Symposium FC
Electrochemical Energy Storage Systems: the Next Evolution


Session FC-1 - Batteries

FC-1:IL01  Multinuclear Solid State NMR Studies of Lithium Battery Materials
S.G. GREENBAUM, Hunter College of the City University of New York, New York, NY, USA  

Structural studies of materials under development for lithium battery technology are often hampered by the lack of long-range order found in well-defined crystalline phases. In particular, powder x-ray diffraction is unable to provide detailed spatial information about amorphous compounds. Our laboratory utilizes solid state nuclear magnetic resonance (NMR) methods to investigate structural and chemical aspects of lithium ion cathodes, anodes, electrolytes, interfaces and interphases. NMR is sensitive to small variations in the immediate environment of the ions being probed, and in most cases, is a reliably quantitative method. A summary of several recent NMR investigations undertaken in our lab on materials provided by collaborators will be presented, including (i) 7Li and 31P studies of nanoporous Li3PS4 which exhibits ionic conductivity over two orders of magnitude higher than that of the corresponding bulk crystalline compound; (ii) 6Li and 7Li investigation of Li1.2Mn0.53Ni0.13Co0.13O2, in which it is demonstrated that molten salt flux treatment facilitiates the transformation of the starting materials into a true solid solution; (iii) 7Li and 19F studies of charge transfer in CFx/Ag2V4O11 hybrid cathodes for medical batteries. Time permitting, we will also show some recent results for newly developed sodium ion battery materials.

FC-1:IL02  Study of New Active Materials for Rechargeable Sodium-ion Battery
H. IBA, S. NAKANISHI, Battery Research Division, Toyota Motor Corporation, Susono, Shizuoka, Japan

Rechargeable batteries have been desired for high energy, high power, safety and sustainability to meet the requirements of large-scale applications such as hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs) and electric vehicles (EVs). Therefore, much effort has been devoted to develop a variety of batteries. Very recently, sodium-ion batteries have gained considerable attention from the reasons as follows. The first is an abundant of sodium working as an ionic career instead of lithium and the other is the various (de-)intercalation structures which are not familiar with lithium equivalences. The diversity is characteristic of SIBs and it has been recognized that electrode material with new intercalation structure would still exist. Hence, extensive researches on novel electrode materials have been carried out in the world to overcome the disadvantage of low energy densities as compared with the current lithium-ion batteries. In the course of our material research, we discovered the novel Na4Co3(PO4)2P2O7 cathode material, which has multiple sodium-ion pathways in the structure and shows unique intercalation capabilities.1) In this presentation, we will report our works about the novel active materials for sodium-ion battery.
Ref: 1) M. Nose et al., J. Power Sources, 234 (2013) 175-179

FC-1:L03  Understanding and Predicting Organic Electrode Materials of Rechargeable Lithium Batteries via Computational Approaches: The New Deal
C. FRAYRET1, D. TOMERINI1, C. GATTI2, Y. DANTEN3, M. BECUWE1, F. DOLHEM4, P. POIZOT5, 1LRCS-CNRS UMR 7314, Université de Picardie, Amiens, France; 2CNR-ISTM, Istituto di Scienze e Tecnologie Molecolari, Milano, Italy; 3ISM-CNRS UMR 5255 , Talence, France; 4LG-CNRS-FRE 3517, Université de Picardie, Amiens, France; 5IMN-CNRS UMR_C 6502, Université de Nantes, Nantes, France

In the search for cost-effective and less ecological footprint Lithium ion batteries, redox-active organic compounds offer great promise to contribute to the future supply of energy, but extensive efforts in research, development and demonstration are still needed to overcome the scientific, technical, economic and environmental challenges to developing a sustainable and commercially viable electricity production system. With the help of advanced theory and computational techniques, effective design and deep exploration of such innovating battery materials can be accelerated. Their organic character offers the possibility of accessing prediction of some of their properties through molecular or cluster approaches coupled to sophisticated electronic structure analyses. However, this new field raises new questions and may require more sophisticated methods than those used for conventional inorganic counterparts (e.g. crystal structure prediction). On the basis of various systems mainly belonging to the quinonic, terephtalate or oxocarbon families, answers given through our active research and joined efforts with experimentalists contribute to the conceptual knowledge of these compounds and pave the road towards improved organic electrode materials development.

