technologies for the electricity generation in buildings will require a growing number of energy storage systems (ESSs) in the next years in order to reduce the mismatch between the highly variable on-site electricity generation and the building load. Retired electric vehicle batteries (EVBs), before recycling, can be used for this purpose, considering that they have about 80% of the original energy capacity. In this context, the study aims at examining an ESS made by retired EVBs, in order to identify its optimal size for reducing the mismatch in a net zero energy building equipped with a photovoltaic plant and to assess the life cycle energy and environmental impacts/benefits of the energy system. The case study is represented by a real building for which monitored data on load and on-site generation are available. The functional unit (FU) of the analysis is the electrical energy required by the building in a time scale of 12 years (98,823 kWh). The main outcomes of the study are: the determination of the storage size realized with retired EVBs for the load match optimization in the analysed building, and the eco-profile of the energy system that deliver the performance described by the FU. The study represents an original environmental sustainability analysis, combining the load match analysis and the life cycle approach, of the synergy, inspired to the principles of the circular economy, between the building and the automotive sector.

B.B.30
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B5 : ROBERT KOSTECKI
09:00
Authors : Marisa Falco, Laurent Castro, Jijeesh Ravi Nair, Federico Bella, Fanny Bardé, Giuseppina Meligrana, Claudio Gerbaldi
Affiliations : GAME Lab, Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino, Italy (Marisa Falco, Jijeesh Ravi Nair, Federico Bella, Giuseppina Meligrana, Claudio Gerbaldi); Research & Development 3, Advanced Technology 1, Toyota Motor Europe, Hoge Wei 33 B, B-1930-Zaventem, Belgium (Laurent Castro, Fanny Bardé)

Resume : Among the oxide ceramic super lithium ion conductors, garnet-type Li7La3Zr2O12 (LLZO) has recently attracted much attention because of its relatively high ionic conductivity at room temperature (>10-4 S cm–1), negligible electronic conductivity and absence of harmful decomposition products upon contact with atmospheric moisture. Recent efforts have been dedicated to the formulation of composite hybrid polymer electrolytes (CPEs), where the ceramic material is embedded in a polymeric matrix. CPEs are stiff while preserving flexibility, are easily processed, and can be conceived to attain improved ionic conductivity and interfacial contact with the electrodes [1]. Here, a polymer based matrix containing poly(ethylene oxide) (PEO), lithium bis (trifluoromethylsulphonyl)imide (LiTFSI), tetra(ethylene glycol dimethyl ether) (G4) and a photoinitiator was added with LLZO particles, thoroughly mixed, formed into a film and crosslinked under UV radiation to obtain a composite hybrid electrolyte [2]. This easy procedure allows obtaining self-standing CPEs with desirable properties of flexibility, shape retention upon thermal stress, improved interfacial contact with the electrodes and ionic conductivity suitable for practical application. Lab-scale lithium metal cells assembled with the CPEs and LiFePO4 cathodes demonstrated specific capacities up to 125 mAh g-1 at 1C rate and could work for hundreds of cycles at ambient temperature. [1] C.K. Chan, T. Yang, J.M. Weller, Electrochim. Acta 253 (2017) 268. [2] L. Porcarelli, C. Gerbaldi, F. Bella, J.R. Nair, Sci. Rep. 6 (2016) 19892.

B.5.1
09:30
Authors : Jeanette Münderlein, Marc Steinhoff, Hendrik Axelsen, Dir Uwe Sauer
Affiliations : ISEA, RWTH Aachen

Resume : The increasing trend of replacing traditional fossil fuels by renewable energy sources in the last 5 years leads to a more sustainable energy supply. However, the positive development is also connected with new challenges. In particular the volatile energy generation and the fluctuating consumption causes imbalances in the power grid. Furthermore, the trading interactions on the electricity exchange market result in frequency deviations. To ensure a stable energy supply robust balancing systems are necessary. This challenging issue can be solved by the integration of battery storage systems (BSS). Based on this motivation the M5BAT project was established. Within this project, a 5 MW and 5 MWh battery storage system was built. The system is composed of five different battery technologies like valve-regulated lead acid, vented lead acid and different lithium-ion technologies (LMO, LTO, and LFP). The setup consists of ten strings, which can be operated independently from each other. One of the aims of the project is the investigation what kind of battery type or which combinations of batteries can be used in an economical way. This will be analyzed for different marketing strategies. Within this context frequency control reserve (FCR) market has a great profitable potential in Germany. In order to ensure a holistic understanding and to derive a resilient evaluation of the BSS, it was operated with 2 MW in the frequency control market. The trading of the FCR takes place on the electricity exchange market according to the “pay-as-bid” approach and with a one-week timeline. The operation is controlled by a sophisticated and intelligent energy management system (EMS). The EMS assumes the function to allocate the requested performance to each string. Within the first part of the paper, the strategy for the power distribution among each string and their influence on the efficiency will be explained and evaluated. Thereby, not only the EMS has a high influence on an economical operation but also the converter settings and dimensions. The effects and their impact will be discussed in detail. For this analysis, the energy throughput for each trading week will be determined with regards to the degrees of freedom (DOF). Based on the real operating BSS the savings can be reliably evaluated. Besides this, another very important part of high impact on the profitability is the technical building equipment (TBE) like air conditioning and ventilation. In the last part of the paper, the setup, the mode of operation and the resulting power consumption will be presented. From this holistic consideration of the BSS operation strategies and the FCR market, the overall losses and saving potentials will be determined. Within this contribution, the possibilities, as well as further challenges for the operation of a storage system with different battery technologies, are discussed in detail. Moreover, from the comprehensive results guidelines for the design and a sustainable commercialization strategy are derived.

B.5.2
09:45
Authors : Jianli Cheng*1, Bin Wang1
Affiliations : Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, Sichuan 621900

Resume : Wearable electronics is emerging as a new and promising field that may revolutionize our life in the near future, and it is currently limited by finding matching power systems with high energy density, good flexibility and high stretchability.[1-4] Among them, stretchable fiber-shaped supercapacitors (SFSSs) are considered as one of the most promising candidates as they can be easily realized by winding fiber electrode on elastomeric substrate or assembling fiber electrodes into a helical structure.[5, 6] However, on one hand, it remains challenging to achieve both high energy density and high stretchabilities based on the available technologies. Herein, an all-in-one fiber electrode combining the function of traditional metal wire and energy storage has been designed and synthesized to solve the above problem. A crystalline conductive polymer (CP) fiber that displayed combined high conductivity, flexibility, specific capacitance and wide electrochemical window was discovered to simultaneously realize high energy storage and serve as conducting wire. The designed fiber material from poly(3,4-ethylenedioxythiophene) (PEDOT):poly(styrene sulfonate) (PSS) after treatment by sulfuric acid (denoted as PEDOT-S:PSS) showed high tensile strength of 112 MPa and high electrical conductivity of 1731 S cm-1 due to the structure rearrangement and ordered crystallized structure. The resulting symmetric SFSSs achieved a wide potential window of 1.6 V, specific capacitance of 93.1 mF cm-2 (or 74.5 F cm-3) at 50 µA cm-2 and high energy density of up to 33.2 µW h cm-2 (26.4 mW h cm-3) based on single fiber electrode. To the best of our knowledge, it represents the highest energy density in the available FSSs. They can be repeatedly stretched by 800%, and the specific capacitance can be well maintained after stretching for 200 cycles and bending for 2000 cycles. [1] J. Bae, M. K. Song, Y. J. Park, J. M. Kim, M. Liu, Z. L. Wang, Angew. Chem. Int. Ed. 2011, 50, 1683. [2] X. Wang, K. Jiang, G. Shen, Mater. Today 2015, 18, 265. [3] W. Weng, S. He, X. Sun, H. Peng, Angew. Chem. Int. Ed. 2016, 55, 6140. [4] W. Zeng, L. Shu, Q. Li, S. Chen, F. Wang, X. M. Tao, Adv. Mater. 2014, 26, 5310. [5] Z. Yang, J. Deng, X. Chen, J. Ren, H. Peng, Angew. Chem. Int. Ed. 2013, 52, 13453. [6] Y. Shang, C. Wang, X. He, J. Li, Q. Peng, E. Shi, R. Wang, S. Du, A. Cao, Y. Li, Nano Energy 2015, 12, 401.

B.5.3
10:00
Authors : Lu Guo, Dezhi Kong, Meng Ding, Yang Hui Ying*
Affiliations : Singapore University of Technology and Design

Resume : Membrane capacitive deionization (MCDI) has become more and more attracting due to its easy operation, high safety, environmental friendliness, energy efficient and cost effectiveness. There exist two different operational modes in traditional MCDI, constant current (CC) and constant voltage (CV) modes. And varieties of parameters have been adopted to investigate the difference of CC and CV operational modes, such as flow rate, cell potential, current density and feed water concentration. Most recently, a new parameter faradaic reaction has been introduced into MCDI system. Unlike traditional physical adsorption by the electrical double layers (EDLs) of the porous materials, the salt ions in water will be intercalated into the crystal structure of the electrode materials with the introducing of faradaic reaction, which means the salt adsorption capacity will not be restricted by the surface area of the porous materials any more. Therefore, in this work, the influence of faradaic material in CC and CV operational modes MCDI upon different choices of electrode materials has been analyzed. The salt removal capacity and charge efficiency have been enhanced under the influence of faradaic reaction. And the energy consumption has been much decreased. Meanwhile, faradaic reaction has been proven to be more incline to happen under CC operational mode MCDI, indicating its advantage over CV operational mode with certain choice of electrode materials.

B.5.4
10:15
Authors : Daniel Adjei Agyeman, Kang Yong-Mook
Affiliations : Dept. of Energy Materials Engineering, Dongguk university

Resume : The global effort to improve the lifetime, power densities and energy efficiency of energy storage and conversion technologies, such as batteries, fuel cells, and supercapacitors, has become dramatically more extensive with increased demand from portable electronics and the electrification of transportation. Currently, lithium- oxygen (Li-O2) batteries have been considered as the most promising next-generation electrochemical energy storage technology to meet near future transportation application. Contrary to the traditional Li-ion batteries, Li-O2 batteries abandon the intercalation and conversion reaction electrodes and Li ions react directly with O2 from the air in a porous electrode. This unique battery chemistry and electrode architecture induce an extremely large theoretical specific energy ~ 3600 W h kg-1, which is considered capable of providing enough energy storage capability for electric vehicles to drive more than 500 miles (per charge). In this work, several promising efficient catalysts for Li-O2 batteries have been synthesized as novel cathode catalysts and their electrochemical performance have been investigated in the viewpoint of their electrical conductivity and structural properties

B.5.5
10:30 COFFEE BREAK    
 
B6 : CHIARA FERRARA
11:00
Authors : Asma Marzouk a, Fernando Sotto b, Kie Hankins b, Victor Ponce b, Laura Benitez b,c, Jorge M. Seminario b,c,d*, Perla B. Balbuena b, * and Fadwa El-Mellouhi a,*
Affiliations : a Hamad Bin Khalifa University, Qatar Environment and Energy Research Institute, PO BOX 34110, Doha, Qatar b Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States c Department of Electrical and Computer Engineering, Texas A&M University College Station, Texas 77843, United States d Department of Materials Science and Engineering, Texas A&M University College Station, Texas 77843, United States

