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Materials and devices for energy and environment applications


Materials for electrochemical storage systems for the electric vehicles

Introduction and scope:

Regarding energy density and cost, advanced and novel battery technologies are the key drivers for the success of hybrid and pure electric vehicles.

This symposium aims to join the research community working on Li-ion and post lithium-ion batteries, posing an innovative vision for new concepts and applications mainly to electric vehicles. It will address topics varying from electrode and electrolyte materials synthesis to their characterization, cycle life and application in lab scale cells and in industrial systems.

The main obstacle to a fast widespread use of full and hybrid EVs throughout the world is the need for batteries that possess both high energy and high power densities, demonstrate prolonged cycle life, contain only abundant and cheap raw materials and demonstrate excellent safety features.. The increase of performance, as well as safety, cycle life and eco-compatibility of a Li-ion cell depends mainly on the chosen materials, on the interaction among these materials and on the conditions of charging and discharging. One of the reasons of the recent achievements in the battery field is he recognition of the importance of creating composite nanostructured materials with higher electronic/ionic conductivity.

This symposium will bring together the research community dealing with the ways to overcome the current limitations related to some of above defined challenges, concerning battery materials their performance and ageing phenomena in view of EVs application.

Hot topics to be covered by the symposium:

  • Nanostructured Electrode materials for Li-on batteries
  • Development of green and safe electrolyte chemistries for Li-ion batteries
  • Post-lithium ion batteries
  • Understanding the ageing and degradation processes with the support of modelling

List of invited speakers:

  • Robert Dominko (Institute of Chemistry, Ljubljana, Slovenia)
  • Yair Ein-Eli (Dept. of Material Science, Technion, Haifa, Israel)
  • Steve Greenbaum (Dept of Physics, Hunter College, CUNY, NY, USA)
  • Wladek Wieczorek (Faculty of Chemistry, Warsaw University of Technology, Poland)
  • Margret Wohlfahrt-Mehrens (Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg, Germany)
  • Dimitrios Zarvalis (Aerosol & Particle Technology Laboratory, CERTH, Thessaloniki, Greece)


The best papers will be published in Electrochimica Acta and Journal of Solid State Electrochemistry.

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CATHODES : Bodoardo Silvia
Authors : Idoia Urdampilleta, Iratxe de Meatza
Affiliations : IK4-CIDETEC, Pº Miramón 196, 20009 Donostia-San Sebastián (Gipuzkoa), Spain

Resume : MARS-EV (Materials for Ageing Resistant Li-ion High Energy Storage for the Electric Vehicle) FP7 European project focuses on the development of high-energy electrode materials (250 Wh/kg at cell level) via sustainable scaled-up synthesis and safe electrolyte systems with improved cycle life (>3000 cycles at 100%DOD). Through prototype cell assembly and testing coupled with modelling, the understanding of the ageing behaviour at the electrode and system levels will be improved. Full life cycle and recycling of the developed technology is also assessed. An overview of achievements after 3 of the 4-year workprogram will be provided: • High voltage cathodes: Nanodimensional LiCoPO4 by Flame Spray Pyrolysis; Coated Li-rich NMC with increased capacity and cycle-life. • High capacity anodes: nano-Silicon composites (Si/C) with stable cycling. • Electrode preparation using waterborne binders: Optimised graphite for aqueous anode slurries and development of cathode formulations. • Green and safe electrolytes: additives increasing cycle-life of Li-rich NMC; ionic liquids; solid polymer electrolytes with no-flammability and performance at 20ºC. • New generation eco-friendly low-cost cellulose-based packaging for pouch cells. • Study of ageing and degradation processes: 3D Imaging in-operando tomography for electrode-level modelling (Si anode); Design of Experiment for baseline (NMC, LFP) cell ageing tests; LFP pouch cell P2D+3D thermal model for battery pack optimisation. • Environmental assessment: LCA showing lower impact for LFP aqueous electrode processing; No regulatory (REACH, CLP) restrictions found. Acknowledgement: Project financially supported by the European Commission (FP7) under Grant Agreement No. 609201.

Authors : Svetoslava Vankova, Daniele Versaci, Julia Amici, Anna Ferrari, Rosanna Rizzi, Silvia Bodoardo, Nerino Penazzi
Affiliations : S. Vankova DISAT Polytechnic of Turin , Turin, Italy D. Versaci DISAT Polytechnic of Turin , Turin, Italy J. Amici DISAT Polytechnic of Turin , Turin, Italy A. Ferrari Department of Chemistry, University of Turin, Turin, Italy R. Rizzi Institute of Crystallography (IC-CNR), Bari, Italy S. Bodoardo DISAT Polytechnic of Turin , Turin, Italy N. Penazzi DISAT Polytechnic of Turin , Turin, Italy

Resume : Lithium-ion battery is the most promising electrochemical energy storage technology. LiCoO2 and spinel LiMn2O4 are successful cathodes materials, but they are expensive, not abundant, toxic and thermally unstable. Iron-based materials such as LiFePO4 is an alternative, but their capacity is limited to 170 mAhg-1 [1]. Therefore, orthosilicates (Li2MSiO4, M= Fe, Mn) are now studied [2] because they are cost effective, eco-friendly, abundant, thermally stable. The possibility of exchanging two Li+ ions per Li2MnSiO4, with theoretical capacity exceeding 300 mAhg-1, has attracted great interest. Unfortunately, Li2MnSiO4 suffer of high sensitivity to air, leading to fast oxidation of Mn2+ and sharp decrease of capacity. The special conditions for storage increases significantly its price. Therefore, we consider the pyroxenoid group of minerals, because they are a natural host for Li and Mn ions [3] We report the first results on Li and Mn containing silicates: Mn4LiH[Si5O15] and Mn4(Li, Na)H[Si5O15]. We found that they are stable in air until 50°C. The problem of low electronic conductivity was overcome adding a carbonization agent recycled from waste cellulose during crystallization in argon at 650°C. The synthesized minerals are electrochemically active with capacity of 580 mAhg-1 and with a stable cycle life up to 20 cycles at various C-rates. [1] Padhi A.K., Nanjundaswamy K.S., Goodenough J. B. JES, 1997, 144, 1188; [2] Armand M., Michot C., Ravet N., Simoneau M., Hovington P., European patent, A1, 2001, EP 11340826; [3] Liebau F., American Mineralogist, 1980, 65, 981.

Authors : G. Lefèvre, J.B. Ducros, S. Martinet
Affiliations : CEA-LITEN/DEHT (Département de l'Electricité et de l'Hydrogène pour les Transports)

Resume : In the frame of current electric vehicles deployment, strong efforts are done to find new cathode materials to provide higher energy density, safety and lower cost to the next generation of lithium-ion batteries. Silicate polyanions Li2MSiO4 (M=Fe, Mn, Co, Ni) have been investigated for exchange up to 2 Li per formula unit (~330 mAh/g). Mn-based material was firstly reported by Dominko et al. in 2006. Extraction of its 2 Li ions has been computed to occur above 4V vs. Li. Similarly to LiFePO4, Li2MnSiO4 suffers from low electronic conductivity therefore particle downsizing has been also successfully used. For the first time to our knowledge, we have demonstrated fast and spontaneous reactivity of Li2MnSiO4 nanoparticles with air. Careful preparation in argon prevented formation of insulating Li2CO3 around particles as observed by X-Ray Diffraction and X-ray Photoelectron Spectroscopy and lead to lower polarization and higher capacities. Up to now, discharge capacities beyond 200 mAh/g have been observed by several research groups but with capacity loss. During 1st charge, amorphization occurs due to preference of Mn(III/IV) for different environments than tetrahedral and repulsion between MnO4-SiO4 layers for 2D-Pmn21 polymorph. We showed that limited exchange of 0.3-0.4 Li/f.u. preserved structure integrity. To overcome these phenomena, a new substitution strategy will be presented to stabilize structure and benefit from maximum of the theoretical capacity of Li2MnSiO4.

Authors : You-Hwan Son, Byung-Jin Choi, Jin-Hwan Park
Affiliations : Energy Lab, Samsung Advanced Institute of Technology, 130 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do, 16678, Republic of Korea

Resume : Nickel-rich layered lithium transition-metal oxides, LiNi1−xMxO2 (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we present a nickel-rich lithium transition-metal oxide with a very high capacity (~over 215 mA h g−1), where layered double hydroxide ([M2+1-xM3+x(OH)2][An-]x/n • mH2O, where M2+ and M3+ are divalent and trivalent cation) hybridize on outer layer of each particle. Using this functional hybridization approach by electrostatics attraction between negative charged nickel-rich layered lithium transition-metal oxides and positive charged layered double hydroxide, we are able to successfully prepare cathode materials with the high energy and long life times. Moreover, as advanced approach, hybridization with exfoliated layered double hydroxide is composed of thin and uniform passivation layer on and micrometre-size secondary particles of this cathode material, resulting in a high rate capability. The experimental results suggest that this hybridizing cathode material is promising for applications that require high energy, long maintain life and excellent safety such as electric vehicles.

Authors : Krzysztof Maranski, Mark Copley, James Cookson
Affiliations : Johnson Matthey Battery Technologies

Resume : Olivine-based lithium transition metal phosphate materials (LiMPO4, M = Fe, Mn, Co, Ni) have attracted extraordinary attention as a cathode material in Li-ion batteries. In particular, the presence of strong P-O covalent bonds results in improved safety performance over other cathode materials. LiFePO4 (LFP) has become a highly successfully commercialised cathode material for Li-ion batteries, however, does suffer from a relatively low energy density. The isostructural lithium cobalt phosphate (LiCoPO4) features similar capacity at a higher discharge voltage (4.8 vs. 3.4 V), resulting in theoretical ~40% higher energy density. Similarly to LFP, LiCoPO4 cathodes suffer from poor lithium ion and electronic conductivities, which can be successfully mitigated by nano-sizing and conductive coating strategies. There are numerous routes to synthesise nanoparticles, both chemical and physical. Of these, Flame Spray Pyrolysis (FSP) offers many distinct advantages:  single step route to nanoparticles;  scalable;  ability to make multicomponent materials in one step,  potential access to novel phases ;  absence of solid or liquid waste;  rapid process, allowing easy screening of a number of materials, In this study we demonstrate the successful preparation of nano-dimensional high voltage olivine materials via flame spray pyrolysis. 1. K. Amine, H. Yasuda, M. Yamachi, Electrochemical and Solid-State Letters 2000, 3, 178-179; 2. C. Delmas, M. Maccario, L. Croguennec, F. Le Cras, F. Weill, Nat Mater 2008, 7, 665-671; 3. Q. D. Truong, M. K. Devaraju, Y. Ganbe, T. Tomai, I. Honma, Sci. Rep. 2014, 4.

CATHODES : Iratxe De Meatza
Authors : D. Zarvalis, G. A. Gkanas, G. Kastrinaki, G. Karagiannakis, A.G. Konstandopoulos
Affiliations : Aerosol &Particle Technology Laboratory, CERTH/CPERI, P.O. Box 60361, 57001, Thessaloniki, Greece; Department of Chemical Engineering, Aristotle University, PO. Box 1517, 54006, Thessaloniki, Greece

Resume : Rapid advancement of technologies for production of next-generation Li-ion batteries will be critical to address the requirements for clean, efficient and safe transportation by EVs Electric Vehicles. The challenge of bringing high voltage (5V) cells into the market calls for advancements in the employed cathode materials. Current work discusses the synthesis of LiNi0.5Mn1.5O4 particles by aerosol spray pyrolysis. The synthesis parameters which have been exploited in order to study their effect on the particle nanostructure are the chemistry and concentration of the precursor solution, the synthesis temperature in the tubular reactor and post calcination temperature profiles of the collected particles, while the particles were synthesized in a lab scale reactor for primary evaluation and a pilot scale reactor for the production of larger quantities. The precursor solution chemistry and reactor operating conditions were adjusted in order to obtain the LNMO structure, while the post-calcination profile conditions of the collected powder were studied in order to obtain the two main spinel phases: the ordered (P4332) and the disordered (Fd3m), which affect the electrochemical activity of the material. The temperature profiles which have been studied vary from 700-900oC, with the temperatures over 800oC leading to the disordered phase and larger crystallite sizes. Higher aerosol concentration has led to the formation of a different particle morphology, due to the lower evaporation rate. The morphology of the LNMO particles is near-spherical with various porosity formation depending on the calcination profile. Each of the studied parameter had a significant effect on the electrochemical performance.

Authors : Agnese Birrozzi, Nina Laszczynski, Jan von Zamory, Stefano Passerini
Affiliations : Helmholtz Institute Ulm (HIU), Electrochemistry I, 89081 Ulm, Germany Karlsruher Institute of Technology (KIT), 76021 Karlsruhe, Germany

Resume : In order to increase the energy density of lithium-ion batteries, Li[Li0.2Mn0.56 Ni0.16 Co0.08]O2 cathode material (lithium-rich NMC) has attracted much attention due to its high operating voltage and specific capacity [1]. However, its practical application is still limited due to the poor stability of the cathode / alkyl carbonate-based electrolyte interface. In fact, the working potential of this material is beyond the electrochemical stability window of the conventional carbonate-based electrolytes (< 4.3 V vs. Li+/Li), thus leading to the electrolyte oxidative decomposition [2]. This phenomenon, besides reducing the energy stored in the cell, might even results in the formation of decomposition products (e.g., HF) leading to metal dissolution, and hence material capacity fading. In addition, in the attempt to reduce the battery cost, the substitution of fluorinated binders like polyvinylidene difluoride (PVdF) with aqueous binders such as sodium carboxymethyl cellulose (sodium CMC) [3] gives rise to the aluminum current collector corrosion [4] and the active material degradation, because of the high basicity of the aqueous slurries. The most helpful and efficient strategies [5] to overcome the above mentioned issues are: 1) Preliminary coating of the active material to prevent its reactions with both water and electrolyte; 2) Use of electrolyte additives, which can be sacrificially decomposed to form a protective layer on cathode surface, thus minimizing undesired reactions between the cathode and the electrolyte. This study, therefore, presents an investigation of the effects of the coating and the electrolyte additives with respect to their capability of enhancing the coulombic efficiency and capacity retention of the lithium-rich NMC. The positive influence of both the strategies have been demonstrated combining electrochemical and analytical techniques, such as SEM, TEM, EIS, XRD, XPS and Raman spectroscopy. The coating on the composite electrodes prepared with the aqueous binder is demonstrated to be beneficial in particular with regard to the prevention of aluminum corrosion, leading to a higher cycling stability respect than uncoated material. Also the electrolyte additives were demonstrated to enhance the capacity retention and the coulombic efficiency upon cycling. The feasibility of the material coating and the electrolyte additives employment for practical application will be demonstrated showing full-cell studies with graphite as anode. [1] P. Rozier, J.M. Tarascon, Journal of The Electrochemical Society, 162 (2015) A2490-A2499. [2] S. Tan, Y.J. Ji, Z.R. Zhang, Y. Yang, ChemPhysChem, 15 (2014) 1956-1969. [3] G.T. Kim, S.S. Jeong, M. Joost, E. Rocca, M. Winter, S. Passerini, A. Balducci, Journal of Power Sources, 196 (2011) 2187-2194. [4] S.F. Lux, F. Schappacher, A. Balducci, S. Passerini, M. Winter, Journal of The Electrochemical Society, 157 (2010) A320-A325. [5] N.-S. Choi, J.-G. Han, S.-Y. Ha, I. Park, C.-K. Back, RSC Advances, 5 (2015) 2732-2748.