FC-1:L04  Fundamental Study of Storage Material for High-temperature Rechargeable Oxide Batteries (ROB)
O. TOKARIEV, C.M. BERGER, P. ORZESSEK, L. NIEWOLAK, M. BRAM, W.J. QUADAKKERS, N.H. MENZLER, H.P. BUCHKREMER, Institute of Energy and Climate Research (IEK-1), Forschungszentrum Juelich GmbH, Germany

This work focuses on the research of porous storage materials for a novel high temperature rechargeable oxide battery (ROB). In the battery, a solid oxide cell runs alternately in fuel cell and electrolyzer modes. The stagnant atmosphere in the battery, consisting of H2 and H2O vapor, is used as a reducing and oxidizing agent for a metal-metal oxide material, which serves as the integrated energy storage unit. The storage components have to meet requirements such as; good kinetics of redox reactions, high oxygen storage capacity, and high lifetime, in order to assure a continuous ROB operation.
Because of long-term redox cycling at 800 °C, the structure of the Fe/FeO storage material degrades, making the material incapable of storing oxygen for continuous redox reactions. Hence, the Fe/FeO matrix was supplemented by inert as well as reactive oxides which are capable of promoting and/or inhibiting ageing and the kinetics of redox reactions.
Fundamental analysis after redox cycling shows that the inert oxides hinder to some extent structural degradation, whereas reactive mixed oxides are fully capable of preventing sintering for several redox cycles. The influence of the powder parameters on the thermochemical processes in the ROB were also revealed as significant characteristics.

FC-1:IL06  Battery Architectures Based on Three-dimensional Electrode Designs
B. DUNN, Department of Materials Science and Engineering, UCLA, Los Angeles, CA, USA  

Three-dimensional battery architectures offer a new approach for miniaturized power sources that serve such application areas as sensing/actuation, communication and health monitoring. With 3-D battery architectures, one exploits the third dimension, height, to increase the amount of electrode material within a given footprint area. Moreover, by using 3-D electrode designs which minimize the ionic path length between electrodes, there is the opportunity to achieve both high energy and power density within the small footprint area.
The present paper reviews recent advances in the development of 3-D lithium-ion battery architectures that incorporate periodic electrode arrays. The design rules for such 3-D architectures have been established and methods for fabricating electrode array structures for a variety of materials have been developed. In addition to interdigitated designs, batteries comprised of 3-D electrode arrays of carbon rods with a traditional planar electrode are able to achieve high areal energy densities at reasonable power levels. The batteries and electrode configurations presented here illustrate both the advantages offered by 3-D architectures and the challenges facing this technology.

FC-1:L07  New Gel Polymer Electrolyte with Improved Intrinsic Safety for Use in Lithium-ion Batteries
R. VUKICEVIC, S. OBEIDI, A. LEX-BALDUCCI, M. SCHAEFER, MEET Battery Reseach Center / Institute of Physical Chemistry, University of Münster, Germany

To improve the safety of lithium-ion batteries, liquid electrolytes which are prone to leakage and contain flammable solvents can be substituted by gel polymer electrolytes (GPEs). In GPEs, the liquid electrolyte is immobilized in a polymer matrix avoiding the risk of leakage. However, liquid electrolytes containing solvents with low flash points are frequently used for GPEs rendering them still flammable.
In this contribution we report on a new GPE based on a high flash point liquid electrolyte, which was realized by substituting linear carbonates of state-of-the-art liquid electrolytes for adiponitrile resulting in an increase in flash point by more than 100 °C. In order to obtain good interaction between the polymer matrix and the liquid electrolyte a new polymer consisting of acrylonitrile and oligo(ethylene glycol) phenyl ether acrylate was synthesized. Due to structural similarities of the polymer and the solvents of the liquid electrolyte, the immobilization of a huge amount of liquid electrolyte in the matrix was possible. The resulting GPE displayed a room temperature conductivity of 2.3 mS cm-1, a broad electrochemical stability window, and good performance in NCM/graphite full cells.