Resume : The complexity of the solid electrolyte interphase (SEI) in lithium-ion batteries with graphitic electrodes, has triggered extensive deal of research due to its crucial properties for the long life of the battery. The SEI layer is composed of organic and inorganic species and results from the electrolyte decomposition on the electrode-electrolyte interface upon the first cycling of the battery. A stable SEI layer is crucial to maintaining the chemical and mechanical stability of the electrode, and the electrochemical stability of the electrolyte in order to prevent irreversible capacity loss. This work uses computational crystal structure prediction genetic evolutionary algorithm to simulate the nucleation, the growth and the aggregation of the inorganic products forming the SEI mosaic film. In-depth investigation of the growth mechanisms of LiF and Li2CO3 starting from the first nucleation seeds is undertaken. The nearshore SEI layer cluster aggregation growth mode at the graphite surface is shown to be strongly dependent on its degree of lithiation and surface termination states.  Acknowledgments: This work is sponsored by the Qatar Environment and Energy Research Institute (FE). Computational resources have been provided by the research computing team at Texas A&M University at Qatar. This work is supported by the Qatar National Research Fund (QNRF) through the National Priorities Research Program (NPRP7-162-2-077)

B.6.1
11:30
Authors : Plawan Kumar Jha, Santosh Kumar Singh, Vikash Kumar, Shammi Rana, Sreekumar Kurungot, and Nirmalya Ballav
Affiliations : Plawan Kumar Jha; Vikash Kumar; Shammi Rana; Nirmalya Ballav, Department of Chemistry, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pune, Maharashtra-411 008; India. Center for Energy Science, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pune, Maharashtra-411 008, India. Santosh Kumar Singh; Sreekumar Kurungot, Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory (NCL), Dr. Homi Bhabha Road, Pune, Maharashtra-411 008, India

Resume : Graphene-based materials are emerging as smart alternatives to activated carbon used in commercial supercapacitor. Here, we present chemical reduction of graphene oxide (GO) in aqueous medium by an unconventional mild reducing agent (FeCl2/HCl) where self-assembled reduced graphene oxide (rGO) is isolated and the reducing agent is recycled upon simple treatment of the filtrate with HCl. The fabricated all-solid-state supercapacitor of as-synthesized rGO exhibited significantly higher specific capacitance (171 F/g at 1.1 A/g), remarkable cycling stability (>80% retention of capacitance beyond 100,000 continued cycles), and flexibility (>500 bending cycles), which is comparatively much better than those of rGO derived from conventional reducing agents like NaBH4 and N2H4. Use of organic electrolyte further boosted the supercapacitor performance (282 F/g at 1.8 A/g) of rGO. This work opens up new possibilities for the production of rGO on an industrial scale satisfying the needs of high-performance energy-storage devices.

B.6.2
11:45
Authors : Fu-Ming Wang
Affiliations : Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology

Resume : In January 2017, Samsung announced the reason why the Note 7 explodes and losses of more than 5 billion US dollar. According to their explanations, it was caused by the internal short circuit problem in the lithium ion battery. Currently, there is no effectively solution for eliminating the internal short circuit problem owing to the sudden accident. In this research, a new technology has been developed, which can be used to terminate the thermal runaway and promise the safety performance of lithium ion battery. High voltage Li-excess and Ni-rich layer-type cathode material are employed and combined with this safety electrode additive for investigation. In terms of the results, the new technology LIVING@ additive significantly enhances the cycle performance at 60oC and high voltage. In addition, the following figures illustrated that the battery containing LIVING@ technology is stable and passed the nail penetration test. On the other hand, the battery without LIVING@ cannot be used when the short problem is taking place. The LIVING@ contains self-polymerized hyper branch structure in order to insulate the directly contact between anode and cathode. This electrode additive not only provides high thermal stability on electrochemical reaction, but the columbic efficiency of charge-discharge is also enhanced.

B.6.3
12:00
Authors : J. E. García-Béjar,1 L. Álvarez-Contreras,2 M. Guerra-Balcázar,3 J. Ledesma-García,3 L. G. Arriaga1 and N. Arjona1*
Affiliations : 1 Centro de Investigación y Desarrollo Tecnológico en Electroquímica S. C., Querétaro, C. P. 76703, México. 2 Centro de Investigación en Materiales Avanzados S. C., Complejo Industrial Chihuahua, Chihuahua, C. P. 31136, México. 3 Facultad de Ingeniería, División de Investigación y Posgrado, Universidad Autónoma de Querétaro, Querétaro, C. P. 76010, México.

Resume : Oxygen reduction reaction is a complex reaction that is involved in energy conversion applications such as air-based batteries and fuel cells. The high price of Pt makes necessary the development of highly durable electrocatalysts. In this sense, transition metal oxides mixtures have shown remarkable results in both, air-batteries and fuel cells. In this work, a TMOM based on Ni and Mo with a small content of Tungstic acid (WA) as additive (denoted as MoNiW) was synthesized following a polyol route using polyvinylpyrrolidone, ethylene glycol and ascorbic acid as the stabilizer, reaction media/reducing agent and co-reducing agent, respectively. A Mo-Ni TMOM without WA was synthesized as control, and according with TEM micrographs it presented particle sizes ranging from 40 to 70 nm. The addition of WA to the MoNiW TMOM decreased the particle size to 19.7±0.5 nm, and promoted the formation of particles with defined shapes regardless particle size: semispherical and cubic-like shapes, being the nanocubes indexed to NiO. Evaluation of the oxygen reduction reaction in alkaline medium (0.1 M KOH) was carried using a rotating disk electrode. At 1600 rpm, the MoNiW catalyst exhibited a half-wave potential of 0.68 V vs. RHE with a current density of 3.2 mA cm-2, and in comparison, with commercial Pt/C, the MoNiW catalyst has a overpotential of only 170 mV. Therefore, herein we demonstrated the high activity of a MoNiW electrocatalyst for ORR in alkaline medium as a promising material for energy conversion applications.

B.6.4
12:15
Authors : Julia Amici, Mojtaba Alidoost, Usman Zubair, Daniele Versaci, Carlotta Francia, Silvia Bodoardo, Nerino Penazzi
Affiliations : Politecnico di Torino DISAT Corso Duca degli Abruzzi 24 10129 Torino

Resume : With increasing demands for high-energy density, lithium sulfur batteries are becoming an appealing technology. As a matter of fact, in addition to a high theoretical capacity of 1672 mA h g-1, S is also lightweight, cheap, widely available as well as non-toxic and safe. All these factors combined justify its appeal for large-scale applications. Up to now, the main explanation for not reaching the theoretical values is the unfavorable behavior of polysulfides (PS) formed during cathode reaction. During the discharge reaction, elemental S is reduced to form PS. During the following charging process, the reaction should be completely reversed, however, the good solubility of most PS in most liquid electrolytes induces loss of active material and hence rapid capacity decay upon cycling. Moreover, direct reaction of those PS onto metallic Li anode forms a passivating layer and alters anode surface (dendrite formation). A promising approach to solve these issues is the use of polymer membranes in different positions inside the cell. As a matter of fact, the versatility of polymer matrices combined to a very wide range of compatible additives allows to unite the advantages of different material classes, thus producing a solution to nearly every problem encountered. For instance, a polymer/ceramic composite membrane, based on PVDF-HFP, sandwiched between cathode and separator, can actively confine the PS on cathode surface, limiting the shuttle effect and greatly expanding cycle life. Another type of membrane, methacrylate-based, containing different additives and photo-reticulated directly onto the metallic Li anode to obtain a greater contact, can reduce to a minimum dendrite formation.

B.6.5
12:30 LUNCH BREAK    
 
B7 : CLAUDIO GERBALDI
14:00
Authors : Ivana Hasa, Atetegeb Meazah Haregewoin, Lydia Terborg, Liang Zhang, Sunhyung Jurng*, Brett L. Lucht*, Jinghua Guo, Philip N. Ross, Robert Kostecki
Affiliations : Lawrence Berkeley National LaboratoryBerkeley, CA94720, USA *University of Rhode Island, Kingston, Rhode Island 02881, USA

Resume : Intermetallic (Si, Sn, Sb etc.) electrodes offer significantly higher volumetric and gravimetric energy density compared to the widely used graphite-based electrodes, which make them promising candidates for next generation Li-ion cells for transportation applications. [1] However, numerous studies have demonstrated that the inherently non-passivating behavior of intermetallic electrodes in standard organic carbonate-based Li-ion electrolytes [2] is aggravated by significant volume changes during the charging and discharging processes. Mechanical stresses from volume change lead to particle decrepitation, resulting in electronic isolation of particles, loss of mechanical integrity of composite electrodes and interfacial instability. Particle factures expose fresh electrode surface to the electrolyte during cycling, leading to formation of a thick film of electrolyte reduction products, causing impedance rise, capacity loss and lithium inventory shift in the cell. [3] The solid electrolyte interphase (SEI) layer, which forms at the electrode/electrolyte interface during the initial charge/discharge cycles, is the key component that determines the long-term stability and cycling behavior of negative Li-ion battery electrodes. [4-6] Electrolyte reduction and SEI layer formation on these electrodes usually take place at potentials below 1.8V vs. Li/Li+ and accompany the formation of Li-Me phases, the so-called “Me-Li alloying” process at E <0.8 V vs. Li/Li+. The exact mechanism of the SEI formation processes on Si, Sn, Sb and their alloys with lithium, the SEI composition and the effect on the electrode electrochemical cycling performance is not well understood. Interestingly, model studies on Sn single crystal electrodes in organic carbonate electrolytes revealed a strong correlation between the crystal surface orientation and the SEI composition. [7,8] A similar study of the composition of the SEI on a silicon monocrystal electrode showed strong effects of different SEI formation protocols, presence/absence of intrinsic SiO2, electrolyte composition and impurities e.g., HF. On the other hand, SEI-forming electrolyte additives such as vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are known to alter the composition and properties of the SEI on Si and improve the electrode electrochemical performance. This study involves rigorous diagnostic studies of tin, silicon, Si-based alloys, and composite Si-based model electrodes to determine and understand the key thermodynamic and kinetic parameters, which enable their function and operation in Li-ion battery systems. Advanced diagnostic tools are used to gain fundamental insight into mechanism of intermatallic-based electrodes failure. An emphasis is placed on in situ methods that use multiple techniques at the same time e.g., imaging with spectroscopy. The diagnostic experimental strategies involve evaluations of model silicon and other intermetallic model composite electrodes as well as studies of the properties of the individual components and their interfaces in a carefully designed and well defined experimental systems. The interfacial instability of the electrolyte and the uncertainty associated with the formation of a stable solid electrolyte interphase (SEI) are the key problems being addressed. Acknowledgements This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under the Applied Battery Research for Transportation (ABR) Program and Award Number DE-EE0006443.

B.7.1
14:30
Authors : Faiz Ahmed, Sabuj Chandra Sutradhar, Taewook Ryu, Soojin Yoon, Hanmo Yang, Inhwan Choi, Md Mahabubur Rahman, Whangi Kim*
Affiliations : Department of Applied Chemistry, Konkuk University, Chungju 380-701, Republic of Korea

Resume : Novel non-aqueous organic electrolytes with wide electrochemical window and high ionic conductivity have great potential for rechargeable lithium-ion batteries. Herein, we report the synthesis and performance of three ionic salts such as lithium carbonylbis(fluorosulfonyl)amide, lithium (1,3-phenylenedisulfonyl)bis(sulfamoyl fluoride), and lithium ((4-flurophenyl)sulfonyl)amide, respectively. The electrolyte salts with two lithium shows better performances such as high ionic conductivity, cyclic, and electrochemical stability compared to mono-valent salt ((lithium ((4-flurophenyl)sulfonyl)amide)) due to the high concentration of the lithium ion in the solution and formation of stable solid electrolyte interface (SEI) layer on the electrode surface. Full Li-ion batteries based on these electrolytes (1 M electrolyte solution in ethylene carbonate/dimethyl sulfoxide solvent) using LiCoO2 cathode and graphite anode will exhibit good specific discharge capacity in conjunction with conventional organic solvent-based electrolytes. The structures of the resultant electrolytes were confirmed by 1H-NMR and 19F NMR spectroscopy. The properties and performances of the resultant electrolytes were investigated by differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), cyclic and linear sweep voltammetry (CV and LSV).