Authors : Yuan Chen (1), Huajun Feng (1), Yihua Wang*, (1) , Li Lu (2)
Affiliations : (1) School of engineering, Republic Polytechnic, 9 Woodlands Avenue 9, Singapore 738964 (2) Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576

Resume : Porous-structure foam may cause transport changes of chemical materials, selectivity changes of function group, and so on. Nano-porous metal foams have been a long sought-after class of materials in the quest for high-surface-area conductive and catalytic materials. In lithium ion battery field, nano-porous structuring of electrodes for electrochemical energy storage (batteries) makes high power battery with ultra-fast charging/discharging properties in one minute possible, due to being high-surface-area favorable for fast transport of Li+ and more tolerate of shape deformation when charging/discharging. Turning block metals into three-dimensional nano-porous foams in a low-cost and scalable way keeps being a significant challenge. There are several well-established approaches for preparing nano-porous metal thin films: most notably through de-alloying, recently through deposition of metals on nanostructured templates, and laser etching, etc. However, these approaches are complicated and/or involve expensive equipment. In this paper, we report a low-cost and scalable ultrasonic chemistry synthetic method for producing nano-porous metal copper foams and their electrochemical performance as current collector in lithium batteries. Distributions of nano-pores on the copper surface and synthetic mechanism are presented and discussed.

Authors : W. Olszewski, I. Isturiz, C. Marini, M. Okubo, H. Li, H. Zhou, T. Mizokawa, N. L. Saini, L. Simonelli
Affiliations : ALBA Synchrotron Light Facility, Carrer de la Llum 2-26, 08290 Cerdanyola del Valles, Barcelona, Spain Faculty of Physics, University of Bialystok, 1L K. Ciolkowskiego Str., 15-245 Bialystok, Poland; ALBA Synchrotron Light Facility, Carrer de la Llum 2-26, 08290 Cerdanyola del Valles, Barcelona, Spain; ALBA Synchrotron Light Facility, Carrer de la Llum 2-26, 08290 Cerdanyola del Valles, Barcelona, Spain; National Institute of Advanced Industrial Science and Technology (AIST), Umezono 1-1-1, Tsukuba 305-8568, Japan; National Institute of Advanced Industrial Science and Technology (AIST), Umezono 1-1-1, Tsukuba 305-8568, Japan; National Institute of Advanced Industrial Science and Technology (AIST), Umezono 1-1-1, Tsukuba 305-8568, Japan; Dep. of Physics, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan Dep. of Complexity Science and Engineering, University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561, Japan; Dip. di Fisica, Universita di Roma “La Sapienza” - P. le Aldo Moro 2, 00185 Roma, Italy; ALBA Synchrotron Light Facility, Carrer de la Llum 2-26, 08290 Cerdanyola del Valles, Barcelona, Spain

Resume : Vanadium pentoxide (V2O5) is in general an attractive multifunctional material used in widespread applications in various fields, as well related to lithium-ion batteries [1]. V2O5 possesses an outstanding structural versatility and can be manufactured into nanostructures with superior properties [1,2]. In particular, one-dimensional nanostructures, i.e., the V2O5 nanowires, have attracted considerable attention due to importance of these in basic scientific research and potential technological applications [3,4]. Among the potential cathode materials, V2O5 has been extensively studied because of its low cost, abundance, as well as its high energy efficiency and relatively high theoretical capacity [5,6]. However, due to its slow electrochemical kinetics and poor structural stability, two major problems for this electrode material are its low rate and limited long-term cycling stability [7]. In order to improve these performances, many efforts have been made and nanostructuring has been successful in extending the electrochemical performance of V2O5 [8]. Temperature dependent extended X-ray absorption fine structure (EXAFS) study is a powerful tool to uncouple the static from the dynamic disorder, to have direct access to the local force constant between the atom pairs. We recently demonstrated the correlation between the electrochemical properties, like capacity and kinetics, and the local force strength in cathode materials [9]. Here, we report the local structural investigation of V2O5 bulk nanoparticle and nanowires by temperature dependent V K-edge EXAFS measurements. The V-O local force strength is found to change as a function of nanosizing. In the case of nanowires, different V-O local force strengths have been found for different directions (in the nanowires direction or perpendicular to it). The correlation between the modulation of the local structure induced by the nanosizing and the functional properties are investigated in details. References: [1] J. J. Yu, J. Yang, W. B. Nie, Z. H. Li, E. H. Liu, G. T. Lei, and Q. Z. Xiao, Electrochim. Acta 89, 292 (2013). [2] C. L. Dong, Y. K. Ho, C. C. Chang, D. H. Wei, T. C. Chan, J. L. Chen, W. L. Jang, C. C. Hsu, K. Kumar, and M. K. Wu, EPL 101, 17006 (2013). [3] T. Zhai, H. Liu, H. Li, X. Fang, M. Liao, L. Li, H. Zhou, Y. Koide, Y. Bando, and D. Golberg, Adv. Mater. 22, 2547 (2010). [4] W. Avansi, L. J. Q. Maia, C. Ribeiro, E. R. Leite, and V. R. Mastelaro, J. Nanopart. Res. 13, 4937 (2011). [5] Wang, S. Q.; Li, S. R.; Sun, Y.; Feng, X. Y.; Chen, C. H., Energy Environ. Sci. 2011, 4, 2854–2857. [6] Wang, Y.; Cao, G. Z., Adv. Mater. 2008, 20, 2251–2269. [7] Ban, C. M.; Chernova, N. A.; Whittingham, M. S., Electrochem. Commun. 2009, 11, 522–525. [8] Mai, L. Q.; Dong, F.; Xu, X.; Luo, Y. Z.; An, Q. Y.; Zhao, Y. L.; Pan, J.; Yang, J. N., Nano Lett. 2013, 13, 740–745. [9] W. Olszewski, M. Avila Perez, C. Marini, E. Paris, X. Wang, T. Iwao, M. Okubo, A. Yamada, T. Mizokawa, N. L. Saini, and L. Simonelli, J. Phys. Chem. C 2016, 120, 4227−4232.

POST- LITHIUM ION : Diana Golodnitsky
Authors : Jan Bitenc, Klemen Pirnat, Tanja Bančič, Anna Randon Vitanova, Robert Dominko
Affiliations : a National institute of chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia b Honda R&D Europe (Deutschland) GmbH, Carl-Legien-Strasse 30, 63073 Offenbach, Germany

Resume : Rechargeable magnesium (Mg) batteries are considered as sustainable option for electrochemical energy storage due to natural abundance of magnesium and possibility to use metallic magnesium as anode. This together with high specific theoretical capacity (2205 mAhg-1 and 3.832 mAhcm-3) and with a reduction potential of −2.356 V versus standard hydrogen electrode (NHE) puts a lot of motivation to explore all possibilities of that battery system. Metallic magnesium is known as a highly passivating metal and it requires a special attention to the electrolyte development. Recent progress in the field of non-nucleophilic electrolytes with high oxidative stability1,2 openes the possibility to employ these types of electrolytes with organic materials where weak intermolecular forces enable the reversible electrochemical interaction of Mg cations coupled with fast diffusion.3,4 In this contribution we demonstrate use of several different organic based polymers as an active cathode material which presents a robust approach towards sustainable Mg batteries with high power and good cycling properties. Redox active quinone groups in the polymer matrix together with Mg powder anode separated by non-nucleophilic electrolytes show excellent electrochemical activity and stability during cycling. All electrochemical tests were performed in the two electrode modified Swagelok laboratory cells. The mechanism of redox reaction has been tested with in operando IR spectroscopy. [1] S. Kim, T. S.

Authors : Romain Berthelot, Fabrizio Murgia, Lorenzo Stievano, Laure Monconduit, Danielle Laurencin and Marie-Liesse Doublet
Affiliations : Institut Charles Gerhardt de Montpellier (ICGM - UMR5253), Université de Montpellier, 2, pl. E. Bataillon, CC1502, 34095 Montpellier Réseau sur le Stockage Electrochimique de l’Energie (RS2E – FR3459), Université de Picardie, 33, rue St-Leu, 80039 Amiens

Resume : Investigating post-Li-ion systems such Mg-batteries is a promising challenge in the quest for high energy density. Mg offer theoretical capacities that compete with Li. However, in contact with conventional electrolytes, the passivation film limits the cationic diffusion. Compatible electrolytes are reported but show narrow electrochemical window. Searching for alternative anode materials might help in developing performant Mg-batteries. We focus on the electrochemical behavior of electrode materials based on p-block elements (Bi, Sb, etc.) Micrometric powders as active materials are tested vs. Mg with organohaloaluminate electrolyte. An important focus is devoted to the investigation of the electrochemical mechanisms especially through operando XRD. Electrodes formulated from Bi powder exhibit the best performance. The alloying reaction forming Mg3Bi2 occurs at a stable low potential and is highly reversible. In comparison Sb- or Sn-based electrodes hardly alloy with Mg. A reversible alloying reaction is also noticed with In. However, with a dramatic fading is observed upon cycling or with increasing current rates. Bi is also combined with lighter but less active elements in order to search for synergistic effects. Intermetallic InBi, solid-solution compositions Bi1-xSbx, and composite Bi/Sn materials are obtained by mechanical alloying. Electrochemical mechanisms present unexpected pathways with intermediate phases and/or conversion-alloying process. Solid-state 25Mg NMR is also applied to electrode characterization and experimental observations are also coupled with a theoretical analysis from DFT for explaining the poor electrochemical behavior of Sb, despite its similarities with Bi.

Authors : H. Anne (a), D. Saurel (a), F. Nobili (b)
Affiliations : (a) CIC Energigune - Parque Tecnológico de Alava, C/Albert Einstein 48, 01510 Miñano, Spain,+34945297108 (b) School of Science and Technology, Chemistry division, University of Camerino, Via S. Agostino 1, I-62032 Camerino, MC, Italy;

Resume : LiFePO4 is one of the few commercial Li-ion battery cathode materials owing to its low cost, stability and good electrochemical performance. It is also one of the most studied for its puzzling transformation mechanism varying from bi-phasic to solid solution depending on particle size, defects, rate or temperature [1]. The sodium battery parent compound, NaFePO4, has an even more complex transformation mechanism than LiFePO4 as reported by our group [2], while the differences of Li and Na diffusion kinetics remain to be fully understood. Indeed, the literature shows a very large values dispersion for the diffusion coefficient and its activation energy for LixFePO4, while the very few reports that can be found for NaxFePO4 present notable discrepancies [3]. In addition, in both cases most of the reports are limited to the end members as, at the intermediate compositions, the biphasic transformation hinders proper experimental estimation of the diffusion coefficient. Within this scope, based on potentiostatic intermittent titration technique and in-situ electrochemical impedance spectroscopy, we experimentally estimated the diffusion coefficient and its activation energy on the whole composition range for both LixFePO4 and NaxFePO4. Differences and similarities will be discussed in regard of their implication on both materials electrochemical performance. [1] Malik et al., J. Electrochem. Soc. 160, A3179 (2013) [2] Galceran et al., Phys. Chem. Chem. Phys. 16, 8837 (2014) ; Saracibar et al., Phys. Chem. Chem. Phys. 18, 13045 (2016) [3] Zhu et al., Nanoscale 5, 780 (2013) ; Tripathi et al., Energy Environ. Sci. 6, 2257 (2013) ; Ong et al., Energy Environ. Sci. 4, 3680 (2011) ; Nakayama et al., Solid State Ion. 286, 40 (2016)

Authors : Pedro Lopez-Aranguren Oliver, Anh Ha Dao, Christian Jordy
Affiliations : SAFT 111/113 Boulevard Alfred Daney 33074 Bordeaux Cedex, France

Resume : Lithium-sulfur (Li-S) all-solid-state batteries are considered as a promising candidates for the utilization in large-scale applications including stationary uses for load leveling, electric vehicles and so forth [1,2]. Advantages of all-solid-state batteries over organic liquid electrolyte based lithium ion batteries are: a wider choice of electrolytes and electrodes, questions related to safety and avoiding the Li dendrite formation, leakage and vaporization of liquid electrolytes [3]. Elemental sulfur is a very attractive material to be used as positive electrode material because of its high theoretical specific capacity of 1675 mAhg-1 at an average potential of 2.2 V vs. Li/Li+[4]. The electrochemical reaction of the S/Li couple (2Li++ 2e- ⇆ Li2S) includes the formation of lithium sulfide (Li2S) which corresponds to the discharged state in a Li-S battery. Li2S can be used as positive electrode material with a theoretical capacity of 1166 mAhg-1. Li2S has received much attention due to the potential to use non-lithium anodes. Instead, high-capacity anode materials such as silicon can be used as negative electrodes with improved safety. In the present work, all-solid-state batteries were developed using lithium borohydride (LiBH4) as solid electrolyte. LiBH4 is known as a fast Li conductor at its hexagonal phase at ca. 120 oC [5] and it already shown a good performance in sulfur all-solid-state batteries [6]. S and Li2S were selected as active materials for the cathode. To resolve the insulating problem of S and Li2S, conductive carbon was used as an additive in the positive electrode composition. High energy ball milling was performed in order to improve the contact between the active materials and carbon. The final positive material composition resulted in the mixture between the high energy ball milled composite and the electrolyte. The all-solid-state batteries performed in this work were assembled in a three-layer configuration of positive material/ electrolyte/ Li Metal (Figure 1). The positive material and the electrolyte were pressed at room temperature to obtain a pellet with a tight interface between the active materials and the electrolyte. The pelletized batteries were placed into stainless steel cells for the electrochemical measurements. Our battery using S as active material exhibited an initial discharge capacity of 920 mAhg-1 at 0.02C and 120 oC. Moreover, it demonstrated a high operation stability with a discharge capacity of ca. 700 mAhg-1 at 0.1C in the 30th cycle (Figure 2). We found out several differences in the cycling performance of the initial discharged cells using Li2S in comparison to that of S. An extensive range of characterization tools such as FTIR, DSC, BET and SEM were applied in order to elucidate the differences on the performance of both active materials and their interaction with the electrolyte. [1] Goodenough, J. B.; Park, K.−S., J. Am. Chem. Soc. 2013, 135, 1167 [2] Takada, K., Acta Mater. 2013, 61, 759 [3] Kato, Y.; Kawamoto, K.; Kanno, R.; Hirayama, M., Electrochemistry 2012, 80, 749−751 [4] Ya-Xia Yin, Sen Xin, Yu-Guo, Li-Jun Wan. Angew., Chem. Int. Ed. 2013, 52, 13186 [5] A.unemoto, M. Matsuo, S. Orimo, Adv. Funct. Mater. 2014, 24, 2267 [6] A. Unemoto, S. Yasaku, G. Nogami, M. Tazawa, M. Taniguchi, M. Matsuo, T. Ikeshoji, S. Orimo, Appl. Physics. Letters, 105, 2014

POSTER : Gianni Appetecchi
Authors : Katja Fröhlich, Evgeny Legotin, Atanaska Trifonova
Affiliations : Austrian Institute of Technology, Electric Drive Technologies, Giefinggasse 2, 1210 Vienna, Austria

Resume : Lithium Nickel Manganese Cobalt Oxide, shortly called NMC, is one of the most promising cathode materials for Lithium-ion batteries to serve in automotive electric drives. Nowadays, this commercially available electrode material is produced in different ways, such as solid state, sol-gel routes, and the coprecipitation method. All these syntheses are very expensive in terms of time and cost. Therefore, the synthesis route is a very important factor for energy efficient large-scale production of battery materials and further reduction of Li-ion battery costs. A flame pyrolysis route was adapted in our research for production of NMC in a single step. Different synthesis parameters were varied in order to obtain the cathode material with the targeted stoichiometric composition and microstructure. The prepared powders were fully characterized physicochemically regarding particle size and distribution, surface area, and porosity. Actual composition was verified by ICP-AES analysis and the crystal structure was characterized with x-ray diffraction. Additionally, the materials’ electrochemical performance was recorded from half-cell measurements versus lithium metal. Cyclic voltammetry measurements were performed to obtain the real specific capacities of the NMCs from different synthesis conditions. The presented results show optimized process parameters. Further implementation in a large-scale production pilot line is ongoing. The electrochemical behavior of the optimized material will be discussed in comparison to the parameters obtained from the commercial sample. Acknowledgement This work was financially supported by the Austrian Federal Ministry for Transport, Innovation and Technology (bmvit) and the Austrian Research Promotion Agency (FFG).