B.7.2
14:45
Authors : M. Lo Faro, S. Trocino, S. C. Zignani, V. Antonucci and A. S. Aricò
Affiliations : CNR-ITAE, Via salita Santa Lucia sopra Contesse 5, 98126 Messina, Italy

Resume : This communication delas with the evaluation of a Fe-air battery cell for application as electric energy storage device at intermediate temperature (500-700 °C). Zhao et al. suggested an architecture similar to a reversible SOFC/SOEC cell combined with an active Fe-electrode placed in the same closed fuel electrode chamber [1]. The operation of such cell consisted in a combination of a reversible SOFC/SOEC cell with the redox cycle of Fe-Fe2O3 and requires a recirculation of H2/H2O. The net electromotive force is given by the Fe-redox couple. Although they achieved good performance, such architecture is affected by cells stacking constraints. In this work we explored the feasibility of a simply architecture consisted of a sandwich based on Fe2O3-CGO as Fe electrode, La0.8Sr0.2Ga0.8Mg0.2O3 (LSGM) or Gd0.1Ce0.9O2 as supporting electrolyte and La0.6Sr0.4Fe0.8Co0.2O3 (LSFCO) as O2 electrode. Such type of cell had an architecture similar to a SOFC cell. However, such cell did not require any gas recirculation, whereas no internal manifold of gas is expected in a stack of these cells. The cell battery based on CGO showed a significant propensity to the spontaneous discharge due to low electrical stability of the Ce(IV) and due to its large capability for the oxygen storage. On the other hand, LSGM based cell battery showed at 650 °C a stable cycling behaviour (over 100 cycles) quite high current capacity (450 mAh g-1), energy density (400 mWh g-1), and voltage efficiency (75%).

B.7.3
15:15
Authors : Longtao Ma, Chunyi Zhi
Affiliations : Department of Materials Science and Engineering, City University of Hong Kong

Resume : The exploitation of a high-efficient, low-cost and stable non-noble metal-based catalyst with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) simultaneously, as air electrode material for rechargeable zinc-air battery is significantly crucial. Meanwhile, the compressible flexibility of a battery is the prerequisite of wearable or/and portable electronics. Herein, we present a strategy via single-site dispersing Fe-Nx species on a two dimensional (2D) highly-graphitic porous nitrogen-doped carbon layer to implement superior catalytic activity toward ORR/OER (with a half-wave potential of 0.86 V for ORR and an over-potential of 390 mV at 10 mA·cm-2 for OER) in alkaline medium. Furthermore, an elastic polyacrylamide (PAM) hydrogel based electrolyte with the capability to remain great elasticity even under highly corrosive alkaline environment, is utilized to develop a solid-state compressible and rechargeable zinc-air battery. The creatively developed battery performs a low charge-discharge voltage gap (0.78 V at 5 mA·cm-2) and large power density (118 mW·cm-2). It could be compressed up to 54% strain and bended up to 90o without charge/discharge performance and output power degradation. Our results reveal that single-site dispersion of catalytic active sites on porous support for bi-functional oxygen catalyst as cathode integrating specially designed elastic electrolyte are feasible strategies for fabricating efficient compressible and rechargeable zinc-air batteries, which could enlighten the design and development of other functional electronic devices.

B.7.4
15:15
Authors : Lucie Blondeau, Magali Gauthier, Eddy Foy, Suzy Surblé, Hicham Khodja
Affiliations : NIMBE; CEA; CNRS; Université Paris-Saclay; CEA Saclay 91191 Gif-sur-Yvette France

Resume : Magnesium batteries are promising candidates as an alternative to Li-ion batteries thanks to its high abundance, low cost, safety and theoretical capacity (2.2Ah/g -3.8Ah/cm3). Nonetheless metallic Mg reacts with conventional electrolytes to form a barrier on its surface, rendering cation exchange impossible, and thus dramatically limiting reversible stripping/deposition of Mg. An interesting alternative for the development of Mg batteries is to replace Mg metal with another negative electrode, compatible with conventional electrolytes. Recently, it has been showed that p-block elements (Sn, Sb, In, Pb, Bi) can electrochemically alloy with Mg and possess adequate stability in conventional electrolytes [1]. To evaluate a possible synergy effect between different elements as already observed for SnSb [2] and BiSb [3], we synthetized InSb powder through high energy ball-milling. This alloy may be of great interest as it would combine the high theoretical capacity of Sb (660mAh/g) and the lowest working potential reported for In in a Mg battery. Here we demonstrate that the combination of In and Sb has a beneficial effect on the reaction mechanisms and enables higher specific capacities compared to In-based electrodes. The characterization of the peculiar electrochemical behavior of InSb will also be described in details. 1. Murgia et al., Electrochem. Commun. 60, 56 (2015) 2. Parent et al., Nano Lett. 15, 1177 (2015) 3. Arthur et al., Electrochem. Commun. 16, 103 (2012)

B.7.5
15:30 COFFEE BREAK    
 
B8 : EL-MELLOUHI FADWA
16:00
Authors : Chiara Ferrara
Affiliations : Department of Chemistry, , Via Taramelli 12, 27100 Pavia, Italy

Resume : Elemental phosphorous is emerging as one of the most intriguing anode materials for Li, Na, and K rechargeable batteries due to its specific capacity of 2596 mAhg-1. At the same time, the performances obtained from different tests are far from the theoretical values (~600-1000 mAhg-1). Moreover, no clear indications about the phosphorous form most suitable for electrochemical applications is emerged until now. Elemental phosphorous exists as different allotropes, including white phosphorous, WP, red phosphorous, RP, and black phosphorous, BP. Orthorhombic BP, the most stable polymorph, presents a 2D structure, making it particularly intriguing as anode material. The preparation of ortho-BP is thus a central issue in development of anodes based on elemental P. Among the variety of complex synthesis approaches, high energy ball milling, HEBM, starting from the commercially available RP appears to be the most convenient. Even if HEBM is one of the most diffuse preparation method and several experimental procedures have been proposed, no systematic exploration of the synthesis parameters has been tackled to date. Here, we report on a detailed investigation of the role of the synthesis conditions, together with the characterization of the obtained products. A careful spectroscopic investigation coupled with multivariate analysis allowed us to state how the different HEBM parameters (speed, filling factor, duration) can be tuned to control the nature of the final products.

B.8.1
16:30
Authors : Pierre Lannelongue, Charlotte Bodin, Camille Douard, Antonella Iadecola, Steven Le Vot, Olivier Fontaine, Thierry Brousse, Frédéric Favier
Affiliations : Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier, France - Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France ; Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier, France - Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France ; Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France - Institut des Matériaux Jean Rouxel (IMN), CNRS UMR 6502, Université de Nantes, Nantes, France ; Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France ; Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier, France - Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France ; Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier, France - Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France ; Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France - Institut des Matériaux Jean Rouxel (IMN), CNRS UMR 6502, Université de Nantes, Nantes, France ; Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, 34095 Montpellier, France - Réseau sur le Stockage Electrochimique de l’Energie, CNRS FR 3459, 80039 Amiens, France

Resume : The design and fabrication of high volumetric energy density supercapacitors lead to high density materials to be considered as electrode material. So far, most of the studies have been carried out on mono-cationic oxides such as RuO2, MnO2 or Fe3O4, while polycationic oxides, for which more than a single redox center are potentially involved, have been mostly neglected. As such, we have investigated Ba0.5Sr0.5CoxFe1-xO3-δ phases, with 0.75 ≤ x ≤ 0.90, so-called BSCFs, as pseudocapacitive electrode materials. Our motivations towards these perovskite phases are on their high density (close to 6 g.cm-3) and on both Co and Fe as potentially active redox centers. BSCF phases have been prepared by a glycine-nitrate process at 850°C and resulting powders show the same structural arrangement and identical morphology characteristics in the whole series of compositions. Electrochemical performances have been evaluated by cyclic voltamperometry at room temperature, in 5M LiNO3 aqueous electrolyte. Prepared BSCFs showed promising pseudocapacitive behavior and performances obtained are dependent on the Co/Fe ratio. A maximum capacitance of 87 F.g-1 at 5 mV.s-1 was obtained for the electrode based on the BSCF material with x = 0.80. This specific capacitance corresponds to a volumetric capacitance of about 500 F.cm-3 (as shown in the figure below), i.e. five times greater than that of activated carbon based electrode. This demonstrates the potential of high density oxides as electrode materials for improving the volumetric energy density of supercapacitors. Charge storage mechanism was investigated by in situ X-Ray Absorption Spectroscopy, performed on the ROCK beamline at SOLEIL Synchrotron (France). Experiments were carried out at both Fe and Co K-edges in the aim to determine the Co and Fe valency at various states of charge. Data analysis demonstrates that both Co and Fe are electrochemically involved in the charge storage mechanism. Their respective contribution to the capacitance depends on BSCF composition and on the scan rate, in accordance with the redox kinetics at Fe vs. Co centers. Thanks to these in situ measurements, an advanced description of the involved charge storage mechanism is provided.

B.8.2
16:45
Authors : C. Busacca, N. Briguglio, O. Di Blasi, V. Antonucci, A. Di Blasi
Affiliations : CNR-Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano” (ITAE) Salita Santa Lucia sopra Contesse n°5, 98126, Messina, Italy

Resume : Spinel nickel manganite-carbon nanofibers composites (NiMn2O4/CNF) are prepared by electrospinning method and investigated as electrode materials for vanadium redox flow battery (VRFB). The presence of spinel NiMn2O4 structure as well as the formation of graphitic carbon are detected by X-ray diffraction (XRD). A complete covering of carbon nanofibers by NiMn2O4 nanoparticles is evident by scanning electron microscope (SEM). Cyclic voltammetry (CV) measurements recorded high electrochemical performance in terms of peak to peak separation (E= 0,1 V). Charge-discharge tests carried out at high current density value (150 mA/cm2) show an energy efficiency value EE > 70 %. The catalytic performance obtained by NiMn2O4/CNF can be ascribed to the higher oxygen species content as well as the synergetic effect of the more graphitic carbon and the structural defects within the spinel NiMn2O4 structure [1]. In addiction, the nickel inclusion in manganese oxides (MnxOy) promotes the formation of spinel NiMn2O4 phase with a high surface area (193 m2/g) and high electrical conductivity [2]. These latter properties are probably the responsible for an increase of the NiMn2O4/CNF kinetic reaction at the electrode/electrolyte interface. References: [1] A. Di Blasi, C. Busacca, O. Di Blasi, N. Briguglio, G. Squadrito, V. Antonucci, Applied Energy 190 (2017) 165–171. [2] P. Ahuja, S. K. Ujjain, R. K. Sharma*, G. Singh, RSC Advances 4 (2014) 57192-57199.

B.8.3
17:00
Authors : A. Matinez-Lazaro1, E. Ortiz-Ortega1, J. Ledesma-García2, L.G. Arriaga1
Affiliations : 1 Centro de Investigación y Desarrollo Tecnológico en Electroquímica, Pedro Escobedo, Qro., C.P. 76703, México; 2 División de Investigación y Posgrado, Facultad de Ingeniería, Universidad Autónoma de Querétaro, 76010, México

Resume : The present work evaluates NiFe2O4 3D hollow spheres as low-cost transition material with high catalytic activity towards water splitting using a microfluidic electrolysis system. The H2 production was evaluated by cronoamperometry at different flow rates at a voltage of 1.6V using 1M KOH as the electrolyte. The main feature of microfluidic electrolysis system was the porous electrodes that allow to increase the available surface area. The results showed that the NiFe2O4 3D hollow spheres maintain 2.5 mA during the experimental time, with a very similar catalytic activity to electrocatalytic materials commonly used such as IrO2 and Pt, consequently NiFe2O4 3D hollow spheres has a great potential candidates as Pt-free material for H2 production. Keywords: water splitting, microfluidic electrolysis system, Pt-free materials

B.8.4
17:15
Authors : Fadoi BOUJIOUI, Alexandru VLAD and Jean-François GOHY
Affiliations : Institute of Condensed Matter and Nanosciences (IMCN), UCLouvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve, Belgium.

Resume : Lithium batteries (LiBs) are the most used rechargeable batteries for portable electronic devices. The development of flexible, safe, cheap and efficient batteries has become a necessity in our modern society. This implies the development of new chemistries for the electrolyte and the active electrode materials. For electrochemical energy storage technologies, the polymeric materials are searched due to their broad range of properties such as adjustable mechanical properties, sustainability or ionic/electrical conductivity. Redox polymer is a class of polymers based from groups which change redox form (loss and gain of electrons) in contact with electrical potential stimuli. One of the best known is the poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA) which display ultra-fast electron-transfer process (10-1 cm/s), good theoretical specific capacity (111mAh/g) and a reversible redox process (3.6V vs Li/Li ). Fluorinated copolymer bearing cyclic carbonate pendant groups, such as poly(vinylidene fluoride-co-(2-oxo-1,3-dioxolan-4-yl)methyl 2-(trifluoromethyl)acrylate) random copolymer, was studied as solid polymer electrolytes. The added lithium salt was dissolved in the poly(VDF-co-MAF-CyCB) amorphous phase and allowed the formation of an ionic conducting phase exhibiting ionic conductivity values as high as 2x10-4 S/cm at room temperature for an optimum cyCB/Li molar ratio of 5. This material displays good mechanical properties (up to 107 at 102 rad/s) and lithium ions transference numbers (0.68 at 40 °C). Here we will discuss about the use of PTMA as cathode active material and the poly(VDF-co-MAF-CyCB) copolymer as promising solid polymer electrolytes in energy storage devices. [1] F. Boujioui, O. Bertrand, B. Ernould, J. Brassinne, T. Janoschka, U. S. Schubert, A. Vlad and J.-F. Gohy, Polym. Chem., 2017, 8, 441-450. [2] F. Boujioui, F. Zhuge, H. Damerow, M. Wehbi, B. Améduri and J.-F. Gohy, J. Mater. Chem. A, 2018,6, 8514-8522

B.8.5
Start atSubject View AllNum.Add
12:30 LUNCH BREAK    
 
B9 : VINCENZO BAGLIO
14:00
Authors : James Somerville, Robert House, Peter Bruce
Affiliations : University of Oxford

Resume : The next generation of Li-ion rechargeable batteries is contingent on the development of new cathode materials with a greater capacity to store charge. Current state-of-the-art materials can deliver in the region of 180-200 mAh g-1 of charge storage capacity, however these materials are fundamentally limited by the amount of redox active transition metal present. One possible route to unlock significantly extended capacities is to invoke charge compensation using oxygen as well as the transition metal of lithium transition metal oxides. To harness the opportunities such materials offer, it is necessary to understand the nature of O-redox processes in the solid state and the factors that control them. O-redox in 3d transition metal oxides will be discussed, leading to a new high capacity manganese-based cathode that utilizes the full capacity of the Mn as well as charge storage on oxygen.

B.9.1
14:30
Authors : Samppa Jenu, Ivan Deviatkin, Marja Myllysilta, Saara Tuurala, Ari Hentunen
Affiliations : VTT Technical Research Centre of Finland Ltd, Espoo, Finland

Resume : The use of lithium-ion batteries (LIBs) is expected to expand further due to the increased use of renewable energy, such as solar and wind. LIBs utilized in stationary applications enable reliable supply of electricity stored in the batteries, while LIBs used in electric vehicles (EVs) can be charged with the renewable energy sources installed in private households. The end-of-life (EOL) for LIBs in EVs is conventionally determined by 80% state of health (SOH) and for stationary applications - 60% SOH. Before the EOL is reached, the number of obtained full cycles can be increased by considering the degradation stress factors. The degradation stress factors are all the operating practices and conditions that accelerate the battery degradation. Those include high current, high cycle depth, high average state of charge (SOC) or extreme temperatures. When using the LIBs, the reduction of the environmental impact primarily occurs through avoided use of conventional vehicles with internal combustion engines or avoided consumption of electricity from grid. In such a way, a higher reduction of the environmental impact from LIBs is expected due to increased number of full cycles facilitated by consideration of the stress factors and cautious management of batteries. Such a reduction will help to reduce the cradle-to-grave environmental impact of the LIBs, which can be assessed using the life cycle assessment (LCA) methodology. This study combines the technical aspects of LIBs to LCA.

B.9.2
14:45
Authors : D. Zaura-Campos, M. Villén-Guzman, J. M. Rodríguez-Maroto, C. Vereda-Alonso, C. Cómez-Lahoz, J. M. Paz-Garcia
Affiliations : : Department of Chemical Engineering, University of Malaga (Spain)

Resume : Lithium ion batteries are key in the modern society as they are present in many energy storage devices and have a promissing future perspectives in the field of electric cars and energy accumulators from renewable sources. Herein, we present results from charge and discharge cycles on batteries with controlled conditions. The ciclability of comertial lithium-polymer “pouch” batteries, has been studied under different charge/discharge rate and temperatures. The relationship between the state of charge and the cell voltage has been obtained, and the degradation of the cells energy capacity after a number of cycles has been measured. Furthermore, the experimental results have been compared with simulations based on Newman’s model for Lithium Ion Batteries, carried out using Comsol Multiphysics software. The results show the correlation between temperature, C-rate and degradation in lithium ion batteries batteries. It is specially remarcable the decrease of the apparent capacity of batteries at low temperatures, and the increase of the degradation at higher temperatures. These results are essential for the design of control mechanisms that can prevent battery failure.

B.9.3
15:00
Authors : Juan Ugalde
Affiliations : Institut de Chimie Moléculaire et des Matériaux d'Orsay, Université Paris-Sud, 91400 Orsay, France Groupe PSA, 92250 La Garenne-Colombes, France.

Resume : The electric vehicle industry has known a rapid development in the recent years. Indeed, increasing concerns regarding global warming, such as CO2 emissions, led automakers to implement cleaner technologies in their vehicles. For instance, to be competitive with thermal engine vehicles, a lot of work is carried out to enhance the energy storage systems of the electric vehicles (EV) in order to improve their autonomy and performance. Thus, it is essential for automakers to understand how driving conditions affect the battery ageing as it results on capacity and power fade. These parameters estimation can be made by using different approaches, from detailed electrochemical equations to mathematical data based models. Yet, none has so far performed enough to obtain a real time battery ageing estimation in EV application. In this work, a semi-empirical approach is presented and aims to model the electro-thermal behavior as well as the ageing of LIB’s. (i) The fatigue approach consists in adding the constraints related to a cycling conditions in order to determine a capacity and power loss [1]. (ii) The entropy profiles [2] will help to find a deeper correlation with the battery state of health and to determine the entropic heat [3]. Indeed, temperature is known to be one of the most important factor affecting the LIB ageing. Our model will help to understand the temperature dynamics inside the cells and will be validated with several temperature measuring tools such as thermocouples and Electrochemical Impedance Spectroscopy technique [4]. The robustness of this model relies on the mixing of several parameters (capacity, resistance and entropy profiles) coupled to a thermal model to estimate the battery ageing as well as to understand its electro-thermal performance. Our main goal is to optimize the EV life of the battery throughout a good knowledge of the cycling conditions impact on its ageing. [1] Q. Badey “ Etude des mécanismes et modélisation du vieillissement des batteries lithium-ion dans le cadre d’un usage automobile“. 2012. [2] P j. Osswald et al. “Fast and accurate measurement of entropy profiles of commercial lithium-ion cell“. Electrochimica Acta, vol. 177, 2015, pp.270-276. [3] D. Bernardi, E. Pawlikowski, J. Newman, “A General Energy Balance for Battery Systems”, Journal of the Electrochemical Society (ECS), vol. 132, no. 1, Dec. 1984, pp. 5-121. [4] R. Srinivasan, “Monitoring dynamic thermal behavior of the carbon anode in lithium-ion cell using a four-probe technique“, Journal of Power Sources, vol. 198, 2012, pp. 351-358.

B.9.4
15:15
Authors : Jaione Martínez de Ilarduya, Laida Otaegui
Affiliations : CIC EnergiGUNE; CIC EnergiGUNE

Resume : Transition metal layered oxides are attractive cathode materials due to their ease of synthesis, good tap density and high energy density. In this work, Na0.95Ni0.32Ti0.32Mg0.16Mn0.21O2 is selected as the cathode active material and full cells are assembled using hard carbon as the anode component. Reversible capacities of ca. 140 mAh g-1 and 200 mAh g-1 are obtained at C/10 respectively for the cathode and the anode in half cell configuration using electrode formulations which are suitable for lab-scale studies. With the aim of increasing the electrode loading and therefore the energy density, initial tests have been done by increasing the active material content up to 94 wt. %. In addition, carbon black and binder ratio has been optimized in order to improve the interaction between different elements of the slurry, make a good balance between the adhesion and ion-blocking effect of the PVDF binder, improve the electron conducting effect of the conductive additive and decrease the inactive material content. Optimized cathodes with 88 wt. % of active material content are used for full cell fabrication with balanced anode electrodes. Those cells delivered 190 mAh g-1 and 140 mAh g-1 for the first charge and discharge capacity, respectively, being the average discharge voltage 2.9 V. Cyclability tests show 72% of capacity retention after 100 cycles which make this combination of materials an attractive choice for the development of a sodium-ion battery.

B.9.5
15:30 COFFEE BREAK    
 
B10 : ALESSANDRA DI BLASI
16:00
Authors : Giovanni Brunaccini, Francesco Sergi, Davide Aloisio, Nico Randazzo, Marco Ferraro, Vincenzo Antonucci
Affiliations : Consiglio Nazionale delle Ricerche – Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”

Resume : Nowadays, resilient grids meet growing interest for their capability of supplying critical load even in case of power fault coming from grid disturbance and disasters. To do this, such grids involve redundant apparatus and predictive control schemes. For high value services, unexpected system unavailability is source of economic losses to the providers. Hence, beside the internal energy storage devices, such plants had better to have redundancy of energy sources (e.g. electrical grid and natural gas network) and tailored power flows control strategies still valid even in the case of external energy shortage. In this work, a supply system was developed both matching the requirements (both DC and AC) of the served ICT equipment, and capable of offering grid services as an experimental prosumer site. As fundamental design targets, energy conversion efficiency and cost reduction were addressed by developing a hybrid fuel cell/battery (SOFC/SNC) based prototype, and optimizing the size of each used device. Starting from field tests measurements, the hybrid generator was analyzed in a resilient grid scenario. Then, digital simulations compared different battery management algorithms and assessed the trade-off between battery exploitation and system resiliency against grid or gas network fault. The prototype showed satisfactory performance both for resilient microgrids and applications in which the continuous availability is a critical point (e.g. ICT equipment and data centers).