Authors : K. Goldshtein1, D. Schneier1, N. Aloni, M. Goor, K. Freedman1, E. Peled1, and D. Golodnitsky1,2
Affiliations : K. Goldshtein1, D. Schneier1, N. Aloni, M. Goor, K. Freedman1, E. Peled1, and D. Golodnitsky1,2

Resume : We report on the formation of composite silicon-based multiphase nanopowders as promising active-anode materials for high-energy-density, high-capacity-retention lithium-ion batteries. Simple synthetic routes based on grinding and pyrolysis were developed for the preparation of core-shell Si, SiNi and SiCu composite particles attached to carbon nanotubes. The particles were characterized by a variety of analytical and electrochemical methods. It was found that neat silicon and alloyed nanoparticles are wrapped by carbon nanotubes and coated by nanometer-thick amorphous carbon. Li/LiPF6 EC:DEC/Si-C-MWCNT cells with anodes composed of about 80% core-shell Si-C composite (36% Si in the anode) ran for more than 1000 cycles with a degradation rate of 0.07%/cycle. The SiNi/MWCNT composite anode revealed a remarkably higher capacity-retention rate at initial cycles and higher C-rate capability. Li/SiNi/MWCNT cells ran for about 250 cycles demonstrating a reversible capacity of about 620mAh/gSi at 120μA/cm2 at cycle 210, and 800mAh/gSi at 50μA/cm2 at cycle 240. The lithium/silicon cell with modified alloyed anodes exhibited 1000mAh/anode reversible capacity for more than 200 cycles. The full cell comprising high-voltage cathode and modified alloyed anode ran at C/4 rate for over 300 cycles with 600mAh/g reversible capacity. Acknowledgments This work is funded by EU FP7, MARS-EV” Project, and by the Israel Academy of Science.

Authors : E. Peled1, F. Patolsky1, D. Golodnitsky1, 2, K. Freedman1, G. Davidi1, D. Schneier1
Affiliations : 1. School of Chemistry, Faculty of Exact Sciences, 2. Applied Materials Research Center, Tel Aviv University, Tel Aviv, 6997801, Israel.

Resume : We report on the scalable synthesis and characterization of novel-architecture three-dimensional high-capacity amorphous SiNW-based anodes, with focus on the study of their electrochemical-degradation mechanisms. We achieved an unprecedented combination of remarkable performance characteristics: high loadings of 3-25 mAh/cm2, a very low irreversible capacity (10% for the 3-4mAh/cm2 anodes), current efficiency greater than 99.5%, cycle stability both in half cells and in a LiFePO4 battery and fast charge–discharge rates (up to 2.7C at 20mA/cm2). These SiNW-based binder-free 3D anodes have been cycled for over 500 cycles, exhibiting a stable cycle life. Notably, it was found that the increase in the continuous SEI layer thickness, and the concomitant increase in resistivity, represents the major cause of the observed capacity loss of the SiNW-based anodes, as we demonstrated by cleaning and reusing cycled anodes. We also demonstrate the effects of different types of coatings on the SEI and on cycling stability of the cell. Our data reveal that NW-based anodes of novel architecture are expected to meet the requirements of lithium-ion batteries for both portable and electric-vehicle applications.

Authors : L.Silvestri [1], L.Cirrincione [2], P.Stallworth [2], S.Greenbaum [2], S.Panero [1], S.Brutti [3], P.Reale [4]
Affiliations : 1. Dipartimento di Chimica, Sapienza Università di Roma; 2. Department of Physics and Astronomy, Hunter College; 3. Dipartimento di Scienze, Università della Basilicata; 4. ENEA, Centro Ricerche Casaccia

Resume : NaAlH4 has recently emerged as a potential anodic material in lithium ion batteries. Through a conversion reaction[1], it is able to achieve more than 1700 mAh/g upon first discharge[2,3]. Despite its high specific capacity, NaAlH4 suffers from poor cycle efficiency, mostly due to the severe volume expansion following the conversion reaction and resulting in damage to electrode mechanical integrity with loss of electrical contact. Large improvements in terms of electrochemical reversibility have been achieved by mixing NaAlH4 with carbon under High Energy Ball Milling[2]. Mechanochemical treatments promote the creation of an intimately mixed carbon-hydride composite material in which carbon acts as a coating agent and limits large volumetric changes, preventing grain growth and sintering. Furthermore, the improved thermal hydrogen desorption kinetics suggest an increased hydride mobility in the complex with respect to the bare alanate. In order to better understand the role of mechanochemical treatments on the electrochemical properties of NaAlH4, we report a comprehensive study of our NaAlH4/C composite by the use of advanced techniques, including solid state NMR, Temperature Programmed Desorption and Electrochemical Impedance Spectroscopy. 1. Y. Oumellal et al., Nat. Mater., 2008,11(7), 2. L. Silvestri et al., J. Phys. Chem. C, 2015, 119(52), 3. J. A. Teprovich, J. Phys. Chem. C, 2015, 119(9).

Authors : S. M. Stankov, A. Trifonova, I. Gocheva and R. Hamid
Affiliations : AIT Austrian Institute of Technology GmbH, Donau-City-Straße 1, 1220 Vienna, Austria

Resume : The high theoretical capacity (197 mAh g-1) and operational potentials, respectively high energy density, make lithium vanadium(III) phosphate, Li3V2(PO4)3 (LVP) of a particular interest. The de-intercalation process occurs on four stages (plateaus) at 3.6 and 3.68, 4.2 and over 4.5 V versus Li/Li+, the first two of which correspond to the first lithium extraction, with the higher potentials corresponding to second and third lithium extractions. Unfortunately, a decline in discharge capacity at high potentials limits the upper cut-off of the potential to 4.4 V and reduces the theoretical specific capacity to 131.5 mAh g-1 for two moles of lithium per mole LVP. This decline in capacity at high potentials is associated with structural instability. Partial substitution of vanadium and or phosphorus represents one possible route to greater stability. In the present work, we investigate partial substitution of V3+ by Mg2+ in LVP. Two different approaches of charge balance were studied: direct ratio between vanadium and magnesium (Li3MgxV2-(2x/3)(PO4)3) and addition of lithium (Li3+xMgxV2-x(PO4)3). The samples were synthesized via a two-step sol-gel auto-combustion method. The physicochemical properties of the material were determined by X-ray powder diffraction (XRD), Thermogravimetric (TG) and differential thermal (DT) analyses, and Scaning Electron Microscopy (SEM). The obtained samples were tested in galvanostatic rate capability mode and cyclic voltammetry.

Authors : E. Peled1, N. Aloni1, M. Goor1, D. Golodnitsky1, 2
Affiliations : 1. School of Chemistry, Faculty of Exact Sciences, 2. Applied Materials Research Center, Tel Aviv University, Tel Aviv, 69978, Israel

Resume : A major cause of capacity fading of silicon anodes is the growth of the primary and secondary SEI. Thus, space must be allocated for this SEI growth. We report here on a novel anode structure consisting of a carbon-fiber scaffold on which SiNPs were coated. The space between the carbon fibers enables electrolyte penetration and SEI growth. We achieved an unprecedented combination of remarkable performance characteristics: high loadings of 2-4mAh/cm2, a very low irreversible capacity (˜20% for the 3-4mAh/cm2 anodes), current efficiency greater than 99%, cycle stability both in half cells and in full battery and fast charge–discharge rates (up to 1C-rate). The capacity of the fiber-scaffold anode was in the range of 900 to 1400mAh/g of anode – three to four times that of the commercial graphite anode. These anodes have been cycled for over 100 cycles, exhibiting a stable cycle life (cells are still running). It was found that the growth in the thickness of the SEI layer and the concomitant increase in its resistivity, represents the major reason for the observed capacity loss of the anode. Our data reveal that the novel-architecture anode is expected to meet the requirements of lithium-ion batteries for portable applications.

Authors : F. Rondino1, P. Prosini2, C. Cento2, A. Rufoloni3, F. Fabbri3, V. Orsetti1, A. Santoni1.
Affiliations : 1 Department FSN-TECFIS-MNF, ENEA C.R. Frascati, via E. Fermi 45, Frascati, Italy 2 Department DTE-PCU-SPCT, ENEA C.R. Casaccia, via Anguillarese 301, 00123 Rome, Italy 3 Department FSN, ENEA C.R. Frascati, via E. Fermi 45, 00044 Frascati, Italy

Resume : Lithium-ion batteries represent one of the most advanced systems for electrochemical energy storage. In the challenge to improve charge capacity, Si is considered one promising material to replace the conventional C-based anode, due to its highest known theoretical capacity of 4200 mAhg−1. However, its use has been hindered by the huge volume change (up to 400%) occurring during charge/discharge cycles, causing particle pulverization and thus electrochemical capacity fading. In this context, Si nanowires (SiNWs) can bypass the “bulk” Si drawbacks thereby increasing the active surface and providing a good electrical contact to the current collector. In this work, we show recent results on SiNWs grown in a Chemical Vapour Deposition furnace on an 1 cm2 stainless steel substrates functionalized by different dispersions based on Au, Cu and Ag nanoparticles of 10nm and 20nm diameter. According to vapour liquid solid mechanism, the accumulation of Si atoms from the Si2H6 precursor on the metallic nanoparticles induces the wire growth. The effects of the metallic catalyst, substrate temperature and Si2H6 pressure on the morphology and density of SiNWs are shown. The electrochemical properties of Si-NWs/LiFePO4 Li-ion cell have also been investigated. SiNWs were first electrochemical characterized in a Li metal battery and then coupled with a LiFePO4 cathode. A three electrodes Li-ion cell was prepared using metallic Li as the reference electrode and the electrochemical properties of the cell was evaluated by galvanostatic charge/discharge cycles.

Authors : E. Simonetti, M. Carewska, M. Di Carli, M. Moreno, G.B. Appetecchi
Affiliations : ENEA, Agency for New Technologies, Energy and Sustainable Economic Development Via Anguillarese 301, Rome 00123, Italy E. Simonetti , G.B. Appetecchi from Department SSPT-PROMAS-MATPRO; M. Carewska, M. Di Carli, M. Moreno from Department DTE-PCU-SPCT.

Resume : An appealing approach for overcoming the room temperature conductivity drawback of lithium polymer batteries is the incorporation of ionic liquids (ILs) into the polymeric electrolytes, SPEs [1]. However, compatibility towards 4 V cathodes in combination with fast transport properties is required for realizing high energy density devices operating at high power. For instance, SPEs based on different hosts (PEO, PMMA) were properly designed and developed. Our basic concept is to incorporate large IL contents to obtain phase separation, but without depleting the mechanical characteristics. This should allow formation of highly-conductive, internal pathways, enhancing the ionic conductivity. Also, the release of IL is expected to protect the polymer host from cathode material, extending the operative voltage of SPE, and to improve the interface with the Li anode. FSI-based ionic liquid were selected for their fast transport properties, low melting point and good-film forming ability. Free-standing, IL-based SPEs were prepared, exhibiting good chemical stability and conduction values overcoming 10-3 S cm-1 and 10-4 S cm-1 at 20 and -20 °C, respectively. Thermal and impedance measurements evidenced structural reorganization, resulting in IL percolation pathway within and on the SPE sample surface. Acknowledgements The authors thank the European Commission for the financial support within the MARS-EV Project (7th Framework Program, Grant agreement n°: 609201). References [1] S. Passerini, M. Montanino, G.B. Appetecchi, Lithium Polymer Batteries based on Ionic Liquids, in Polymers for Energy Storage and Conversion, Vikas Mittal editor, John Wiley and Scriverner Publishing, USA, 2013.

Authors : D. Versaci1, M. Minella2, M. Alidoost1, J. Amici1, C. Francia1, C. Minero2, A. Battiato3, S. Bodoardo1.
Affiliations : 1 Electrochemistry group, Department of Applied Science and Technology, Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino, Italy; 2 Department of Chemistry and NIS Inter-departmental centre, University of Torino, via P. Giuria 5, Torino,10125, Italy; 3. Department of Physics and NIS Inter-departmental Centre, University of Torino, via P. Giuria 1, Torino, 10125, Italy;

Resume : To optimize the Li-ion system in view of the requirements of the Hybrid Electric Vehicles (HEV) market (essentially high power density), new anode materials have to be considered, aiming at substituting graphite, which cannot sustain the high currents needed to reach, high power and is limited from the safety viewpoint [1]. Titanium oxide (anatase) is an interesting possible anodic material due to its high chemical stability, low cost, environmental sustainability combined to interesting electrochemical performances [2]. The coupling of TiO2 with carbonaceous conductive phases, e.g. TiO2-graphene composite, where the graphene acts as an electronic conductivity enhancer, can overcome its major drawback [3]. The present communication reports the results obtained by a TiO2-graphene composite prepared as anodic active material for high power Li-ion cells. Its preparation is simple, cheap and easily up scalable to industrial level. To obtain these objectives commercial anatase has been used as raw material and GO photocatalytic and in situ (directly on the electrode) photocatalytic reduction strategies have been taken into account. A similar approach has never been adopted before for Li-ion battery applications. Different amounts of GO have been considered in the experimental investigations finding, for the photocatalytic reduced GO composites a specific capacity of 180 mAh/g at 1C and still 40 mAh/g at 40 C (theoretical anatase capacity 330 mAh/g). [1] T. Horiba, Lithium-Ion Battery Systems, Proc. IEEE 102, 2014, 939-950. [2] S. Casino et al., J. Alloys Comp. 594, 2014, 114-121. [3] J. Qiu, P et al., ACS Appl. Mater. Interfaces 4, 2012, 3636-3642.