B.10.1
16:15
Authors : Itziar Aldalur1, María Martínez-Ibañez1, Eduardo Sánchez-Díez1, Michal Piszcz2, Heng Zhang1, Michel Armand1
Affiliations : 1CIC Energigune. Parque Tecnológico de Alava, Albert Einstein 48, 01510 Miñano, Álava, Spain 2Warsaw University of Technology, Faculty of Chemistry, Polymer Ionics Research group, Noakowskiego 3, PL-00664 Warszawa, Poland

Resume : Solid polymer electrolytes (SPEs) have been emerging as attractive candidates for meeting the demand in safe and high energy density batteries, attributed to their low flammability and ease in process. However, ionic conductivities of SPEs are several orders of magnitude lower than those of the conventional liquid electrolytes, hence preventing ambient-temperature operation of all solid-state lithium polymer batteries (ASSLPBs). Moreover, SPEs are usually characterized by a low lithium-ion transference number (TLi+ < 0.5) and consequently are more susceptible to polarization phenomena that eventually limit the power density and cycle life of ASSLPBs. To overcome above-mentioned limitations, extensive work has been devoted to the search of polymeric matrices that could allow the obtaining of SPEs with improved ionic conductivity at room temperature. Among which, chemical modification such as cross-linking or copolymerization are the main used strategies. In addition, the anion concentration gradient that takes place in conventional dual-ion conductors is one of the factors responsible for low TLi+. The main strategy to overcome this polarization problem is the development of single lithium-ion conducting solid polymer electrolytes (SLIC-SPEs), where the anion is immobilized by different means. In this talk, the physicochemical and electrochemical properties of our recently developed SPEs are presented. In particular, SLIC-SPE comprised of a flexible and highly conductive comb-like polymer grafted with polyether amine oligomer side chains and a polystyrene-based polysalt is conceived so as to decrease the working temperature and to avoid problems related to polarization.

B.10.2
16:30
Authors : Robert Mücke, Fadi Shaheen, Chih-Long Tsai, Martin Finsterbusch, Dina Fattakhova-Rohlfing, Olivier Guillon
Affiliations : Forschungszentrum Jülich, Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), 52425 Jülich, Germany

Resume : Composites of e.g. Li7La3Zr2O12 (LLZ) and LiCoO2 (LCO) are used as cathodes in all-solid-state batteries. However, LCO undergoes a volume change of approximately 4% during delithiation. The typical microstructure of a screen printed cathode was reconstructed in 3D with FIB/SEM using an enhanced binarization method and an elastic finite element simulation yielded compressive stresses in the LCO phase up-to 1.0 GPa and tensile stresses in the LLZ phase up-to 1.3 GPa, respectively. These resulting stresses will cause plastic deformation, fatigue and early failure of the cell. Volumetric stress histograms were used to quantify and compare the stress states for free standing cathodes, electrolyte-supported design (50 µm cathode on 400 µm electrolyte) and cathode-supported design (100 µm cathode on 4 µm electrolyte). In any case, the calculated stresses were critical for one of the components. Microstructural features such as pore chord length could be linked to the calculated anisotropic stress state providing hints for a strategy for stress minimisation. A honeycomb LLZ framework with a segmented LCO coating could lower stresses drastically below the yield stress. As the practical viability of such structures is rather difficult, the influence of microstructural parameters of typical screen printed layers like the volume ratio of the two phases, the grain size, and the porosity on the resulting stresses were also investigated using computer-generated microstructures.

B.10.3
16:45
Authors : A. Impagnatiello, C. F. Cerqueira, P. E. Coulon, A. Morin, G. Rizza, M. C. Clochard
Affiliations : LSI, CEA DRF/IRAMIS – Ecole Polytechnique CNRS, UMR 7642, Ecole Polytechnique CEA LITEN, Grenoble

Resume : Fuel cell is a device based in electrochemical reactions that convert chemical energy in electrical energy, using a constant source of fuel, unlike in batteries. One of most used fuel cell is Proton Exchange Membrane Fuel Cells (PEMFCs) studied for many applications like automobile and mobile phone. In a PEMFC the fuel is O and H gas. Anode and cathode are immersed in an electrolyte and are separated by a membrane able to transport protons (H ). In anode take place the hydrogen oxidation reaction while at the cathode the oxygen reduction. This latter is a slow kinetic process and it required a catalyst that consists of platinum nanoparticles supported in carbon. This catalyst is subject to degradation implying a reduction of the PEMFC life time. Electrochemical experiments of cyclic voltammetry (CV) are implemented to study the degradation of PEMFC. During cyclic voltammetry the PEMFC is in operando conditions, the potential at the electrodes is so cyclically varied in order induce an aging of the device. The catalyst degradation is monitored on the basis of the cyclic voltammogram, but no clue is given about the nanoscale processes on the catalyst responsible of its degradation. In order to obtain this information, CV experiments have carried in-situ of a transmission electron microscope (TEM). The catalyst degradation during CV can be monitored also by nanoscale images. Mandatory international experimental protocols are related to ex-situ CV. Our work investigates the relationship between ex-situ and in-situ CV of the Pt catalyst. The electron beam increases the aging that can be imparted improving in-situ CV versatility. Such results make in-situ CV experiments more linkable to real scenarios and so interesting for industry.

B.10.4
17:00
Authors : Antoine Desrues [1,2], John P. Alper [1,3], Florent Boismain [1], Cédric Haon [3], Sylvain Franger [2], Nathalie Herlin-Boime [1]
Affiliations : [1] : NIMBE, UMR 3685, CEA-CNRS, CEA Paris-Saclay, 91191 Gif-sur-Yvette [2] : ICMMO, UMR 8182, Université Paris-Sud/Université Paris-Saclay, Orsay [3] : LITEN, CEA Grenoble, Université Grenoble Alpes, 38054 Grenoble

Resume : Nanometric silicon appears as an interesting candidate to improve the capacity of lithium-ion batteries anodes because its theoretical specific capacity is over 10 times that of current commercial graphite electrodes. A major issue with nanosilicon anodes is the continuous formation of solid electrolyte interphase (SEI) due to the significant volume changes in the material during lithiation-delithiation. Coating the silicon surface with carbon has proved to protect it, as a more stable SEI is obtained. For this purpose, we synthesize core@shell silicon-carbon nanoparticles by using a double-stage laser pyrolysis reactor [1]. This gas-phase technique allows one-step synthesis of a silicon core coated by a carbon shell. The size and the size distribution, as well as the shell’s thickness, can be controlled by the modification of parameters. This wall-less process leads to clean interfaces. In this work the synthesis of carbon coated crystalline nanosilicon (30 nm) with various carbon contents, up to 20 % w/w, will be presented. These Si@C particles present a clear silicon-carbon interface as shown by STEM-EELS. The galvanostatic performance comparison indicates that the coulombic efficiency is improved by a greater carbon content and power rate experiments indicate that an optimum exists. Finally, by using electrochemical impedance spectroscopy (EIS), a comparison of SEI resistances for coated and non-coated particles will be presented. [1] Sourice et al, ACS Appl. Mater. Interfaces 2015

B.10.5
17:15
Authors : Hartmut Popp, Corina Täubert, Alexander Bergmann
Affiliations : Center for Low-Emission Transport, AIT Austrian Institute of Technology, 1210 Vienna, Austria; Institute of Electronic Sensorsystems, Graz University of Technology, 8010 Graz, Austria

Resume : Lithium-Ion batteries (LIB) are widely used in many types of mobile applications nowadays and the demand will even increase with the wider implementation of electric vehicles and stationary storage systems. Therefore, research and development efforts are directed towards improving both performance and diagnostic methods of LIBs. Recently, the mechanical behavior of the cells started to be investigated more into detail, since it can be correlated to their State-of-Charge (SoC) or, in general, State-of-Health (SoH), and thus becoming an accurate diagnostic method. A significant example would be the volume change during lithiation and de-lithiation processes, which is quite significant at the anode side – i.e. graphite and especially silicon-based materials. Changes in volume are nowadays mainly monitored by dilatometer measurements. This work introduces a promising additional in-situ, non- invasive technique to monitor the mechanical properties of cells. The mechanical frequency-response-function (FRF), which is well-known in several applications such as civil engineering, mechanical engineering and structural dynamics, is here applied to LIBs. All investigations were carried out on two types of commercial pouch cells with NMC as cathode and graphite as anode. One of the cell is high-energy optimized, while the other one is optimized for lifetime. Except for their thickness, the cells exhibit the same dimensions, which allows for a good comparison. The cells are excited by means of an electrodynamic shaker, and their response is measured by using an impedance head. It is shown that the FRF is able to determine relevant mechanical parameters of the cell such as damping and stiffness. This data then can be correlated with different operational parameters and conditions of the cell – e.g. SoC and cell temperature. As only low forces of a few Newton are needed, the method has high potential for miniaturization and for cost reduction. To validate the method, dilatometry measurements are performed on full cells, too. In order to better evaluate these results, also the individual electrodes – both anode and cathode – from the commercial cells were tested separately in half-cells (vs. lithium metal) by means of cyclic voltammetry and dilatometry. For this purpose, cells were dismantled under an inert gas atmosphere and all components were removed and evaluated. In addition to the electrochemical characterization, other electrode properties were investigated by means of several characterization techniques – e.g. XRD, SEM, BET and thermal analysis. The work will present all these activities and show the potential but also the boundaries of FRF as method for cell diagnostics.

B.10.6
17:30
Authors : Ruby Singh1,2, Ralf Witte1, Xiaoke Mu1,3, Robert Kruk1, Ben Breitung1,2, Horst Hahn1,2
Affiliations : 1 Institute of Nanotechnology, Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany 2 Joint Research Laboratory Nanomaterials – Technische Universität Darmstadt & Karlsruhe Institute of Technology, 64287 Darmstadt, Germany 3 Karlsruhe Nano-Micro Facility (KNMF), Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany

Resume : The approach to reversibly control the magnetic properties of a transition metal compound could be recently shown using a concept derived from intercalation based lithium ion batteries. By using an intercalation process of Li into a host structure, the reduction of a participating element (e.g. transition metal ion) can be achieved, and therefore the resulting change of the magnetization can be measured. The feasibility of this procedure has been proven by the successful reversible reduction of the ferromagnetic γ-Fe2O3 (maghemite) inside a SQUID, and the in-situ measurement of the magnetization.[1] In this study, we are transferring the concept shown for intercalation materials towards FeF3·3H2O as conversion material and show for the first time an operando tuning of magnetization during a conversion reaction. The reduction of FeF3·3H2O leads to a change in the magnetization over reversible cycling and is discussed to be a two-step process.[2,3] This could be confirmed by this study by comparing the changes in the magnetization with features appearing in the corresponding cyclic voltammogram. Additionally, the partial irreversibility of the FeF3·3H2O reduction/oxidation could be monitored. For the measurements, a customized electrochemical cell was used applying a two-electrode setup with Li as counter electrode. As electrolyte, a solution of LiTFSI in EMIM-TFSI was utilized in order to be compatible with the SQUID preconditions. Furthermore, the sample composition and structure were thoroughly examined at different charge states with ex-situ methods like ADF-STEM, EELS or Mössbauer spectroscopy which as well confirmed the formation of Fe(0) in the discharged active material. Magnetic characterizations at different charge states and temperatures will also be shown, i.e. ZFC/FC and hysteresis curves. [1] S. Dasgupta, B.Das, M. Knapp, R. A. Brand, H. Ehrenberg, R. Kruk, and H. Hahn, “Intercalation-driven reversible control of magnetism in bulk ferromagnets”, Adv. Mater., vol.26, 4639–4644, 2014. [2] L. Liu, H. Guo, M. Zhou, Q. Wei, Z. Yang, H. Shu, X. Yang, J. Tan, Z. Yan, and X. Wang, “A comparison among FeF3·3H2O, FeF3·0.33H2O and FeF3 cathode materials for lithium ion batteries: Structural, electrochemical, and mechanism studies”, J. Power Sources, vol.238, 501-515, 2013. [3] F. Badway, F. Cosandey, N. Pereira, and G. G. Amatucci, “Carbon Metal Fluoride Nanocomposites: High-Capacity Reversible Metal Fluoride Conversion Materials as Rechargeable Positive Electrodes for Li Batteries”, J. Electrochem. Soc., vol.150(10), A1318-A1327, 2003.