Authors : D. Versaci1, R. Nasi1, U. Zubair1, J. Amici1, M. Sgroi2,A. Dumitrescu3, C. Francia1, S. Bodoardo1, N. Penazzi1.
Affiliations : 1.Electrochemistry group, Department of Applied Science and Technology, Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino, Italy; 2.C.R.F. S.C.p.A, Group Materials Labs Environment & Chemical Analysis, Strada Torino 50, 10043 Orbassano (TO), Italy; 3.Lithops s.r.l., Strada del Portone 61, 10137 Torino, Italy;

Resume : In the commercial Li-ion batteries production, the electrodes active materials slurries are prepared using polyvinylidene fluoride (PVdF) as binder, thanks to its good adhesion properties and electrochemical stability [1]. Unfortunately there are some disadvantages related to the use of PVdF: most important the requirement of toxic and environmentally unfriendly solvents, such as N-methyl-pyrrolidone (NMP) and, secondly, the high costs [2]. On these premises it seemed straightforward to investigate the suitability of some water-soluble, inexpensive and eco-friendly binder (Gelatin, Sodium Alginate, Tragacanth Gum, Vinyl Glue, Chitosan) as an alternative to the well-known PVDF/NMP couple [3], in negative electrodes graphite slurries. All the electrodes, assembled with the different binders under study, were firstly electrochemically characterized and, in a second time, the rheological properties of these materials were also investigated to better understand their industrial scale-up feasibility with a particular focus on possible future applications. In addition, the results have been compared to the also commonly used carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR) binder combination. Some of this water-soluble binders, besides good electrochemical performances, showed a high adhesion to the current collector and a good electrochemical stability under the experimental conditions employed, which makes them interesting for the next generation of Li-ion Batteries. [1] B. Lestriez, C. R. Chimie 13, 2010, 1341-1350. [2] P.P. Prosini et al., Electrochimica Acta 150, 2014, 129-135. [3] S-L Chou et al., Phys. Chem. Chem. Phys., 16, 2014, 20347-20359.

Authors : Idoia Urdampilleta, Oscar Miguel, Hans-Jürgen Grande
Affiliations : IK4-CIDETEC, Pº Miramón, 196, 20009 Donostia-San Sebastián (Guipúzcoa), Spain.

Resume : The research at UME is centered on the development of materials for electrochemical applications in energy storage (Li-ion; post-Li technologies; electrochemical capacitors; etc.), conversion (fuel cells and electrolysers) and related technologies (environmental electrochemistry). The UME competences range from the synthesis to the optimization, processing and electrode engineering. Special attention is paid on the fundamental understanding of the functioning of materials and components, for proper selection regarding specific technologies. Concerning battery technology the activities focus on the improvement of traditional systems and the development of emerging batteries technologies (post-Li-ion; Li-S; metal-air; etc.) with a good cost-performance ratio. Particular importance is given to materials (electrodes and electrolyte) integration, optimization and feasibility conducted through electrode engineering, which also includes multiphysic models (1D/3D) to understand performance, degradation mechanism and cells design optimization as a function of the electrode structure and composition. UME has accumulated vast experience on aqueous slurry processing and scale up (10 kg), developing Li-ion cells with both electrodes prepared in water media using waterborne binders, and hence demonstrating more than 100 m length double-side coated electrode rolls (pre-industrial coating pilot line) to manufacture pouch cells (1-30Ah). It is a vital approach for the LIB industry towards the manufacturing of cheaper and greener batteries. Consequently, CIDETEC offers basic/technical support to interested industrial and academia partners to further develop their electrochemical energy storage devices.

Authors : Daniela Fontana, Mihaela-Aneta Dumitrescu, Matteo Destro, Damir Nefat
Affiliations : Lithops S.r.l.

Resume : Lithops is the first Italian Li-ion technology developer and provider, established in 2010. Lithops has installed the first pilot plant for the production of Li-ion pouch cells in Italy, covering from active material mixing to cell forming, and has gained almost six years of experience in designing, assembling and testing industrial cells. At the end of 2015 Lithops became part of the SERI Group, being incorporated in its subsidiary FIB (owner of the FAAM brand). The Group aims to develop the first Italian Li-ion batteries vertical supply chain, from raw materials to second life battery reuse. Lithops and FAAM plan to start up an industrial plant for Li-ion cells and battery production by the end of Q2 2017 with a total capacity up to 100 MWh/y, main markets being ESS and high power cells for specialty. Among the projects conducted in these years, Lithops has developed proprietary high power Li-ion technology (up to 20C continuous both in charge and in discharge). Lithops' cells show outstanding cyclability, maintaining more than 70% of the usable capacity after 10000 of charge/discharge at 10C (50% DOD), with very good thermal behaviour, and can reach 40C as peak power. These products are thought for specialty applications in fields where high power is required, such as automotive, aerospace, military, biomedical, stationary for hybrid systems.

Authors : G. A. Gkanas, G. Kastrinaki, D. Zarvalis, G. Karagiannakis, A.G. Konstandopoulos
Affiliations : Aerosol &Particle Technology Laboratory, CERTH/CPERI, P.O. Box 60361, 57001, Thessaloniki, Greece ; Department of Chemical Engineering, Aristotle University, PO. Box 1517, 54006, Thessaloniki, Greece

Resume : The development of lithium ion battery (LIB) with high performance has established it as a leading energy storage device for portable electronics, and an attractive solution for up-scaled applications such as electric vehicles. The latter applications call for advancements in energy and power densities of current technologies. The specific capacities of conventional electrode materials, such as graphite on the anode side can be increased with the exploitation of alternative electrode materials such as tin and tin oxides. Current work discusses the synthesis of SnO2 particles by aerosol spray pyrolysis (ASP) and sol-gel routes in order to study their nanostructure by exploiting their characteristics towards crystal structure, particle size, morphology, surface area and pore size distribution. The synthesis parameters, such as the precursor solution chemistry and the calcination temperature profiles, target to the synthesis of SnO2 particles at different size distributions and morphologies and especially in acquiring a hollow/porous particle morphology providing increased cycling performance through its nanostructure in order to compensate the significant volume change occurring during the charging / discharging phases. Three different mixing routes, namely dry mixing, liquid and aerosol route, have also been exploited for the synthesis of carbon/SnO2 particles. The above technologies have been assessed by the evaluation of the electrochemical performance of the respective materials.

Authors : S. Lunghammer, M. Wilkening
Affiliations : Christian Doppler Laboratory for Lithium Batteries, and Institute for Chemistry and Technology of Materials, Graz University of Technology (NAWI Graz), Stremayrgasse 9, 8010 Graz, Austria; DFG Research Unit 1277, Mobility of Li Ions in Solids, Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria

Resume : Currently, Li-ion batteries play a capitol role in modern electrochemical energy storage. In order to further improve the systems already available an in-depth understanding of the fundamental processes determining, e.g., rate capability and life cycle. In particular, Li ion transport, which is related to Li ion self-diffusivity, largely affects the performance of a battery. Besides the well-known zero-strain anode material Li4Ti5O12 [1], taking advantage of an extraordinary high cycling performance, ramsdellite-type Li2Ti3O7 represents another attractive negative electrode material to realize small rechargeable Li-ion batteries. In contrast to Li4Ti5O12, Li2Ti3O7 crystallizes with a channel-like structure; thus, the ions are expected to sense the spatial restrictions during diffusion. Depending on which sites are occupied by the lithium ions, the site occupancy is still a matter of debate; Orera et al. [2] report on two possible hopping processes. The present study is aimed at answering the question what are the elementary Li ion jump processes taking place in Li2Ti3O7. Nuclear magnetic resonance (NMR) spectroscopy might be of help to shed light on this issue. By using both high-resolution 6Li NMR exchange spectroscopy and 6,7Li time-domain NMR techniques we studied local structures and short-range as well as long-range ion dynamics. Considering results from magic angle spinning NMR, we conclude that Li ions preferentially occupy intra-channel sites. This spatial restrictions does, however, not slow down Li ion exchange as it has been reported for channel-structured Li3BS5 [3], recently. Because of the relatively large diameter of the channels and the high concentration of vacant positions inside the channels of Li2Ti3O7, rapid Li ion exchange is seen by both NMR relaxometry and line shape measurements. [1] W. Schmidt, P. Bottke, M. Sternad, P. Gollob, V. Hennige, M. Wilkening, Chem. Mater., 27 (2015) 1740. [2] A. Orera, M. T. Azcondo, F. García-Alvarado, J. Sanz, I. Sobrados, J. Rodríguez-Carvajal, and U. Amador, Inorg. Chem., 48 (2009) 7659. [3] S. Nakhal, D. Wiedemann, B. Stanje, O. Dolotko, M. Wilkening, M. Lerch, J. Solid State Chem., 238 (2016) 60.

Authors : Tarekegn Heliso Dolla, Patrick Ndungu
Affiliations : University of Johannesburg, Department of Applied Chemistry, Doornfontein, Johannesburg, South Africa

Resume : This study aims at investigating crystal structure and electrochemical performance of MnxNiyCo3-x-yO4 and their composite with multiwall carbon nanotubes (MWCNTs) with different non-stochiometries (0≤x,y≤1) by varying x and y. Currently, MnxNiyCo3-x-yO4 (0≤x,y≤1) with different non-stochiometries and their composites with MWCNT were synthesized using citric acid precursor method. The effects of substituting Co with different amounts of Mn and Ni on the crystal structure have been investigated to some extent and the effect on electrochemical performance will be investigated soon. The composites with multiwall carbon nanotubes have also been synthesized using the same method for MnxNiyCo3-x-yO4. The XRD pattern has shown that there is no siginifacnt change in the peak position of the mixed oxides due to the addition of the MWCNT. Detailed XRD, retiveld refinement, cyclic voltammetry and galvanostatic charging and discharging will be done to fully understand the crystal structure and electrochemical performance of the mixed oxides and their composite.

Authors : Vijay Shankar Rangasamy (a*), Savitha Thayumanasundaram (a), Jin Won Seo (b), Jean-Pierre Locket (a)
Affiliations : (a) aDepartment of Physics and Astronomy, Katholieke Univerisiteit Leuven, Celestijnenlaan 200D, B-3001, Leuven, Belgium (b) Department of Metallurgy and Materials Engineering, Kasteelpark Arenberg 44 - bus 2450, B-3001 Leuven, Belgium

Resume : Among emerging cathode materials for Lithium ion batteries, Li2MSiO4 is the most promising candidate because of the possibility of reversible extraction of two lithium ions per formula unit corresponding to a theoretical capacity of about 333 mAh/g. In this study, Li2FeSiO4 (LFS) was prepared by the Polyol method using diethylene glycol (DEG). XRD pattern of LFS shows sharp peaks well matched with ICDD database. TGA analysis reveals the weight losses corresponding to the evaporation of solvent and decomposition of precursors. Electrochemical performance of the LFS was analyzed by assembling CR 2032 coin type cells with Li as anode and 0.2m PYRTFSI-LiTFSI ionic liquid electrolyte as electrolyte at room temperature. Cyclic voltammetry analysis reveals redox peaks at 3.1 V and 2.3 V in forward and reverse bias, respectively. Galvanostatic charge - discharge cycles of LFS reveals the extraction of one Li ion, corresponding to a specific capacity of about 170 mAh/g at the rate of C/20 at room temperature. In-situ impedance spectroscopy reveals two semicircles and a spike in the Nyquist plot corresponding to SEI layer, Charge-transfer resistance and Warburg impedance, respectively. Conductive coating using multi-walled carbon nanotubes (MWCNTs) and the electrochemical performance of the LFS/CNT composite will also be discussed.

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POST LITHIUM ION : Robert Dominko
Authors : Peter Axmann, Giulio Gabrielli, Marilena Mancini, Andreas Klein, Margret Wohlfahrt-Mehrens
Affiliations : ZSW - Zentrum für Sonnenenergie- und Wasserstoff-Forschung, Baden-Württemberg

Resume : Due to their high energy and power density, excellent efficiencies and long life time lithium ion batteries have become the dominating energy storage technology for the new generation of Plug-in hybrid electric vehicles (PHEV) and full electric vehicles (EV). However, there is still considerable improvement needed to achieve extended driving range and to reduce significantly the cost of battery packs. For these reasons, the development of new high capacity, safe and lower cost cathode materials is necessary. State of the art is the use of layered oxides like LiCoO2, Li(Ni1/3Mn1/3Co1/3)O2 (NMC) and Li(Ni1-x-yCoxAly)O2 (NCA) or use of the more safe LiFePO4 with olivine structure. In order to further improve the specific capacity and to reduce the cost of the cathode material current research activities focus on the development of various compositions of LiNi1-x-yCoxMnyO2 with higher nickel content or on the development of so called HENMC with various compositions of solid solutions of Li2MnO3 and Li(Ni1/3Mn1/3Co1/3)O2. An alternative approach for further improvement of energy density is the development of high voltage cathode materials which are able to operate above 4.5 V vs. Li/Li+. The application of these cathodes leads to a higher cell voltage, resulting in higher energy density, lower costs and a lower complexity of the complete battery system. High voltage LiMn1.5Ni0.5O4 (LMNO) with spinel structure is one of the most promising candidates, because of the high operating voltage, high rate capability and good thermal stability. Moreover, it is easy to obtain via low cost synthesis methods from abundant raw materials. However, the high voltage can also lead to side reactions with the electrolyte, which cause impedance increase and capacity fading during cycling or storage especially in full cells using graphite as anode. The long term stability can be significantly improved by adjusting the composition, the particle morphology and by surface coating. It is possible to insert additional lithium into the spinel structure on a lower voltage plateau, which leads to additional specific capacity. The synthesis of Li2-xMn1.5-yMyNi0.5O4 (0≤x≤0.5) combine both the high voltage and the high specific capacity approach, reaching reversible capacities up to 280 mAhg-1. The presentation will summarize the state of the art of various positive active materials under development and highlight ongoing research developments and discuss perspectives and limitations.

Authors : Jesus Santos-Peña, Barthèlemy Aspe, Cécile Autret, Christine Damas, Bénédicte Montigny
Affiliations : a) Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l’Energie (EA 6299) Université François Rabelais, Parc de Grandmont, 37200 Tours, France b) Laboratoire de Recherche Correspondante CEA/DAM, Le Ripault, F-37260, Monts, France c) Research Group Materials, Microelectronics, Acoustics, Nanotechnologies (GREMAN) UMR 7341 Université François Rabelais/CNRS, Faculty of Sciences and Techniques, Parc de Grandmont, 37200 Tours, France

Resume : Hard carbons (hereafter called HC) are choice materials for negative electrode purposes in sodium ion batteries due to their high specific capacities. However they show a cycling life limited to 300 cycles and charge/discharge curve profiles characterized by the presence of sloping regions at relatively high potential associated to the lithium insertion in the graphene layers. Nowadays a major effort has been devoted in determining the influence of HC textural properties on its electrochemical performance, analyzing samples obtained by pyrolisis at elevated temperature of organic compounds. Such studies are justified by major adsorption of sodium ions in the last step of the discharge curve, which should be enhanced by increasing the specific surface area. At our knowledge, influence of particle size has been somewhat missed in such studies. Thus, we have prepared a HC by pyrolising cellulose at 900°C and submitted the resulting powder to ballmilling for different periods. A number of electrochemical and physicochemical techniques allowed us to confirm that reducing the particle size in the same system provokes an increase in the electrolyte reduction comsuption during the cycling, creating thick solid electrolyte interfaces. Such films block the sodium ions adsorption. However a constant voltage step at the end of the discharge is efficient to save partly this drawback. From this results we propose in the second part of this presentation an electrochemical study of a composite based on optimised submicrometric HC and Ni-Sn nanoparticles in sodium half cell.

Authors : Soo Yeon Lim, Jang Wook Choi
Affiliations : (EEWS) and Center for Nature-inspired Technology (CNiT) in KAIST Institute NanoCentury, Korea Advanced Institute of Science and Technology (KAIST),291 Daehakro, Yuseong-gu, Daejeon 305-701, Republic of Korea

Resume : Sodium-ion batteries (SIBs) have been intensively investigated to meet the increasing demand for large-scale energy storage systems. However, it is still challenging to construct a functional full cell due to the limited material pool for both anodes and cathodes. Utilizing the wide range of vanadium redox states, herein, we report vanadium-based ortho-diphosphate, Na7V4(P2O7)4PO4 (or Na7VODP) as both cathode and anode active phases in a full-cell. The amphoteric nature allows Na7VODP to engage two vanadium redox couples, V3+/V4+ and V2+/V3+, for cathode and anode operations, respectively, within the stable voltage window of organic electrolytes. Na7VODP exhibits an activity at 1.01 V vs. Na/Na+ with a reversible capacity of 71.7 mAh g-1 and good capacity retention (80.5 % retention after 100 cycles). Through an Ex-situ X-ray photoemission spectroscopy (XPS), X-ray absorption near-edge structure (XANES) and In-situ synchrotron X-ray diffraction (XRD), it was revealed that Na7VODP reacts with Na ions based on a single-phase reaction in the low voltage range of 0.5 ~ 2.0 V by engaging V2+/V3+, in contrast with two biphasic reaction observed in the high voltage region of 2.0 ~ 4.2 V with V3+/V4+. Upon pairing into both electrodes, a Na7VODP full-cell shows an output voltage of 2.81 V.

Authors : M. Zarrabeitia1*, M.A. Muñoz-Márquez1, F. Nobili2, E. Castillo-Martínez1†, T. Rojo1, 3, M. Casas-Cabanas1
Affiliations : 1 CIC Energigune, Albert Einstein 48, 0150 Miñano, Spain 2 Scuola di Scienze e Tecnologie-Sezione Chimica, Università di Camerino, Via S. Agostino 1, 62032-Camerino, Italy 3 Departamento de Química Inorgánica, Universidad del País Vasco UPV/EHU, P.O.Box. 664, 48080, Spain † current address: Department of Chemistry, Lensfield Road, Cambridge, CB2 1EW, United Kingdom

Resume : Na-ion batteries (SIBs) are becoming an attractive alternative to Li-ion batteries because of their low cost owing to sodium abundance, geographical distribution and ease to process. Moreover, cheaper current collectors made of aluminium instead of copper can be used in both electrodes. While for cathode materials many lithium analogues can be successfully used in SIBs, [1] the challenge is to find alternative anode materials due to the impossibility of Na+ insertion into graphite and the formation of a stable SEI layer (Solid Electrolyte Interphase). Na2Ti3O7 negative electrode is the oxide with the lowest insertion voltage at 0.3 V vs. Na+/Na and delivers high specific capacity close to 200 mAh/g, [2] becoming a very promising anode candidate both in terms of energy density and cost. However, the reported capacity reaches only 50-70% after 10 cycles [3, 4, 5] therefore, the capacity retention needs to be improved. One of the important factors to take into account is the formation of a stable SEI layer since the reversible Na+ insertion/extraction occurs at low voltage and electrolyte reduction is expected. In order to understand the reasons behind the poor capacity retention, the SEI layer and kinetic transport properties have been studied by X-ray photoelectron spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). Ex-situ XPS combined with depth profiling has allowed the study of the composition and stability of the SEI layer on Na2Ti3O7 electrode. Furthermore, the analysis of the Auger parameter has been used to accurately determine the composition without any interference from surface charging effects. [6] The study of the electronic and ionic transport has been carried out by EIS experiments. An interesting change of the transport properties, and particularly of electron conductivity, during the Na+ insertion/extraction process is revealed for the first time experimentally confirming recent DFT calculations. [4]. Moreover, the instability of the SEI layer has been also observed by EIS. The results obtained will be thoroughly discussed and strategies to overcome the poor capacity retention will be proposed. References: 1. V. Palomares, M. Casas-Cabanas, E. Castillo-Martínez, M.H. Man, T. Rojo, Energy Environ. Sci., 2013, 6, 2312-2337. 2. P. Senguttuvan, G. Rousse, V. Seznec, J.M. Tarascon, M.R. Palacín, Chem. Mater., 2011, 23, 4109-4111. 3. M. Zarrabeitia, E. Castillo-Martínez, J.M. López Del Amo, A. Eguía-Barrio, M.A. Muñoz-Márquez, T. Rojo, M. Casas-Cabanas, Acta Mater., 2016, 104, 125-130. 4. H. Pan, X. Lu, X. Yu, Y.S. Hu, H. Li, X.Q. Yang, L. Chen, Adv. Energy Mater., 2013, 3, 1186-1194. 5. A. Rudola, K. Saravanan, C.W Mason, P. Balaya, J. Mater. Chem. A, 2013, 1, 2653-2662. 6. M.A. Muñoz-Márquez, M. Zarrabeitia, E. Castillo-Martínez, A. Eguía-Barrio, T. Rojo, M. Casas-Cabanas, ACS Appl. Mater. Interfaces, 2015, 7, 7801-7808.

POST LITHIUM ION : Margret Wohlfahrt- Mehren
Authors : Mattia Giannini (1 2 3), Afef Mastouri (1 4), Arnaud Demortière (1 3 4), Mathieu Morcrette (1 3 4), Claude Guéry (1 4), Goran Dražić (2 3), Carine Davoisne (1 3 4)
Affiliations : (1) Laboratoire de Réactivité et Chimie des Solides (CNRS UMR 7314), Université de Picardie Jules Verne, 33 rue Saint Leu, 80039 Amiens, France; (2) National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia; (3) ALISTORE European Research Institute, FR CNRS 3104, France; (4) Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France

Resume : Lithium-Sulfur batteries (LiSB) are viewed as the future of Li-ion batteries for their high theoretical capacity and low-cost. However, some problems need to be addressed before LiSB can be commercialized. One of these issues is the formation of Li2S - an insulating and insoluble species - on the cathode upon discharge. Gaining a better understanding on the effect of materials electrodeposition at the electrode during discharge/charge is crucial for the development of LiSB. To this end, we have used electron microscopy to investigate the microstructural, crystallographic and chemical evolution of carbon nanoparticles, uniformly coated with amorphous sulfur, which were discharged at different rates (from 1C to 0.05C). Scanning Electron Microscopy highlights that the morphology of the discharge products is C-rate dependent, going from an amorphous phase at 1C to a crystalline, porous, desert-rose-like deposits at 0.05C. A careful analysis of the discharge products was performed by means of High- to Atomic- Resolution TEM associated with EELS. In the case of slow cycling, the discharge product crystalized as cubic Li2S nanocrystals up to 30 nm in size. They were observed either as isolated particles or aggregate clusters. These observations suggest that changing the discharge rate allows controlling the formation of Li2S from an amorphous to a crystalline phase.

Authors : Christoph Guntlin (a) (b), Tanja Zünd (a) (b), Michael Wörle (b), Kostiantyn V. Kravchyk (a) (b), Maryna I. Bodnarchuk (b), and Maksym V. Kovalenko (a) (b),
Affiliations : (a) Laboratory of Inorganic Chemistry, Department of Chemistry and Applied Bioscience, ETH Zürich, CH-8093 Zürich, Switzerland (b) Laboratory for Thin films and Photovoltaics, Empa – Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland

Resume : The performance demands placed on batteries for the use in electrical mobility and portable devices are enormous. Cathode materials remain a bottleneck for the further increase on energy density. A promising candidate compound featuring low cost and high natural abundance is iron trifluoride (FeF3). It has been demonstrated that FeF3 intercalates lithium with near theoretical capacity of 237 mAh/g [1], also with promising rate capability [2]. However, there remains a strong need to develop low-cost synthesis methods for this material in a nanoscale form, needed for maximizing the performance. Herein, we show a new synthesis for nanocrystalline FeF3 based on a thermal decomposition of an organic precursor. Such inexpensive FeF3 can be charged and discharged in a lithium half-cell at a reversible capacity of 155 mAh/g within 1 min (10 A/g) or even faster. After 100 cycles, a capacity retention of 88 % has been achieved. In a sodium-ion half-cell, a capacity of 160 mAh/g at a current rate of 200 mAh/g could be measured. [1] Liu, J et al. Journal of Materials Chemistry A 2013, 1, 1969 [2] Ma, D. L. et al. Energy & Environmental Science 2012, 5, 8538

Authors : Usman Zubair, Mojtaba Alidsoot, Julia Amici, Carlotta Francia, Silvia Bodoardo, Nerino Penazzi
Affiliations : DISAT, Politecnico di Torino, Corso Duca degli Abruzzi, 24 - 10129 Torino, ITALY

Resume : Future of portables devices, electric vehicles and smart grids demands long life and high energy density batteries. Li/S batteries – a post Li ion technology – provide a sound answer to such requests, as they offer high theoretical capacity (1675 Ah kg-1) and high energy density (2500 Wh kg-1). The development of Li/S system faces several challenges such as low degree of sulfur utilization, gradual capacity fading, poor rate capability and lower Coulombic efficiency mainly due to low conductivity of S (5 × 10−30 S cm−1), solubility of intermediate polysulfides, shuttling of polysulfides and lack of morphology restoration. One of the promising strategy is to encage S in conductive matrices to reduce polysulfides solubility while increasing the cathode electronic conductivity. A sustainable solution is proposed here to produce conductive carbon matrices from bio-based materials. Microporous carbons are manufactured by carbonizing β-cyclodextrin nanosponges and/or pea maltodextrin. Sulfur is incorporated via solvent impregnation and thermal diffusion. Then, the as prepared carbon-sulfur composite is wrapped with reduced graphene oxide or conductive polymers like polyaniline.. The obatained cathode material showed an initial discharge capacity of 1130 Ah Kg-1 at C/10, maintaining its capacity to 626 Ah Kg-1 at C/5 with capacity loss of 0.016% per cycle for more than 60 cycles.

Authors : J. Amici (1), S. Martinez Crespiera (2), D. Amantia (2), E. Knipping (2), C. Aucher (2), L. Aubouy (2), J. Zeng (1), M. Alidoost (1), C. Francia (1), S. Bodoardo (1), N.Penazzi (1)
Affiliations : (1) Department of Applied Science and Technology (DISAT), Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino, ITALY; (2) Leitat Technological Center, Carrer de la Innoviació, 2 08225 Terrassa, Spain.

Resume : Global warming and reduction of fossil-fuel supplies demand the pursuit of renewable energy sources and sustainable storage technologies. The rechargeable Li-air battery, coupling the light Li metal with the inexhaustible source of O2 of the surrounding air, represents an exciting opportunity. However, for many practical applications such as EV, air is the only viable option to supply the battery. In this context, moisture and gases other than O2 may cause side reactions and corrosion of the Li anode. We report a facile strategy to fabricate a highly effective O2 selective membrane based on highly hydrophobic fluorinated polymer and cyclodextrins. Several other major issues are responsible for the limited actual capacity and cycle ability. In principal, the high recharge potentials needed to decompose the insulating Li2O2 and the parasitic products formed from the electrolyte decomposition during cell discharge result in important energy losses. Palladium nanoparticles, due to the strength of O2 binding on the Pd surface, have very high intrinsic ORR activities in non-aqueous electrolytes. The use of carbon nanofibers (CNFs) as a support assures high surface area and high pores volume compared to other carbon-based materials. Pd doped mesoporous CNFs produced by electrospinning were used at the cathode of the Li-air pouch cell. Galvanostatic cycling tests in a potential/time controlled mode showed an outstanding cycling life superior to 1500h with more than 150 cycles.

Authors : Margarida Gama, Alexandra Saraev
Affiliations : thinkstep AG

Resume : Electric Vehicles symbolize the future of sustainable road transport. The ELIBAMA (European Li-Ion Battery Advanced Manufacturing) project had a duration of 3 years and came to an end in October 2014. The aim of this project was enhancing and accelerating the creation of a strong European automotive battery industry structured around industrial companies already committed to mass production of Li-ion cells and batteries for EVs. It was part of the European 7th Framework Program and of the European Green Cars Initiative, counting 17 partners - among which Daimler, Fraunhofer, Renault and Saft. It exploited eco-design methods of manufacturing battery cells, in order to guarantee gains in cost reduction and environment-friendliness across the value chain of the battery production. It main focus was the development of more eco-friendly processes for anode and cathode manufacturing (e.g. dry blend powder coating and aqueous based technologies), fast and homogenous electrolyte filling processes, cell design and assembly. Furthermore, it allowed developing new technologies to improve downstream quality, test the batteries and reduce the rate of defective products at the end of the manufacturing chain. The end-of-life for the Li-ion batteries was also considered within the scope of the project, where the pyrometallurgical process is state of the art, but other technologies involving hydrometallurgical processes are under development. The improvements were monitored and validated from the environmental point of view by an integrated assessment, using LCA methodology and considering the framework for eco-design. thinkstep (former PE INTERNATIONAL) undertook an independent assessment, playing the moderator role among the consortium partners and enhancing the communication from the different parts. Furthermore, thinkstep provided the battery manufacturers in the project with a flexible eco-design tool based on the data acquired during the project, in combination with GaBi databases and software, offering to these partners, the possibility of performing own internal assessments to the desired level of detail, without having to disclosure any additional information to third parties, avoiding the potential confidentiality issues which are a major challenge in this field. The methodology and framework used for performing the environmental integrated assessment of this project, allowing the identification of hotspots through the LCA, will be explained in this paper. The tool used by the partners to make their own environmental assessments will also be addressed, as an example of an approach to allow environmental screenings avoiding the need of providing information to third parties. The results from the project will be presented and discussed. The current status of the technologies developed and perspectives on potential further developments from the partners who participated in this project will be collected, analyzed and presented as an overview for the future.