B.10.7
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B11 : SERGI FRANCESCO
09:00
Authors : Claire Deilhes, Benoit Chavillon, Eric Mayousse, Jean-Christophe Fidalgo, Philippe Azaïs
Affiliations : Gemalto, 525 Avenue du Pic de Bertagne 13420 Gémenos, France: Claire Deilhes;Jean-Christophe Fidalgo & Université Grenoble Alpes, CEA, LITEN, DEHT, 38000 Grenoble, France: Claire Deilhes; Benoit Chavillon; Eric Mayousse; Philippe Azaïs

Resume : Increasing the energy density of credit card payments is essential in order to enable multiple functions and higher levels of security. Required energy density is about at least 1000 Wh/L. Currently, the maximum density energy reached for the Li-ion secondary cell is about 700 Wh/L at low discharge rates. These values are not high enough and difficult to reach in small objects. Moreover, primary Li metal cells can reach higher values but demonstrate high toxicity and poor safety. The choice of primary Li-air technology for energy storage is strongly motivated by the breakthrough brought by a theoretical energy density of about 10 times higher than the current Li-ion storage. This is due to the utilization of oxygen as positive material which is never ending supply in this battery because brought by air. With this consideration, the limitating material in these batteries becomes Li, which has a high energy density, so it becomes possible to achieve an energy density higher than 1000 Wh/L. Here, we will present a Li-air technology developed at CEA Tech which is a break with current Li-O2 systems: electrolyte is able to dissolve O2 in it and is not toxic and inflammable. As a result, the reaction at the cathode is only in liquid phase, the triple point is not required and the battery is not limited by air flux because O2 could be stored in solution.

B.11.1
09:15
Authors : Yagmur Celasun, Jean-François Colin, David Peralta, Sebastien Martinet
Affiliations : Univ. Grenoble Alpes, CEA, LITEN, DEHT, F-38000 Grenoble, France E-mail of the Corresponding Author: yagmur.celasun@cea.fr

Resume : Overlithiated rock salts are promising cathode materials for Li ion high energy applications. Despite the earlier results, they can offer much higher capacities (>250 mAh/g) than the stoichiometric compositions. This high capacity is associated to Li rich content that forms a good percolation network along the Li diffusion channels [1]. Lithium titanium sulfide (Li2TiS3), which has been reported by Sakuda et al. [2], demonstrated excellent capacity owing to the multielectron redox reactions. Upon cycling, more than two lithium ions were reversibly intercalated through the structure and the capacity reached 425 mAh/g. Besides these promising results, low electronic conductivity as well as poor cycling stability were also reported. To eliminate such disadvantages, doping can be an effective solution. Here, we propose new doped lithium titanium sulfide materials, which have been prepared by high energy ball milling. New material showed better cycling stability than the current material. For a comparison, we will also provide a comprehensive study of Li2TiS3 through fine characterization tools (XRD, SEM, EDX, ICP, GITT, ex situ and in situ XRD) in order to examine electrochemical and structural properties as well as the degradation mechanism. References: [1] J. Lee et al., Science, 343, 519-521 (2014) [2] A. Sakuda et al., Sci. Rep, 4, 4883 (2014)

B.11.2
09:30
Authors : Faiz Ahmed, Sabuj Chandra Sutradhar, Taewook Ryu, Soojin Yoon, Hanmo Yang, Inhwan Choi, Md Mahabubur Rahman, Whangi Kim*
Affiliations : Department of Applied Chemistry, Konkuk University, Chungju 380-701, Republic of Korea

Resume : Novel methyl imidazole-based fluorine containing electrolytes with wide electrochemical window and high ionic conductivity have great potential for rechargeable lithium-ion batteries. In this report, we synthesized and characterized a series of methyl imidazolium based fluorine containing electrolyte from the reaction with methyl imidazole, 1,2-dimethyl imidazole, 1,3 propane sultone, 1,4 butane sultone, and sulfonyl fluoride, respectively. The electrolyte with FSI- anion shows better performances such as high ionic conductivity, cyclic, and electrochemical stability compared to TFSI- anion based electrolytes due to the formation of stable solid electrolyte interface (SEI) layer on the electrode surface. Full Li-ion batteries based on these electrolytes (1 M electrolyte solution in ethylene carbonate/dimethyl sulfoxide solvent) using LiFePO4 cathode and graphite anode will exhibit good specific discharge capacity in conjunction with conventional methyl imidazole-based electrolytes. Moreover, FSI- anion based electrolyte shows excellent thermal stability. The structures of the resultant electrolytes were confirmed by 1H-NMR and 19F NMR spectroscopy. The properties and performances of the resultant electrolytes were investigated by differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), cyclic and linear sweep voltammetry (CV and LSV).

B.11.3
09:45
Authors : Kwangjin Park
Affiliations : Department of Mechanical Engineering, Gachon university, 1342 Sungnamdaero, Sujeong-Gu, Sungnam Si, Gyeonggi-do, [13120], Republic of Korea

Resume : We investigated that the recycling of protective layer for Ni rich layered oxide material for Li ion batteries. To decrease the electrochemical performance according to leaving of cathode powder in air was confirmed by various analysis due to formation of lithium residuals. The surface of protective layer was covered by the lithium residuals and that lead to cancel the coating effect. The residual lithium was decreased and the cell performance was recovered by applying the recycling process in this work. After the recycling process, the performance became similar to that immediately after the initial coating, and the coating layer showed a resurgence, which was confirmed by SEM and TEM images. The initial capacity for the initial coated Ni rich NCM and the sample after recycling was 209 mAh/g and 206 mAh/g at 1C, respectively. The cycle retention for the initial coated NCM and the sample after recycling was 93.4% and 92.6% after 50th cycles at 1C. It is concluded that the coating layer and the electrochemical performance was recovered by recycling process.

B.11.4
10:00
Authors : R.Veena1, K.Srimathi1, S.Raman1, P. Panigrahi1, Juwon Lee2, N. Ganapathi Subramanian2*
Affiliations : 1 Centre for Clean Energy and Nano Convergence (CENCON), Hindustan Institute of Technology and Science, Padur - 603103, Chennai, India 2 Quantum Functional Semiconductor Research Centre (QSRC) and Nano Information Technology Academy (NITA), Dongguk University, 26 Phildong3ga, Chung gu, Seoul 100-715, Republic of Korea.

Resume : Lithium transition metal borates (LiMBO3, M= Mn, Co, Fe) has drawn considerable attention due to their promising properties such as high theoretical capacity (222 mAh/g), high energy density, lightweight, high stability against oxygen loss, abundance and environment-friendly material. In this work, Lithium manganese borate (LiMnBO3), Lithium cobalt borate (LiCoBO3) and Lithium manganese cobalt borate (LiMn0.5 Co0.5BO3) materials were synthesized by sol-gel technique. The crystal structure, morphology and electrochemical performances of the lithium transition metal borates were analyzed by X-ray diffraction (XRD), X-ray Photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), Transmission electron microscopy (HRTEM) and galvanostatic charge-discharge measurements. XRD result revealed the presence of monoclinic phase with C2/c space group. XPS analysis confirmed the valence state of the metal ions. Galvanostatic charge-discharge measurement result revealed that the sol-gel derived Lithium transition metal borates exhibited excellent electrochemical performance. The LiMnBO3, LiCoBO3 and LiMn0.5 Co0.5BO3 cathodes delivered the first discharge capacity of 106, 98 and 110 mAh g-1 at C/10 rate and stable cyclic performance was observed for all the three cathodes.

B.11.5
10:15
Authors : Maral Hekmatfar, Agnese Birrozzi, Arefeh Kazzazi, Thomas Diemant, R. Jürgen Behm, Gebrekidan Gebresilassie Eshetu, Stefano Passerini
Affiliations : Maral Hekmatfar; Agnese Birrozzi; Arefeh Kazzazi; Gebrekidan Gebresilassie Eshetu; Stefano Passerini : Helmholtz-Institut Ulm (HIU), Helmholtstrasse 11, 89081 Ulm, Germany Karlsruher Institut für Technologie (KIT), P.O. Box 3640, 76021 Karlsruhe, Germany Thomas Diemant; R. Jürgen Behm : Institute of Surface Chemistry and Catalysis, Ulm University, Albert-Einstein-Allee 47, D-89069 Ulm, Germany

Resume : Development of high energy density lithium ion batteries is recently the scope of interest due to the growing demand for electric vehicles. A common approach is to implement high voltage cathodes, among which lithium-rich NMC (LRNMC) seems to be a promising candidate. One of the barriers to its utilization, however, is the performance fade. Even though extensive studies have been done on LRNMC structural changes upon delithiation/lithiation cycling, interactions occurring at the electrode/electrolyte interface are barely investigated. In this work, the passivation film (SEI) formation on LRNMC cathodes was studied at different states of charge by X-ray photoelectron spectroscopy (XPS). Furthermore, SEI characteristics at charged and discharged states have been compared. Finally, the effect of tris(pentafluorophenyl)borane (TPFPB) electrolyte additive and high temperature on the film composition was studied. At different delithiation (i.e. charge) states, a stable formation rate organic SEI compounds was observed while it altered for the inorganic ones. Moreover, different SEI thickness in the charged and discharged states confirms the repetitive attests decomposition/dissolution of some SEI components at high voltages. XPS results reveal that TPFPB additive participates in the SEI formation which contributes to a thicker passivation layer. Lastly, we confirm the SEI thickness growth on LRNMC cathode at elevated temperature following the exacerbated electrolyte degradation.

B.11.6
10:30 COFFEE BREAK    
 
B12 : JANET LEDESMA GARCIA
11:00
Authors : F. Sergi1, G. Brunaccini1, D. Aloisio1, N. Randazzo1, M. Musio2, R. M. Polito2, M. Pietrucci2, E. Mocci2, M. Ferraro1 and V. Antonucci1
Affiliations : 1 National Research Council of Italy - CNR Institute of Advanced Energy Technologies “Nicola Giordano”- ITAE Salita S. Lucia sopra Contesse, 5 - 98126 Messina, Italy 2 Terna S.p.a., Innovation & Storage, Strategy & Development Division, Viale Egidio Galbani, 70 – 00156 Roma, Italy

Resume : Power grids are deeply changing in recent years due to the rapid deployment of renewable energies and a growing worldwide energy demand. Energy storage systems are promising technologies to provide electric networks with ancillary services. Currently, few data referred to batteries operation in power network ancillary services utilization are available. This could limit the evaluation of battery technologies in relation to those applications. Li-Titanate technology is characterized by a high specific power and it guarantees high safety in stressful conditions. In this context, the performance of a Li-Titanate Toshiba® battery, subjected to a frequency regulation cycle, was studied by CNR-ITAE. In the meantime, the manufacturer (Toshiba) tested the battery module in CC (Constant Current) charge/discharge cycles. This paper reports the results coming from the testing campaign at CNR-ITAE throughout 250 test days. A comparison between battery degradation obtained during frequency regulation and constant current tests was analyzed. Battery performance indicators (such as SOH, capacity and efficiency reduction) were evaluated. Finally, in order to optimize the size of energy storage systems based on lithium titanate technology operating under primary frequency regulation conditions, an evaluation tool was implemented.