ELECTROLYTES : Steve Greenbaum
Authors : Władysław Wieczorek
Affiliations : Warsaw University of Technology Polymer Ionics Research Group

Resume : Nowadays ambient temperature batteries gain worldwide interest as vital part required for long-time performance of various devices from portable electronics to electric and hybrid vehicles. Although lithium-ion batteries seems to be at the industrial stage novel systems which can replace them due to better capacity, longer lifetime economical and environmental issues are intensively studied. To this end not only novel electrode materials but also electrolytes are needed. In the present work some examples of strategies used to design new electrolytes from computational modeling via synthesis of electrolyte component up to examples of application in post lithium-ion batteries will be presented. The presentation will start from the development of novel salts (particularly anions) which plan to be used in electrolytes of possible multiple application. In our group in co-operation with CIC and Chalmers University various salts based on heterocyclic compounds with five-membered rings, such as 4,5-dicyanoimidazole or 4,5-dicyanotriazoles derivatives were obtained. In this presentation some recent results which enable us to design new liquid and polymeric electrolytes will be highlighted. Additionally the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate will be presented. This modification leads to the reorganisation of solution structure, what entails release of free mobile lithium cation solvate and hence

Authors : B. Stanje[1][2], D. Rettenwander[3], S. Berendts[4], R. Uecker[5], G. Redhammer[3], M. Wilkening[1][2][6]
Affiliations : [1]Christian Doppler Laboratory for Lithium Batteries, and Institute for Chemistry and Technology of Materials, Graz University of Technology (NAWI Graz), Stremayrgasse 9, 8010 Graz, Austria; [2]DFG Research Unit "Mobility of Lithium Ions in Solids", Graz University of Technology, Stremayrgasse 9, 8010 Graz, Austria; [3]Department of Materials Research and Physics, University of Salzburg, 5020 Salzburg, Austria; [4]Technische Universität Berlin, Institut für Chemie, Straße des 17. Juni 135, 10623 Berlin, Germany; [5]Leibniz Institute for Crystal Growth (Forschungsverbund Berlin e.V.), Max-Born-Straße 2, 12489 Berlin, Germany; [6]Alistore-ERI European Research Institute, 33 rue Saint Leu, 80039 Amiens, France

Resume : The development of all-solid-state electrochemical energy storage systems, such as lithium-ion batteries with solid electrolytes, requires stable, electronically insulating compounds with exceptionally high ionic conductivities. Considering oxides, garnet-type Li6La3Zr2O12 and derivatives, see Zr-exchanged Li6La3ZrTaO12 (LLZTO), have attracted great attention because of its high Li+ ionic conductivity of up to 10-3 S\cm-1. Despite numerous studies focusing on conductivities of powder samples, only a few use time-domain NMR methods to probe Li ion diffusion parameters in single crystals. Here we report, for the first time, on temperature-variable 7Li NMR relaxometry measurements using both laboratory and spin-lock techniques to probe Li jump rates in single crystalline Li-bearing garnets with high ion mobility. Time-domain NMR offers the possibility to study Li ion dynamics on both the short-range and long-range length scale. The techniques applied yield a fully consistent picture of correlated Li ion jump diffusion in LLZTO; the data perfectly mirror a modified BPP-type relaxation response being based on a Lorentzian-shaped relaxation function. The rates measured could be parameterized with a single set of diffusion parameters. Dynamic information about the elementary jump processes, such as jump rates and activation energies, was extracted from complete diffusion-induced rate peaks that are obtained when the relaxation rate is plotted vs inverse temperature.

Authors : Anwar Ahniyaz, Ningxin Zhang, Jürgen Kahr, Wolfram Kohs
Affiliations : Anwar Ahniyaz (SP Sveriges Tekniska Forskningsinstitut AB); Ningxin Zhang (AIT Austrian Institute of Technology GmbH); Jürgen Kahr (AIT Austrian Institute of Technology GmbH); Wolfram Kohs (AIT Austrian Institute of Technology GmbH)

Resume : The public acceptance of electric cars is generally influenced by an affordable, competitive pricing and an operating distance comparable or at least similar in size to that of nowadays used cars. Both factors are determined by the batteries used. Although lithium-ion batteries work quiet stable today, their capacity is not totally satisfying in respect of electric vehicles. To overcome these energy limitations, electrode materials with an increased specific capacity or/and cathode materials with a higher working potential are the two possible approaches. Both ideas are investigated in the eCaiman project funded by the European Union (H2020) which we would like to present here. A new graphite, optimized to be combined with an aqueous binder system, is under development. High voltage cathode and high capacity anode composites are synthesized and electrolyte components for 5 V battery systems are currently under development. In the present work we would also like to give a closer insight into the chemical interactions of high voltage cathode materials and carbonate based electrolytes when stressed by potentials beyond 4.5 V. The currently known electrolyte systems are known to be unstable and to decompose oxidatively at high potentials and cannot fulfil the demands of a 5 V battery system. Two electrolyte additives potentially known for their good high voltage properties are used for the investigations and the electrochemistry and the decomposition of the components is studied by GC-MS / IR techniques. A commercially available cathode material is used as a reference and compared to some high voltage spinel type LNMC materials, synthesized by project partners.

Authors : Savitha Thayumanasundaram a*, Vijay shankar Rangasamy a, Jin Won Seo b, Jean-Pierre Locket a
Affiliations : a Department of Physics and Astronomy, Katholieke Univerisiteit Leuven, Celestijnenlaan 200D, B-3001, Leuven, Belgium b Department of Metallurgy and Materials Engineering, Kasteelpark Arenberg 44 - bus 2450, B-3001 Leuven, Belgium

Resume : In Lithium-ion batteries, polymer electrolytes are preferred in order to meet all-solid-state requirements such as flexibility, leak-proof packing, processing feasibility etc. In this study, a polymer blend of 10 mol% PAA and 90 mol% PVA was optimized based on its thermal, mechanical and structural properties. The ionic liquid electrolyte, 0.2m PYRTFSI-LiTFSI was added to the polymer blend in different molar ratios. A maximum ionic conductivity of 1 mScm–1 is observed at 90 °C for the membrane with 70 mol-% IL. Cyclic voltammetry of the polymer electrolytes shows peaks corresponding to lithium stripping ( 0.3V vs Li /Li) and deposition (-0.32V vs Li /Li) process indicating the occurrence of highly reversible redox process. Linear sweep voltammetry of the polymer electrolyte reveals that they are stable up to 4.5 V, making these electrolytes suitable for high voltage cathode materials. A lithium transference number (tLi ) of 0.4 was determined for the polymer electrolytes by using chronoamperometry and impedance measurements. Galvanostatic charge-discharge studies of the polymer electrolytes in a lithium half-cell were tested with LiCoO2 as cathode, shows a capacity of about 100 mAh/g at 60 °C. The coin-type half-cell with 70 mol-% Il doped polymer electrolyte and LiFePO4 as cathode delivers a capacity of about 180 mAh/g. 1) Bruno Scrosati, et. al. (2010) J. Power Sources, 195(9) 2419. 2) Thayumanasundaram, al. (2015), Eur. J. Inorg. Chem., 2015 (7) 1290.

Authors : Mayte Gil-Agustí, Leire Zubizarreta, Marta García, Alfredo Quijano
Affiliations : Instituto Tecnológico de la Energía, Avda. Juan de la Cierva, 24, 46980 Paterna, Valencia; Universitat Politècnica de València, Camino de Vera s/n 46022 Valencia

Resume : The motivation and advantages for using solid polymeric membranes as electrolytes in a lithium battery are to enhance endurance when varying electrode volume during life cycling, reduce reactivity with liquid electrolyte, improve safety and reach better shape flexibility. The basic requirements of a suitable electrolyte for electric vehicle battery are high ionic conductivity, low melting and high boiling points, electrochemical stability, and safety. In the study, the influence of different components on the polymer electrolyte was evaluated. Properties of fluorinated polymer electrolyte were studied using selected lithium salts and plasticizers. To achieve this goal, different polymer membranes were synthesised and characterised. The effect of different amounts of Lithium salt and plasticizer on the ionic conductivity of polymer membranes were tested. And, additionally, thermal stability and mechanical properties were also taken into account. The thermal properties were characterised by differential scanning calorimetry (DSC) in the temperature range of -90ºC- 200ºC, and thermogravimetric analysis (TGA) in the temperature range of 25-300 ºC. Tensile testing was performed with full scale forces in the range of 150N. Ionic conductivities of the polymer membranes were measured by electrochemical impedance spectroscopy (EIS), sandwiching a given polymer membrane between two blocking electrodes. Electrochemical stability of the membranes was also evaluated by linear sweep voltammetry (LSV) in the voltage range of 0-7 V (vs Li/Li+). Promising results were obtained for a polymer membrane based on PVdF-HFP matrix, LiPF6 as lithium salt, and a surfactant as plasticizer.

ANODES : Dimitrios Zarvalis
Authors : Arlavinda Rezqita, Atanaska Trifonova
Affiliations : AIT Austrian Institute of Technology GmbH Vienna University of Technology

Resume : We studied the effect of different electrolyte additives such as vinyl carbonate (VC), succinic anhydride (SA), and lithium bis(oxalato)borate (LiBOB) on the electrochemical performance of Si slurry based anodes. The electrochemical behavior of composite electrode was evaluated through amperometric and and rate capability tests. The effect of electrolyte additives on the surface morphology of the Si/MC anodes was also studied using Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS) techniques. It was found that the various electrolyte compositions affect the formation and quality of Solid Electrolyte Interphase of electrodes in a distinct way. These phenomena and their impact on the cycling performance of mesoporous silicon anode will be demonstrated.

Authors : Xin-Bing Cheng, Hong-Jie Peng, Rui Zhang, Chen-Zi Zhao, Jia-Qi Huang, Fei Wei, Qiang Zhang
Affiliations : Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, China 100084

Resume : Li metal is considered as the “Holy Grail” of energy storage systems due to its extremely high theoretical specific capacity (3860 mAh g−1) and the lowest negative redox potential (−3.040 V vs. standard hydrogen electrode). The bright prospects give rise to worldwide interests in the metallic Li for the next generation energy storage systems, including highly considered rechargeable metallic Li batteries such as Li-O2 and Li-sulfur (Li–S) batteries. However, the formation of Li dendrites induced by inhomogeneous distribution of current density on the Li metal anode and the concentration gradient of Li ions at the electrolyte/electrode interface is a crucial issue that hinders the practical demonstration of high-energy-density metallic Li batteries. To suppress Li dendrite growth on the Li metal anode, we proposed several electrode designs: (a) A novel 3D nanostructured anode with metallic Li contained in fibrous Li7B6 matrix.[1] Comparing with other microstructured anode materials, the nanostructured anode is with a large specific area, which reduces the current density to suppress Li dendrite growth. Li deposits on the nanostructured anode with metallic Li embeded in fibrous Li7B6 matrix are always with smaller size than that on the plate Li metal anode. (b) A dual-phase Li metal anode containing polysulfide-induced SEI and nanostructured graphene framework.[2] Free-standing graphene foam provides several promising features as underneath layer for Li anode, including (1) relative larger surface area than 2D substrates to lower the real specific surface current density and the possibility of dendrite growth, (2) interconnected framework to support and recycle dead Li, and (3) good flexibility to sustain the volume fluctuation during repeated incorporation/extraction of Li. The synergy between the LiNO3 and polysulfides provides the feasibility to the formation of robust SEI in an ether-based electrolyte. (c) 3D reduced graphene oxide (rGO) with a very large SSA (1666 m2 g-1), pore volume (1.65 cm3 g-1), and electrical conductivity (435 S cm-1) as Li depositing framework.[3] Such unstacked graphene with huge SSA provides the feasibility to demonstrate the proof-of-concept of the regulation of Li depositing morphology through the ultralow local areal current density in LMBs. (d) 3D glass fiber (GF) cloths with large quantities of polar functional groups (Si-O, O-H, O-B) to realize uniform distribution of Li ions on Li metal anode and thus the dendrite-free Li deposits.[4] When GFs are introduced on the anode surface, the polar functional groups on the surface of GFs can adsorb considerable Li ions to compensate the electrostatic interactions between Li ions and protuberances of anode surface, avoiding the accumulation of Li ions around protuberances. The Li ions tend to evenly redistribute within the GF frameworks. Because the GF is nonconductive, Li ions can only epitaxially grow from former Li layer. Consequently, a dendrite-free morphology of Li deposits is achieved. Reference [1] Cheng X-B, Peng H-J, Huang J-Q, Wei F, and Zhang Q. Small 2014, 10, 4257. [2] Cheng X-B, Peng H-J, Huang J-Q, Zhang R, Zhao C-Z, and Zhang Q. ACS Nano 2015, 9, 6373. [3] Zhang R, Cheng X-B, Zhao C-Z, Peng H-J, Shi J-L, Huang J-Q, Wang J, Wei F, Zhang Q. Advanced Materials 2016, 28, 1504117. [4] Cheng X-B, Hou T-Z, Zhang R, Peng H-J, Zhao C-Z, Huang J-Q, Zhang Q. Advanced Materials 2016, 28, 1506124.

Authors : Fabian Pawlitzek, Dr. Benjamin Schumm, Dr. Holger Althues, Prof. Dr. Kaskel
Affiliations : Fabian Pawlitzek, Prof. Dr. Kaskel, Dresden University of Technology, Inorganic Chemistry Department, Bergstraße 66, 01069, Dresden, Germany; Dr. Benjamin Schumm, Dr. Holger Althues, Fraunhofer Institute for Material and Beam Technology IWS,Winterbergstraße 28, 01277, Dresden, Germany;

Resume : Rechargeable lithium ion batteries (LIB) as state of the art devices are considered as one of the most promising technologies to meet the challenges for future energy storage. Although such batteries gained commercial success, there are still some limitations in order to realize high-power requirements, especially for electric and hybrid electric vehicles. Here, we present a new concept of high-power LIB combining nanostructured active materials with a binder-free 3D current collector based on vertically aligned carbon nanotubes (VACNT) on metal foils. The benefit of this special material combination is found in low internal resistances what is the key issue for realizing high-power devices. This is achieved by using synthesis methods which assure very effective electrical contacting of active material with VACNT as well as VACNT with metallic current collector. Therefore, an atmospheric pressure CVD process is used for the direct growth of VACNT on metal foils. Subsequently in-situ growth of anode (LTO, lithium titanium oxide) and cathode material (LMO, lithium manganese oxide) on VACNT by a scalable chemical solution deposition is used. As a result impressive rate capabilities in half cells against lithium, e.g. 110 mAh/g at 300C for LTO, as well as in full cell setup for LTO/ LMO up to 60C are achieved. Consequently, the unique nanocomposite structure with its superior electrical conductivity make decorated VACNT a promising material for High-Power LIB.

Authors : Laura Crowther-Alwyn, David Guérin, Elisa Zeno
Affiliations : Centre Technique du Papier, Domaine Universitaire, CS 90251, 38044 Grenoble Cedex 9, France

Resume : This presentation will be focused on the materials and technologies developed within the European project MARS-EV (Grant Agreement n°609201) as well as the latest developments of Centre Technique du Papier, internally and in other selected projects. This new generation of cellulose-based packaging materials for pouch cells take the best advantages of cellulose (renewable material, non toxic, good weight/strength ratio) while greatly improving its barrier properties. The technologies include water-based coating of paper with polymers, grafting of materials’ surface with fatty acids by chromatogeny, and stratification of materials using micro-fibrillated cellulose (MFC) as barrier layer.