B.12.1
11:15
Authors : Maryam Aghajamali, Hezhen Xie, Fengyuan Shan, Morteza Javadi, Peter Kalisvaart, Jillian Buriak, Jonathan G.C. Veinot
Affiliations : Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada, T6G2G2

Resume : Driven by the rapidly growing demand for electric and hybrid vehicles, as well as portable consumer electronics there is an ever increasing need for high-performance lithium ion batteries (LIBs). Silicon is one of the most promising LIB anode materials because of its high theoretical specific capacity (>4200 mAh/g). Unfortunately, with this impressive capacity comes critically limiting characteristics that include low electrical conductivity and large volume changes during lithiation/delithiation (>300%) that can lead to material pulverization and rapid capacity fade. Hybrid materials offer potential solutions to these limitations because when combining the components new composite properties can emerge. Graphene aerogels are flexible high surface area porous materials that are electrically conductive. It is reasonable that a graphene aerogel host containing nanoscale Si guest could provide an advanced hybrid material that addresses the challenges facing Si LIB electrodes. In this presentation, the preparation, properties and prototype LIB applications of mesoporous graphene aerogels containing sub-10 nm diameter silicon nanocrystals will be discussed.

B.12.2
11:30
Authors : Jong Ho Won, Hyung Mo Jeong, Jeung Ku Kang
Affiliations : Graduate School of Energy, Environment, Water and Sustainability (EEWS) and NanoCentury, KAIST Institute, Daejeon 305-701, Republic of Korea; Department of Nano Applied Engineering, Kangwon National University, 1 Kangwondaehak-gil, Chuncheon-si, Gangwon-do, 24341 Republic of Korea; Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, 291 Daehak-ro, Yuseong-gu, Daejeon 305-701, Republic of Korea

Resume : The demand for energy storage with higher energy density is increasing day by day and intensive researches are being carried out. Many kinds of research have been concentrated on the anode of lithium-ion battery with high energy density. However, the practically usable anode electrode material is very limited for a number of reasons. And commercial cathode still has low capacity, the effect of full-cell configuration using a high capacity anode is insignificant, which is an obstacle to the development of the entire energy storage device. The newly proposed conversion type cathode has a storage capacity of 10 times that of the existing intercalate cathode. Sulfur is an interesting cathode material due to its high theoretical capacity of 1,673 mAh / g, large quantities, very low cost and low toxicity. Theoretically, S-based cathodes are configured full cell battery with a Si or lithium metal anode can achieve four or five times the theoretical specific energy of a commercial C-LiCoO2 system. Despite the theoretical capacity of the sulfur, the practical steps mentioned above could not be reached because of insulating properties and large volume expansion of sulfur, and dissolution of the intermediate reaction product in the electrolyte results in the poor lifetime. In this study, we use a polymer with a channel to enclose sulfur particles to prevent volume expansion and dissolution, in addition, try to approach to impart mass transfer capability through hybridization with conductive graphene. The polymer with a channel is synthesized through a low-temperature heat treatment based on the difference of the vaporization temperature according to the degree of polymerization of the polymer. Through the channel, the lithium ion and the electron to be delivered to the sulfur contained in the polymer. All of the synthesis processes attempted in this study are scalable and very easy to mass-produce. The polymer used in this study is an aliphatic rubbery synthetic polymer and has a vaporization temperature of 60 ° C or less when it is in a monomer state. However, the vaporization temperature rises sharply according to the degree of polymerization, and when it is completely cured, it has a vaporization and decomposition temperature of 300 degrees or more. But in this work, the polymer in the hybrids mostly had a very low degree of polymerization in the MALDI-TOF analysis of the synthesized whole hybrids. This is because of the polymerization reaction, which originated from sulfur, terminated very quickly and the reaction was complete when the polymer met the sulfur and graphene particles. Due to the very low degree of polymerization of the polymer, the polymer can be vaporized at temperatures below 90 degrees, which results in many pores and channels on the surface and inside of the polymer from low-temperature heat treatment. Such a pore-forming polymer has superior mass transfer characteristics and high lifetime performance while offsetting the disadvantages of sulfur.

B.12.3
11:45
Authors : Meiying Liang1, Chuanfang (John) Zhang2 and Valeria Nicolosi3
Affiliations : 1. PhD Student, School of Chemistry, CRANN&AMBER Trinity College Dublin, Ireland 2. Doctor, School of Chemistry, CRANN&AMBER Trinity College Dublin, Ireland 3. Professor, School of Chemistry, CRANN&AMBER Trinity College Dublin, Ireland

Resume : Metal chalcogenides (MCs), including metal sulfides, metal selenides and metal tellurides, have attracted tremendous attention for energy storage applications and development of rechargeable lithium-ion batteries due to their unique physicochemical properties (e.g. high electrical conductivity, good thermal stability, earth abundance, etc.). Especially, MCs possess higher theoretical specific capacities for rechargeable lithium-ion batteries compared to traditional intercalation electrode materials. In addition, metal chalcogenides tend to be more electrochemically reversible as compared to metal oxide counterparts due to their faster charge transfer kinetics. Recently, as an alternative anode material for replacing currently commercialized graphite or carbon-based anode materials, various layered inorganic materials are investigated because of their large theoretical capacity. Similarly large numbers of layered MCs are explored as intercalation anode materials for lithium-ion batteries. However, there is still a plenty of room for the development of new efficient anode materials from MCs families, especially 2D MCs (both layered and non-layered) operating in terms of both intercalative and non-intercalative mechanisms, since only a few studies are carried out for this type of materials. In this work, 2D MCs nanosheets (such as GaS, GaSe, GaTe and InSe) were prepared via liquid phase exfoliation approach and their application as anodes of Li-ion batteries was investigated in detail. Among these 2D MC nanosheets, InSe displays the most excellent rate capability and high specific capacity (926 mAh g-1 and 595 mAh g-1 at 50 mA g-1 and 2 A g-1, respectively). In addition, it shows exotic cycling stability. The capacity of it has increased with the increase of cycling numbers, which means the quality of a battery will be improved when the battery is used. This work opens up vast opportunities for InSe and other families of MC nanosheets to be scalably processed into flexible conductive composite films with a broad range of applications such as wearable electronics, optoelectronics, and other energy storage systems.

B.12.4
12:00
Authors : Jaime Sanchez, Afshin Pendashteh, Jesus Palma, Marc Anderson, Rebeca Marcilla
Affiliations : Jaime Sanchez;a Afshin Pendashteh;a Jesus Palma;a Marc Anderson;a,b Rebeca Marcilla;a a Electrochemical Processes Unit, IMDEA Energy Institute, Avda. Ramon de la Sagra 3, Parque Tecnológico de Móstoles, 28935 Móstoles, Spain. b Department of Civil and Environmental Engineering, University of Wisconsin, Madison, USA

Resume : Mixed metal sulfides have recently attracted great attention for energy storage applications due to low cost and enhanced electrochemical performance compared to their oxide/hydroxides analogues [1,2]. Despite of being demonstrated as high performance energy storage electrodes, their charge storage mechanism is not yet fully understood. Herein, NiCoMn mixed sulfide nano-needles were evaluated as novel binder/additive-free electrodes for high-performance energy storage and the charge storage mechanism was tracked through various post-mortem measurements. A facile hydrothermal method was employed to synthesize NiCoMnS2 nano-needles which were then microstructurally probed by XRD, EDX, SEM and TEM analyses. Electrochemical properties of the prepared samples were examined through CV, GCPL and EIS measurements, revealing a high specific capacity of 138 mAh·g-1 (0.71 mAh·cm-2), excellent rate capability and exceptional cycling stability demonstrating a peculiar electro-activation over cycling. Post-mortem XRD and Raman spectroscopy of the sample at various state of the charge suggested formation of possible amorphous phases on the surface of sample. Based on the obtained results a charge storage mechanism was proposed for NiCoMnS2 in alkaline media. In addition, the prepared sample was integrated with rGO electrodes in an asymmetric device, exhibiting a maximum energy density of 36.2 Wh·kg-1 and power density of 16.5 kW·kg-1, with excellent long-term cycling and rate capability. Accordingly, we believe the present work not only sketches electrochemical behavior of NiCoMnS2 but also help better understanding the charge storage origin of mixed metal sulfides. References: [1] X.Y. Yu, X.W. Lou, Mixed Metal Sulfides for Electrochemical Energy Storage and Conversion, Adv. Energy Mater. 1701592 (2017) 1701592. [2] P. Kulkarni, N. Sanna Kotrappanavar, G.R. Balakrishna, D.H. Nagaraju, M.V.V. Reddy, Nanostructured binary and ternary metal sulfides: Synthesis methods and its application in energy conversion and storage devices, J. Mater. Chem. A. 5 (2017) 22040–22094.

B.12.5
12:15
Authors : J. E. García-Béjar,1 L. Álvarez-Contreras,2 M. Guerra-Balcázar,3 N. Arjona,1 J. Ledesma-García,3 and L. G. Arriaga1
Affiliations : 1 Centro de Investigación y Desarrollo Tecnológico en Electroquímica S. C., Querétaro, C. P. 76703, México. 2 Centro de Investigación en Materiales Avanzados S. C., Complejo Industrial Chihuahua, Chihuahua, C. P. 31136, México. 3 Facultad de Ingeniería, División de Investigación y Posgrado, Universidad Autónoma de Querétaro, Querétaro, C. P. 76010, México.

Resume : Air batteries and fuel cells can be considered as promising energy conversion devices for portable applications such as the automotive sector. The oxygen reduction reaction (ORR) and, the dependence on the use of expensive noble metals remains as some of the main limiting factors for fuel cells and air batteries technologies. Transition metal oxides mixtures (TMOMs) have gained interest as novel catalytic materials due to its great stability; being their activity highly dependent on the nature and composition of the mixture. In the present work, we synthesized NiCo2O4 and Co3O4 spinels through a solvothermal methodology, and evaluated their electrocatalytic properties for the oxygen reduction reaction. X-ray diffraction patterns corroborated the crystal structure corresponding to NiCo2O4 and Co3O4; while, SEM micrographs revealed that, Co3O4 presented a nanosheet array forming a hierarchical semi-porous structure. In the case of NiCo2O4, it presented a flowerlike microstructure with sizes ranging from 3 to 5 μm. In terms of the electrocatalytic evaluation for ORR in alkaline medium (0.1 M KOH), both materials exhibited activity for ORR, being the hierarchical structure the Co3O4 material with the highest current density (3.5 mA cm-2). This value was achieved due to the greater active surface area of Co3O4. In terms of overpotential (η) compared with commercial Pt/C (20 wt.%), the Co3O4 and NiCo2O4 presented η values ranging between 160 and 180 mV.

B.12.6
12:30 LUNCH BREAK    
 
B13 : ALESSANDRA DI BLASI
14:00
Authors : Siow Jing Han, Soraya Hosseini, Ali Abbasi, Soorathep kheawhom
Affiliations : Siow Jing Han, Department of Chemical Engineering, Faculty of Engineering, Universiti Teknologi PETRONAS, 32610 Seri Iskander, Perak, Malaysia. jhsiow53095@gmail.com; Soraya Hosseini, Ali Abbasi, Soorathep kheawhom, Computational Process Engineering Research Laboratory, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Bangkok 10330, Thailand.

Resume : A favorable electrolyte/separator for alkaline zinc-air batteries should possess high ionic conductivity, less zincate ion crossover, high electrochemical stability in caustic solution and high electrical resistance. Though commercial microporous films of polyolefins, namely, polyethylene and polypropylene, saturated with electrolyte are widely used as the separator. The microporous structure of the commercial films, which is ordered structure, usually leads to the lower performance of the batteries. Thus, non-ordered and layered-fibrous structures are suggested to improve the battery performances. Herein, separators based on electrospun polypropylene nanofibers were investigated. Electrospun syndiotactic polypropylene (s-PP) nanofibrous mat was fabricated using electrospinning technique. Granular s-PP was dissolved in a solvent mixture of decalin, acetone and DMF to the concentration of 7.5 wt%. The resulting solution was then electrospun under a controlled condition (Potential: 10.5 kV; Distance: 15 cm; flow rate: 0.8 ml/h). A three-electrode configuration cell with a zinc working electrode and a platinum counter electrode was used to examine electrochemical characteristics of electrospun s-PP nanofibers and Whatman filter paper. Also, the performances of the separators were examined using home-made tubular zinc-air batteries with stagnant electrolyte. Cyclic voltammetry elucidated the higher and broader peak for zinc dissolution was appeared on nanofibrous (s-pp) compared to the Whatman filter paper. The galvanostatic discharge results showed that the battery using s-PP nanofibers exhibited an improvement in the discharge capacity more than 40% compared to the Whatman filter paper.