Authors : Pantaleone Bruni a, Luis Aguilera b , Aleksandar Matic b, Fausto Croce
Affiliations : a University “G. d’Annunzio” of Chieti-Pescara; Department of Pharmacy; Italy; b University “Chalmers University of Technology” of Göteborg; Department of Applied Physics’; Sweden; pantaleone.bruni@unich.

Resume : The electrospinning process consists in extruding a polymeric solution through a fine nozzle to which has been applied of a strong applied electric field. This process is able to provide nano-fibers having macroscopic lengths (micrometers) and at the same time, diameters ranging from a few tens of nanometers up to several micrometers. The outcome of the process is a non-woven composite structure. The artifacts obtained show unique properties such as high surface development, small fiber diameters, micrometric thickness, high permeability and low density. In the present study we report on the optimization of the electrospinning process and on the definition of an operating protocol able to provide reproducibly electrospun nanostructured polymeric membranes formed by different polymers like acid D,L-lactide (PDLLA), poly (ethylene oxide) (PEO), Poly (acrylonitrile) (PAN), Poly (vinyl alcohol), Poly(methyl-methacrylate) (PMMA) and Polyvinyl-pyrrolidone (PVP) loaded with particles of silicon oxide. The mats have been characterized by scanning electron microscopy (SEM), Transmission Electron Microscopy (TEM), Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC).

Authors : M.Agostini1*, S.Brutti2,3, P.Reale4, A. Matic1, B.Scrosati5
Affiliations : M.Agostini1*, S.Brutti2,3, P.Reale4, A. Matic1, B.Scrosati5

Resume : The rapid development of electronic technologies makes every day more pressing the demand for long life, high energy and environmental friendly batteries. In this framework, wide research is in progress on cathode materials, because improving energy can’t occur without the implementation of higher voltage electrodes. Among the most promising materials, the lithium nickel manganese spinel (LMNO) deserves a special attention thanks to its environmental friendliness, low cost and interesting electrochemical performance. It has the operating voltage at 4.7V vs Li, high good electronic and lithium ion conductivities, it does not suffer of critical structural deformations upon cycling (e.g. no Jahn-Teller effect) and it has good thermal stability. The main weakness attributable to LMNO is related to its interaction with the electrolyte at high voltage, which can bring to corrosion reactions and electrolyte degradation, and finally to the progressive capacity fade. In the present study, LMNO spinel has been synthesized from oxides, according to an easy and cost effective mixed mechanochemical-ceramic solid-state route, also incorporating a synergic Cr- and Fe co-doping. In particular, High Energy Ball Milling (HEBM) has been used to mix and pretreat reagents, in order to improve powders reactivity and obtain the spinel phase with a finely tuned and very mild thermal treatment. This method allows an easy and reproducible synthesis with a quantitative final yield. The final optimized material is a disordered Fd-3m LMNO spinel doped with Fe(III) centres and coated with an amorphous Cr2O3 layer. This synthetic route produces a final material with a homogeneous morphology and exceptional electrochemical performances in terms of cycle life and rate capability.

POSTER : Gianni Appetecchi
Authors : R. Blanga1, M. Goor1, I. Shechtman1, T. Mukra1, E. Peled1, and D. Golodnitsky
Affiliations : 1-School of Chemistry, 2- Applied Materials Research Center, Tel Aviv University, Tel Aviv, 6997801, Israel

Resume : Composite Li10SnP2S12 (LSPS) – polyethylene oxide (PEO) films, containing 25 to 50% polymer were electrophoretically deposited and tested as possible barrier materials for preventing leakage of polysulfides. It was found by XRD and XPS tests that saturation of LSPS-PEO films by LiI salt, followed by prolonged annealing at 90C, diminishes the crystallinity of neat LSPS and results in the formation of the novel composite: Li10+xSnIx P2S12/P(EO)3:LiI solid electrolyte (x<1). The high room-temperature ion conductivity of amorphous Li10+xSnIx P2S12 compound (0.1-0.3mS/cm) is restricted by slow ion transport via polymer electrolyte (PE) imbedded in ceramics and grain boundaries between PE and sulfide. Increase of polymer content and temperature improve total ion transport in the LISPS-PEO system. Conformal EPD coating of sulfur and lithium-sulfide cathodes by the developed composite electrolyte increased the reversible capacity and Faradaic efficiency of the Li/S and Li/Li2S cells, and enabled their operation at 60C. The study of a mixed electron-ion-conducting polysulfide barrier, which includes the effect of type and concentration of electron-conducting additives on the performance of sulfur and lithium-sulfide cells, will be addressed in the presentation. Acknowledgments This work is funded by EU HORIZON2020, HELIS Project, and by the Israel Academy of Science.

Authors : E. Faktorovich Simon, M. Goor Dar, R. Hadar, A. Natan, D. Golodnitsky, E. Peled
Affiliations : School of Chemistry, Department of Physics and Electrical Engineering & Electronics, Faculty of Engineering, Tel Aviv University

Resume : Sodium/air batteries have recently been studied as an alternative to lithium/air batteries. In spite of lower theoretical specific energy (1980Wh/kg of sodium vs. 3600Wh/kg of lithium), the abundance of sodium provides an advantage over lithium for its use as a metal anode. Sodium/air batteries have a problem of the reversibility of electrode reactions similar to that of lithium/air batteries. Applying an appropriate material as a cathode can contribute to the generation of more reversible products on charge, increasing the cyclability and reducing ORR and OER overpotentials of the battery. In this work, we studied ORR and OER in PEGDME500-based electrolytes, in the presence of Na+ ions, applying four types of carbon: glassy carbon, Black Pearl, SB and XC72R carbon. For this purpose, the three-electrode half-cell was used, utilizing the glassy-carbon electrode as the working electrode, which was tested as a stand-alone electrode, or alternatively was coated by the carbon, with a loading of ~100µg/cm2. It was found that, except for glassy carbon, all the other types of carbon showed very close reduction and oxidation overpotentials. The highest reduction and oxidation currents were obtained with the use of Black-Pearl carbon. Acknowledgments This work was funded by ISAEF and BSF foundations

Authors : Marco Raugei, Patricia Winfield, Walter Sweeting
Affiliations : Oxford Brookes University

Resume : The key rationale for the promotion of battery electric vehicles (BEVs) is to address the problems of emissions and resource depletion associated with current internal combustion engine (ICE) vehicles. It is therefore imperative that BEVs fulfil these objectives throughout their lifetime, meaning that the production, use and end of life (EoL) of their components must minimise impacts. Life cycle assessment (LCA) is a prominent technique used to evaluate the environmental impacts of a product system, from initial raw material acquisition, to final recycling and/or disposal. LCA is being used within the EU PF7 research project MARS-EV (Grant Agreement #609201) with a double goal: (i) to develop a baseline reference model for current-production batteries as commonly used in BEVs today; and (ii) to perform a prospective analysis of future improved battery concepts. We hereby present our preliminary impact assessment results for goal (i), and illustrate the main battery component types and related LCA model structure for goal (ii).

Authors : M.Alidoost,U.Zubair,D.Versaci,J.Amici,C.Francia,S.Vankova, S. Bodoardo, N. Penazzi
Affiliations : Dip. Applied Science and Technology, Politecnico di Torino, Duca degli Abruzzi 24, Torino, Italy

Resume : Due to the high theoretical specific energy (2500 Wh kg-1), Lithium-Sulfur batteries have attracted wide attention as next generation electrochemical energy storage. Main factors limiting their commercialization are the poor cycle life and low capacity retention. Actually the anode is composed by metallic Lithium, which is showing high capacity but low safety and durability. To reduce such issues, alternative anodes are studied, e.g. Silicon with high theoretical capacity (4200 mAh/g). However, Silicon is a semiconductor and presents high volume changes during cycling (up to 300%), causing electrode fractures and capacity fading. Here different silicon/graphene based composites with using reduced graphene oxide as electron conductor are presented. Silicon/graphene composites are obtained through hydrogel and polymer cross-linking methods. The morphological characterization shows a good interface between graphene sheets and the Silicon nanoparticles, so affecting positively the overall electron conductivity. The electrochemical performance in term of capacity and cycle life are promising in view of a possible application as anode both for Li-ion and Li-S cells.

Authors : J. Alberto Blázquez, Aroa R. Mainar, Elena Iruin, Olatz Leonet, Luis Colmenares, Iratxe de Meatza, Idoia Urdampilleta, Hans-Jürgen Grande
Affiliations : 1 IK4-CIDETEC, Pº Miramón, 196, 20009 Donostia-San Sebastián (Guipúzcoa), Spain; 2 Departamento de Ciencia y Tecnología de Polímeros, Facultad de Química, (UPV/EHU), Pº Manuel de Lardizábal 3, 20018 Donostia-San Sebastián (Guipúzcoa), Spain.

Resume : The energy storage systems based on secondary zinc electrodes are potential candidates to fulfill the need for light weight and high discharge rate applications. The zinc anode has merits such as low cost, low toxicity, high specific energy, easy availability and ease of handling, which make it suitable for wide applications in alkaline battery systems. However, the commercialization of rechargeable zinc based energy storage systems has been hindered by the short cycle life of the zinc electrode usually limited by the corrosion and zinc dissolution (shape changes and dendrite growth) in the aqueous alkaline electrolytes [1]. In the last few years, many attempts have been made to develop modified zinc electrodes with reduced solubility of zinc discharge products. The majority have included the use of additives either to the electrode or to the electrolyte [2]. In this context, K. Miyazaki et al. were the first to report recently the mitigation of the dendrite formation of zinc electrodes by anion-exchange ionomers by means of modifying the surface of zinc electrode [3]. In this work high-performance Nafion® coated zinc particles as anode material for secondary zinc based energy storage systems has been obtained. The Nafion® coated zinc particles demonstrate superior electrochemical properties than the conventional zinc particles in terms of improved long term cycle life by reducing zinc dissolution which lead to a better reaction reversibility and a better inhibiting effect on shape change of the zinc anode. [1] Xu, M., et al., J. Power Sources, 283 (2015) 358-371. [2] S. J. Banik and R. Akolkar, Electrochimica Acta (2014). [3] K. Miyazaki, et al., Electrochemistry 80 (2012) 725-727.

Authors : Valentina Dall?Asta, Alessandro Resmini, Cristina Tealdi, Piercarlo Mustarelli, Eliana Quartarone
Affiliations : Department of Chemistry, and INSTM, University of Pavia, Viale Taramelli 16, 27100 Pavia, Italy

Resume : The development of rechargeable batteries characterized by higher energy density, longer life-time and safety compared to the commercially available ones is under constant investigation. Improvements in electrode kinetics can be reached by using nanostructures, which are now developed thanks to the continuous progresses in terms of preparation methods. ZnO is potentially a promising anode system, alternative to alkali metals, because of very high theoretical capacity, low cost, chemical stability and reduced environmental impact. However, large volume changes upon cycling result in capacity fading and reduced lifetime. Here we show that strong improvements in ZnO electrochemical performances can be obtained by developing properly optimized nanoarctitectures. Variously nano-arrays, such as nanorods (1D structures), nanosheets (2D) and a hierarchical brush-like systems (3D), were prepared through hydrothermal synthesis and characterised in terms of physico-chemical and electrochemical properties. Results indicate that, among the investigated nanoarchitectures, the 2D systems are more performing due to the presence of small nanoparticles, with average diameter of about 10 nm, maximizing the array specific surface area and favoring the formation of the LiZn alloy. The additional application on such nanoparticles of a graphite coating preserves the morphology during cycling, and enables further improvement in terms of capacity retention and high rate (dis)charge capability.

Authors : J. Amici (1), J. Zeng (1), S. Vankova (1), C. Francia (1), S. Bodoardo (1), N.Penazzi (1), G. Collins (2), H. Geaney (2), C. O’Dwyer (2)
Affiliations : (1) Department of Applied Science and Technology (DISAT), Politecnico di Torino, Duca degli Abruzzi 24, 10129 Torino, ITALY; (2) Department of Chemistry, University College Cork, Cork T12 YN60, Ireland

Resume : The demand for high-energy storage systems is constantly increasing, as is the interest to explore alternatives to commercially available batteries. The rechargeable Li-O2 battery represents an exciting opportunity to design batteries that may satisfy some of the requirements of our future by coupling the light Li metal with the inexhaustible source of O2 of the surrounding air, resulting in high theoretical specific energy density. Clearly, the electrolyte plays a tremendous role on the performance of Li–O2 batteries, affecting the discharge capacity, the voltage gap, the recharge ability and so on. The continuous exploration of practical electrolytes is vital for developing high-performance Li–O2 batteries. The role of different solvents, namely DMSO, TEGDME and EMITFSI, on the cell electrochemical performance when coupled with pure carbon cathodes were compared. Moreover, in order to limit the side reactions at the cathode/electrolyte interface derived from the use of a totally carbon based cathode, homemade Co3O4 cathodes as well as Ru/RuOx nanoparticles supported on conductive indium tin oxide nanocrystals, as both the electro-catalyst and discharge product host, were studied. Electrochemical tests demonstrated how a synergistic electrolyte-catalyst choice improves long-term stability and significantly reduced charge overpotential, while retaining nearly 100% coulombic efficiency.

Authors : P. Posch, I. Hanzu, M. Wilkening
Affiliations : Christian Doppler Laboratory for Lithium Batteries, and Institute for Chemistry and Technology of Materials, Graz University of Technology (NAWI Graz), Stremayrgasse 9, 8010 Graz, Austria

Resume : Sodium titanates represent promising anode materials in Na-ion batteries. In the present study we report about the hydrothermal synthesis and characterization of sodium titanates with respect to morphology and surface properties. The corresponding electrochemical performance as active material was tested in Na-ion half cells. To prepare the titanates, titanium(IV)oxide nanopowder was mixed with a 10 M sodium hydroxide solution; the resulting dispersion was then autoclaved at 165 °C. Different rising procedures were tested to obtain a product with enhanced specific capacity and durability. The titanate prepared can be described with an ordered rod-like structure; it reveals reversible capacities of up to 72 mAh g-1 at cycling rates of 40 mA g-1. The corresponding Coulombic efficiencies turned out to be 99.47 %. Interestingly, the efficiency rises with increasing cycle number. Cyclic voltammetry experiments, which were performed at various scan rates, showed that two reversible phases are formed during the preparation process. These two phases, referred to as high and low capacity phase, clearly possess different capabilities to store sodium ions. While the high-capacity phase, that is, Na2Ti3O7, shows reversible peaks from 0.2 to 0.5 V at currents of -0.15 to 0.15 mA, the cyclic voltammogram of the low-capacity phase, which is, most likely, Na2Ti6O13, is characterized by peaks at 0.79 and 0.9 V. As can be shown via a systematic study, the rinsing procedure affects the amount of Na2Ti3O7 formed.

Authors : Saker. Salima (a ;b) , Hammache. Houa (a), Aliouane. Nabila (a)
Affiliations : (a) Laboratoire d’Electrochimie, Corrosion et de Valorisation Energétique, Département de Génie des Procédés, Faculté de la technologie, Université de Béjaia, 06000, Béjaia, Algeria. (b) Département de Tronc Commun des Sciences de la Nature et de la Vie, Faculté des Sciences de la Nature et de la Vie, Université de Béjaia, 06000, Béjaia, Algeria

Resume : Electrochemical behaviour and corrosion layers of carbone steel electrode, in the absence and presence of a synthesized tetra-phosphonic acid (TPA), namely (methylenbis(2-hydroxy-5,1 phenylene)) phosphonic acid in 3% NaCl medium were investigated by electrochemical impedance spectroscopy and The morphology of the thin film formed on the inhibited surface of carbone steel was examined using the scanning electron microscope. The addition of phosphonic acid leads to growth in diameter and size of the capacitive semicircle , which probably reflects physical blocking of the metal surface which indicates the formation of a thicker protective film and therefore reduced corrosion. SEM image in the presence TPA shows a large area free of corrosion products and reveals the formation of an inhibitor layer. The results show that the inhibitor has the ability of reducing the corrosion rate of ordinary steel in 3% NaCl.

Authors : Mikel Oyarbide, Haritz Macicior
Affiliations : IK4-CIDETEC, Pº Miramón 196, 20009 Donostia-San Sebastián (Gipuzkoa), Spain

Resume : A lot of scientific effort has been focused in the last years to obtain more advanced lithium ion batteries that are able to cycle for longer time. Nevertheless, special care must be taken into account during the management of the batteries. As it has been documented by several scientific publications, different factors (temperature, current rate and the working state of charge (SoC) window) might reduce the life of the cells considerably. Therefore, a correct use of the batteries is very significant to maximize the life of the cells. In particular, to identify the cell working SoC and to minimize the degradation caused by this phenomenon, a correct SoC and state of health (SoH) estimations are necessary. In this sense, this work has been focused on the development and comparison of different battery SoC and SoH estimator algorithms, applied to 15 Ah LiFePO4-Graphite pouch cell. The SoC has been estimated by using extended Kalman filters. Similarly, the state of health has been estimated using iterative transferred chare method, multiscale Kalman filtering, double Kalman filtering and analysing the charging voltage curve shape. The performance of the estimation algorithms has been evaluated at beginning of life, at mid-life and at end of life. Combining this correct lithium ion battery status monitoring with the aging degradation information (by additional aging test conducted off line) a battery life extension is looked forward by implementing a correct battery management system. Acknowledgement: Project financially supported by the European Commission (FP7) under Grant Agreement No. 609201.

Authors : Romain Berthelot, Fabrizio Murgia, Philippe Antitomaso, Lorenzo Stievano, Laure Monconduit
Affiliations : Institut Charles Gerhardt de Montpellier (ICGM - UMR5253) / Université de Montpellier, 2, pl. E. Bataillon, CC1502, 34095 Montpellier Réseau sur le Stockage Electrochimique de l’Energie (RS2E – FR3459) / Université de Picardie, 33, rue St-Leu, 80039 Amiens

Resume : The Chevrel phase family gathers a variety of chemical compounds MxMo6T8 in which M is a mono-, di- or trivalent element and T is a chalcogen. Discovered in early 70’s, they were mainly investigated for their superconducting or thermoelectric properties. A renewed interest has strongly grown due to their ability of reversibly intercalating mono- or multi-valent cations, and thus as electrode materials for rechargeable battery. Mo6S8 is the positive electrode material used in the first rechargeable Mg battery prototype proposed by the group of Aurbach back in 2000. In this pioneering work, Mo6S8 showed a stable capacity during reversible Mg2+ ions intercalation (60 mAh g-1 for almost 600 cycles). Despite many attempts to find more performing cathodes materials, it is still the reference for positive electrodes in Mg-ion systems. However, this phase cannot be synthetized via a direct route, and is commonly obtained by acidic leaching of the ternary compound Cu2Mo6S8. Herein, Cu2Mo6S8 was successfully synthetized using a simple and cost-effective solid-state microwave-assisted reaction. Contrary to the conventional synthetic routes which requires several days of high temperature treatment under inert atmosphere, the microwave-assisted method allows obtaining the phase after only 400 s using a simplified setup in open air, in addition without any major impurity. The derived binary phase Mo6S8, easily obtained after an acidic treatment, was therefore conditioned and tested as a positive electrode material for Mg batteries, providing electrochemical performance in line with those of the material synthesized via the conventional route.

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Authors : Kartik Pilar, Shen Lai, Lisa Cirrincione, Mallory Gobet, Sophia Suarez*, and Steve Greenbaum
Affiliations : Hunter College of CUNY, New York, NY 10065 USA *Brooklyn College of CUNY, Brooklyn, NY 11210 USA

Resume : Nuclear magnetic resonance (NMR) can reveal the nature of ionic motion from molecular rotation, as probed by T1 measurements, to long-range self-diffusion via pulsed gradient spin echo (PGSE) methods. The dynamic range of standard T1 measurements is restricted to a few fixed spectrometer frequencies and broadband relaxometry based on Fast Field Cycling NMR (FFCNMR) methods can considerably expand this range, spanning three to four orders of magnitude in frequency in a single set of measurements. Our group also employs pressure as a thermodynamic variable, in which it is possible to gain new insight into cooperative motional processes characteristic of large flexible ions in ionic liquid (IL)- based electrolytes. Coupled with other characterization tools such as ionic conductivity, these methods provide valuable insight into charge and mass transport mechanisms. The results of several studies of novel Li battery electrolytes in collaboration with other groups will be discussed. In collaboration with the group of S. Passerini (Helmholtz Institute, Ulm) we present preliminary variable pressure and FFCNMR relaxation results for a family of pyrrolidinium-TFSI (Pyrr-TFSI) ionic liquids, in which the chain length on the Pyrr cations was varied between 3 and 9 carbons, and to which LiTFSI has been added. In collaboration with the group of N. Balsara (U.C. Berkeley), we investigate transport properties of novel fluorinated liquid Li electrolytes via standard pulsed gradient NMR and FFCNMR. Of particular interest is the extraction of meaningful cation transference numbers in the presence of strong ion association.

Authors : Akihiko Sagara (1), Norihito Fujinoki (1), Mitsuhiro Murata (1), Shigeo Yoshii (2,3), Haruhiko Habuta (2), Kimitaka Higuchi (4), Shunsuke Muto (4), Teruyasu Mizoguchi (5), Hiroyuki Inoue (5), Maarten Mees (6), and Philippe M. Vereecken (6)
Affiliations : (1) Advanced Research Division, Panasonic Corporation, 1006, Kadoma, Kadoma City, Osaka 571-8501, Japan, (2) Groupwide CTO Office, Panasonic Corporation, 1006, Kadoma, Kadoma City, Osaka 571-8501, Japan, (3) Institutes of Innovation for Future Society, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan, (4) Institute of Materials and Systems for Sustainability (IMaSS), Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan, (5) Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8505, Japan, (6) IMEC, Kapeldreef 75, B-3001, Leuven, Belgium

Resume : We have investigated the transition of electronic structures of nano-structured electrodes in all-solid-state metal-oxide thin-film batteries. Two metal oxide layers: a NiO thin layer and a TiO2-SiO2 nano-composite layer are stacked and sandwiched between current collectors. The nano-composite layer consists of a highly porous mixture of nano-scaled TiO2 and SiO2. A similar device has been reported as a “physical battery” but the mechanism of its operation was unclear. In order to clarify this, the electron energy-loss near-edge structures (ELNES) of Ni, Ti and O were evaluated by TEM-EELS analysis with high spatial resolution. The EELS spectra were, then, compared between the states before and after electrical charging. We found that the Ni-L3 edge in NiO layer seemed to be shifted to the higher energy side and slightly broadened by the charging process. This suggests that the NiO is oxidized in charging and act as a positive electrode. On the other hand, the Ti-L2,3 white-line in the nano-composite layers was shifted to the lower energy side, where both Ti-L2 and L3 lines have split into two peaks after charging. This suggests crystallization and/or partial reduction of the nano-structured TiO2, acting as a negative electrode. Our findings demonstrate that this type of thin film battery operates by the chemical redox reaction rather than the physical charge accumulation. The detailed reactions involving proton in each electrode will be discussed with the results by the first principles calculation.

Authors : Moshiel Biton, Vladimir Yufit, Farid Tariq, Masashi Kishimoto, Nigel Brandon
Affiliations : Department of Earth Science and Engineering, Imperial College London, London, UK Department of Aeronautics, Kyoto University, Kyoto, Japan

Resume : A new methodology of contrast enhancement for multi modal 3D imaging, including novel advanced quantification, on a commercial Lithium Iron Phosphate (LFP) LiFePO4 cathode is presented. The aim of this work is to improve the quality of the 3D imaging of challenging battery materials by developing methods to increase contrast between otherwise previously poorly differentiated phases. In this study we present a novel method of sample preparation with a new type of epoxy impregnation, brominated (Br) epoxy, which is introduced here for the first time for this purpose and found suitable for multi modal imaging, for both focused ion beam scanning electron microscope (FIB-SEM) tomography and X-ray micro tomography. The Br epoxy improves image contrast, which enables higher FIB-SEM resolution (3D imaging), which is amongst the highest ever reported for composite LFP cathodes using FIB-SEM. In turn it means that the particles are well defined and the size distribution of each phase can be analysed accurately from the complex 3D electrode microstructure using advanced quantification algorithms.

Authors : Gero Neubüser, Sandra Nöhren, Viola Duppel, Thomas Fässler, Rainer Adelung, Lorenz Kienle
Affiliations : Institute for Materials Science, University of Kiel, Gero Neubüser; Institute for Materials Science, University of Kiel, Sandra Nöhren; Max Planck Inst Solid State Res, Viola Duppel, Department Chemistry, Technical University of Munich, Thomas Fässler, Institute for Materials Science, University of Kiel, Rainer Adelung; Institute for Materials Science, University of Kiel, Lorenz Kienle

Resume : Silicon microwires represent novel and promising candidates for high capacity anodes in Li-ion batteries (LIB). Their enormous surface to volume ratio which is essential for ion storage enables a capacity of up to 4200 mAh/g which is about ten times higher than for recent carbon anodes. Within this project structural changes and degradation of silicon microwires during (de-)lithiation are being characterized by ex situ transmission electron microscopy (TEM). Uncycled raw silicon wires showed overall high crystallinity but during charging their volume expands about a factor of four and a SEI (solid electrolyte interface) and intermediate LiSi-phases form. Sophisticated cross-sectional preparation of cycled wires has been performed for an investigation of crystallinity combined with the extension of the amorphous SEI. Aside from the anode the Li-rich Li4.1Si phase has been characterized for the first time by TEM methods showing planar defects representing barriers for the Li-ion transport and subsequently decreasing the anodes´ capacity. Challenging sample preparation is a key point to achieve electron transparent samples from the µm-sized wires. Methods include focused ion beam (FIB) technique, ultramicrotomy to access the interior part of the wires for TEM. Further preparation under inert gas atmosphere as well as transfer to TEM in argon atmosphere was optimized to handle reactive Li-containing samples.

MODELLING : Wladek Wieczorek
Authors : Yair Ein-Eli
Affiliations : Department of Materials Science and Engineering and Nancy & Stephen Grand Technion Energy Program (GTEP), Technion- Israel Institute of Technology Haifa 3200003 Israel

Resume : Electrochemical systems are being thought as the solution for the vast demand for high energy density in both portable and stationary devices. Such systems hold a great promise, while pressure on researchers grows as the need for more “juice” in mobile device (from small hand held electronic to large mobile systems as EV) dramatically increase as technology is rapidly evolving. In this talk, we will address both the anode and cathode materials in advanced Li-ion batteries. Lightweight, loaded and flexible electrode construction materials will be discussed in this talk.

Authors : Arpit Maheshwari, Mihaela Aneta Dumitrescu, Matteo Destro, Massimo Santarelli
Affiliations : Politecnico di Torino; Lithops Srl; Lithops Srl; Politecnico di Torino

Resume : Scientific literature about modelling, especially physics based models, abounds in discharge models for lithium ion batteries. However charge models have received much less attention. Every secondary lithium batteries undergo multiple charge as well as discharge cycles. Vehicles with electric traction usually come with regenerative braking, wherein a battery is subjected to very transient conditions and high charge rates. Moreover, fast charging remains one of the most important factors in electric traction vehicle adoption. One reason for this lack of focus on charge models is that the same set of parameters is assumed to be valid for both charging and discharging. In this work, this hypothesis is tested and a charge model is developed starting with a validated physics based discharge model of a lithium iron phosphate – graphite battery. This validated discharged model is first reversed to get the charge model and is then compared against experiments. It is seen that this model needs to be modified to represent the actual charging behaviour. This process of adapting the model is described in the work. Finally after optimizing the charge model, the parameters that give rise to the different electrochemical and thermal behaviour in these two models are compared and analysed for the differences and similarities. Focus on differences in the heat generation of these models is emphasized because of its importance in designing proper heat management systems for batteries. In particular, it is shown that in the development of the charge model, consideration of hysteresis effect and charge dependent radius is critical.

Authors : M. Heck
Affiliations : S. Lux; A. Maheshwari; J. Schmitt; M. Vetter

Resume : Aging of lithium ion batteries during usage leads to capacity- and power fade. Thus, aging modifies the internal cell properties as a function of the time and usage parameters. In the framework of the large-scale EU-project “Materials for Ageing Resistant Li-ion High Energy Storage for the Electric Vehicle” (MARS-EV), extensive aging tests for studying the degradation of commercial high-energy lithium ion cells have been carried out at the Fraunhofer Institute for Solar Energy Systems (ISE) in Freiburg (Germany). The goal is to implement an aging model into a Particle filter used for precise state of charge estimation. The tests are divided into calendric and cycle ageing test. Cycle tests were carried out for different ambient temperatures, cycle current amplitudes and depth of discharge while for storage tests the state of charge and the ambient temperature were variated. The characterization of the cells at different aging stages was done with a wide range of electrical characterization methods like electrochemical impedance spectroscopy, capacity tests, open circuit voltage measurements and pulse-power tests. Thereby the influence of external aging conditions on the degradation of the cell parameters could be investigated. At a late stage in battery life, an accelerated capacity decrease was observed. In this talk we present an aging model dependent on the usage parameters. Additionally we show the parametrization of a dynamic equivalent circuit model using impedance spectroscopy measurements as well as pulse-power test in time domain. The resulting electrical model was implemented in an algorithm using Particle filter for state-of-charge estimation. The accuracy and precision of the electrical model and the state-of-charge estimator could be verified by comparing simulations and measurements. Current profiles typical for electric vehicles have been tested for this purpose.


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Symposium organizers
Diana GOLODNITSKYTel Aviv University

Ramat-Aviv, Tel-Aviv 69978 Israel
Gianni APPETECCHIENEA, Laboratory of Materials & Physicochemical Processes

Via Anguillarese 301, 00123 S. Maria di Galeria, Rome, Italy
Silvia BODOARDOPolitecnico di Torino Duca degli Abruzzi 24, 10129 Torino - Italy