B.13.1
14:15
Authors : Guillaume Tonin, Alice Robba, Gavin Vaughan, Renaud Bouchet, Fannie Alloin, Céline Barchasz
Affiliations : French Atomic Energy and Alternative Energies Agency (CEA) – Laboratory of Innovation for New Energy Technologies and Nanomaterials (LITEN) – 17 rue des Martyrs, 38054 Grenoble, France ; European Synchrotron Radiation Facility, CS 40220, F-38043 GRENOBLE Cedex 9, France ; Univ. Grenoble Alpes, Univ. Savoie Mont Blanc, CNRS, Grenoble INP (Institute of Engineering Univ. Grenoble Alpes), LEPMI, 38000 Grenoble, France

Resume : High capacity sulfur electrodes are expected to serve to high energy density low cost next-generation lithium rechargeable batteries. Li/S cells involve a series of complex chemical reactions between solid and soluble sulfur species, causing severe morphological changes upon cycling and low practical performances. These changes at both electrodes upon cycling are still key parameters for Li/S batteries, while different strategies can be found in the literature to address these degradation mechanisms. In particular, operando X-ray diffraction techniques are interesting tools, providing qualitative and quantitative information on crystalline active species upon cycling. As well, X-ray absorption tomography allows changes in the global morphology of the electrodes to be studied upon cycling. In this work, X-ray tomography was combined with X-ray diffraction computed tomography, to follow operando the full cell behaviour thanks to morphological and chemical information, and then to investigate the ageing mechanisms of the cell components. Information on both electrodes could be recorded using a representative cell design, with electrolyte amount and pressure controls. As a perspective of this work, such a characterization tool could be applied by material scientists while designing and characterizing new solutions developed for Li/S cells.

B.13.2
14:30
Authors : Cavit Eyövge; Ezgi Onur Sahin; Tayfur Ozturk
Affiliations : Center for Energy Materials and Storage Devices, Middle East Technical University, Çankaya 06800, Ankara Dept. of Metallurgical and Materials Engineering, Middle East Technical University, Çankaya 06800, Ankara

Resume : There is a renewed interest in NiMH batteries with improved energy densities that could approach those of Li-ion batteries. Efforts to improve the energy density concentrates on alternative anode as well as cathode materials. For anode, AB2 and Mg based alloys are candidates with potentials that go beyond the capacity achieved with rare-earth based AB5 compounds. In a recent study [1] we have shown an AB2 alloy which is sluggish in its activation could readily be activated when it was surface modified with hot-alkaline treatment. The treatment resulting in fine porous surface rich in Ni not only activates the alloy but it also increases the discharge capacity by a significant amount. This was attributed to positive effect of porous surface where hydrogen evolution was made difficult by the associated stabilizing effect. For Mg based alloys, we have investigated A2B7 alloy where the amount of Mg is quite low and an amorphous Mg50Ni50 alloy. Here rather than modifying the powders, the electrode itself was modified by nafion coating. The electrodes were tested both in bare and coated form with a notable difference in discharge capacity. Nafion coating increased maximum attainable discharge capacity in both alloys up to 150%. Electrochemical impedance spectroscopy measurements showed that the charge transfer resistance increases with coating. The role of nafion coating in developing Mg based negative electrode materials is discussed. [1] Tan S., Shen Y., Sahin E. O., Noréus D., Ozturk T., "Activation behavior of an AB2 type metal hydride alloy for NiMH batteries" International Journal of Hydrogen Energy 41 (23), 9948-9953,2016

B.13.3
14:45
Authors : S. Didry1, C. Tafoual1, C. Autret1, B. Montigny2, J. Santos-Peña2
Affiliations : 1 - Research Group Materials, Microelectronics, Acoustics, Nanotechnologies (GREMAN) UMR 7341 Tours University /CNRS, CEA, ENIVL Faculty of Sciences and Techniques, Parc de Grandmont, 37200 Tours, France 2 - Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l’Energie (EA 6299), Tours University, Parc de Grandmont, F-37200, France

Resume : Sodium ion technology is one of the most powerful alternatives to other energy storage technologies currently marketed or in a development stage. Compared to classical system as the lead-acid battery, Na-ion technology surpass in energy, specific properties and environmental friendliness. In comparison with the other Li-based technologies (Li-ion, Li-S, Li-Air), Na-ion lowers the device prices for a similar value of autonomy. However, the size of Na+ and its lower redox potential (+0.3V higher than for lithium) are still defying a suitable Na-ion batteries (NIB) technology. Therefore, there is increasing interest in coupling adequate positive and negative electrodes for maximizing the final device energy [1]. Despite the chemical and electrochemical resemblances of Li and Na, a number of negative electrodes for LIB shows very limited or none activity against sodium. For instance, graphite can intercalate 1/70 mole of sodium instead of 1/6 mole of lithium. Due to this limitation there is a wide research on positive electrodes in order to obtain high voltage systems. Current research in sodium-ion positive electrodes is focused on few families of inorganic compounds, namely transition metal layered oxides with O3, P2 and P3 crystal structures [2]. In this work we investigate P2-type electrodes based on NaxLiyM1-yO2 (M=Mn, Ni, Fe, Cr…) electrodes. The presence of partial Li substitution in the transition metal layer may assist the structural stability upon cycling. The active materials were synthesized using a sol-gel or solid state method, and characterized by XRD, SEM, TEM and BET techniques. Cyclic voltammetry and galvanostatic tests were performed using a two-electrodes cell using the metal oxide as working electrode and metallic sodium as pseudo- reference and counter electrode. Electrochemical impedance spectroscopy studies were performed using a three-electrodes cell using the metal oxide as working electrode and metallic sodium as counter and reference electrodes. [1] B.L. Ellis, L. F. Nazar, Current Opinion in Solid State and Materials Science 16 (2012) 168 [2] M.D. Slater, D. Kim, E. Lee, C.S. Johnson, Adv. Funct. Mater. 23, 947–958, 2013.

B.13.4
15:00
Authors : María Arnaiz 1, Juan Luis Gómez-Cámer 1, Jon Ajuria 1, Francisco Bonilla 1, Begoña Acebedo 1, María Jáuregui 1, Eider Goikolea 2, Teófilo Rojo 1, 2, Montserrat Galceran 1
Affiliations : 1 CIC energiGUNE, Albert Einstein 48, Technology Park of Álava, 01510 Miñano (Álava), Basque Country, Spain 2 Inorganic Chemistry Department, University of the Basque Country UPV/EHU, P.O. Box 644, 48080 Bilbao, Spain

Resume : Due to the limited Li resources, research on Na-ion batteries and capacitors is growing exponentially leading to the fast development of Na-based energy storage devices. When high energy density and power density are needed at the same time, hybridization between battery and supercapacitor electrodes can offer the figures of merit required. These devices are assembled by a battery-type and a capacitor-type electrode [1]. Regarding negative electrodes, titanates and hard carbon are the most studied in the recent years. Nevertheless, those materials provide limited energy density. Among the materials for higher energy density applications, Sn- and Sb-based alloys are some of the most promising alternatives [2]. In this communication we report the use of TiSb2 alloy as anode material for sodium ion batteries (NIBs) and capacitors (NICs). The electrochemical performance of TiSb2, synthesized by scalable methods, is investigated in NIBs. Stable cycling with a capacity of about 225 mAh g-1 is achieved for 200 cycles. The reaction mechanism is explored and discussed by means of operando XRD and ex situ TEM analysis. The excellent rate capability observed allows the use of TiSb2 in NICs combined with an activated carbon (AC) as positive electrode. The high energy densities achieved, of 132 Wh kg-1 at 114 W kg-1 and 65 Wh kg-1 at 11 kW kg-1 (Figure 1), are among the best reported values for alloying materials in NICs. However, due to the well-known problem of volume changes upon cycling of alloying materials, the capacity retention needs to be improved. By the use of a cross-linked functional binder as CMC-PAA we enhanced the retention after 1000 cycles from 10% to 63%, paving the way to develop new high-performance anodes for NICs. [1] G.G. Amatucci, F. Badway, A.D. Pasquier, T. Zheng, An Asymmetric Hybrid Nonaqueous Energy Storage Cell, J. Electrochem. Soc. 148 (2001) A930–A939. doi:10.1149/1.1383553. [2] M.Á. Muñoz-Márquez, D. Saurel, J.L. Gómez-Cámer, M. Casas-Cabanas, E. Castillo-Martínez, T. Rojo, Na-Ion Batteries for Large Scale Applications: A Review on Anode Materials and Solid Electrolyte Interphase Formation, Adv. Energy Mater. 7 (2017) 1700463. doi:10.1002/aenm.201700463.

B.13.5
15:15
Authors : Marek Skrzypkiewicz, Konrad Motylinski, Michal Wierzbicki
Affiliations : Marek Skrzypkiewicz(1,2), Konrad Motylinski(1,3), Michal Wierzbicki(1,3) 1. Department of High Temperature Electrochemical Processes (HiTEP), Institute of Power Engineering, Augustowka 36, 02-981 Warsaw, Poland 2. AGH 0 University of Science and Technology, Faculty of Fuels and Energy, Av. Mickiewicza 30, 30-059, Cracow, Poland 3. Institute of Heat Engineering, Warsaw University of Technology, Nowowiejska 21/25, 00-665 Warsaw, Poland

Resume : Currently, one of the considered efficient hydrogen generation methods is high temperature water electrolysis. In recent years high temperature electrolyzers based on Solid Oxide Cells has been gaining interest because of their (i) high reaction rate, (ii) very good efficiency, (iii) no need to use noble metals as a catalysts, (iv) observed unique self-healing of the cells and (v) modular design makes it easy to scale-up the system based on SOEC stack. However, the drawbacks of operation at high temperatures are related to material stability problems which limit the durability of the SOEC. For this paper, SOEC mid-term operation was analysed experimentally. The test was performed on a single, planar 5cm x 5cm fuel electrode supported solid oxide cell, based on Ni-YSZ with effective area of the oxidant electrode of 16 cm2. The over 250 hour test was performed at constant current density (125 mA/cm2) and temperature (700°C). In parallel with experimental studies, numerical activities were performed. The existing and previously validated model of SOC electrochemical performance was enhanced with degradation parameters of the cell. Based on the realized experiments, the modified model was additionally verified. The prediction error did not exceed 5%. In this work, the degradation and performance drop of high temperature SOEC was investigated and discussed both experimentally and numerically. The observed degradation rate during the mid-term operation was 0.38 mV/h.

B.13.6

Symposium organizers
Claudia D’URSOCNR-ITAE

Via Salita Santa Lucia Sopra Contesse, 5-98126 Messina, Italy

durso@itae.cnr.it
Juergen GARCHEUlm University

Chemistry Department - Albert-Einstein-Allee 11, 89081 Ulm, Germany

juergen.garche@uni-ulm.de
Luis Gerardo ARRIAGA HURTADOCIDETEQ-S.C.

Sanfandila Pedro Escobedo QRO C.P. 76703, Mexico

larriaga@cideteq.mx