FC-1:L08  Local Structure of Lithium Orthosilicates Li2MSiO4 (M = Mn, Fe) Cathodic Materials: a Neutron Pair Distribution Function Study
A. MANCINI, L. MALAVASI, Dip. di Chimica, Sezione Chimica Fisica, Università degli Studi di Pavia, INSTM UdR di Pavia, Pavia, Italy

Lithium orthosilicates of transition metals are well known and studied cathodic materials for Li-ion batteries. In particular, Li2MSiO4 compounds with M = Mn, Fe have attracted increasing attention due to their noteworthy properties, such as the possibility of a rapid extraction of two lithium ions per unit formula (in principle), the high capacity (up to 100 mA h g-1), the strong lattice stabilization generated by Si-O bonds and the composition, made by relatively safe, abundant and low cost elements. However, this family of cathodes is also characterized by a rich polymorphism, with the possibility of (at least) three different structures with very little energy differences between them; this fact can be translated in the difficult in obtaining single phase materiale and in complexity in the structural characterization of the single polymorphs. On the other hand, Pair Distribution Function analysis have demonstrated in recent times to be a powerful probe in order to unveil structural details otherwise not detectable with other techniques. With the PDF analysis of the three polymorphs for both the Mn and the Fe lithium orthosilicates, this study aims to give a deep insight into the complexity of their local structures and to correlate them with the electrochemical properties.

FC-1:L09  Effect of Plasma Assisted Nanoparticle Dispersion on Thermal and Mechanical Properties of Electrospun Separators for Lithium-ion Batteries
V. COLOMBO, M. GHERARDI, R. LAURITA, Alma Mater Studiorum - Università di Bologna, Department of Industrial Engineering (DIN), Bologna, Italy; D. FABIANI, M. ZACCARIA, Alma Mater Studiorum - Università di Bologna, Electric, Electronic and Information Engineering Department (DEI), Bologna, Italy; M.L. FOCARETE, C. GUALANDI, Alma Mater Studiorum - Università di Bologna, "G. Ciamician" Chemistry Department, Bologna, Italy

Electrospinning of nonwoven mats represents a suitable approach in the realization of enhanced separators for lithium-ion batteries, due to their high surface area and large electrolyte uptake. The addition of oxide nanoparticles in the fibers can increase mechanical, thermal and electrical properties of the electrospun mats, but a good dispersion of the nanofiller is strictly required in order to obtain these improvements. Mechanical stirring, sonication, ball milling and the addition of dispersing agents are traditional methods used to prevent nanoparticle aggregation in liquids. The exposure of the polymeric solution to a non-thermal atmospheric pressure plasma before nanoparticles addition, followed by mechanical stirring, has allowed the production of nanofibers containig homogeneusly dispersed nanoparticles. This study reports on the realization and characterization of poly(ethylene oxide) nanofibrous separators, loaded with fumed silica nanoparticles dispersed by means of plasma jet assisted process. Membrane morphological characterization and nanoparticle dispersion in the fibers have been observed through SEM and TEM images analysis. Moreover, thermal degradation analysis (TGA) and tests on the mechanical properties of the membrane were implemented.

FC-1:IL10  Materials and Processes in Rechargeable Sodium/Air Batteries
E. PELED, H. MAZOR, M. GOOR, D. GOLODNITSKY, R. HADAR, School of Chemistry, Tel-Aviv University, Tel-Aviv, Israel; Wolfson Applied Materials Research Center, Tel-Aviv University, Tel-Aviv, Israel

The sodium/air redox couple has the potential to deliver a pronounced step-change in the specific energy of batteries. This is particularly important for electric-vehicle (EV) applications. The main problem of using an alkali-metal anode is the formation of metal dendrites on battery charge. Our research addresses the molten-sodium/air battery. Operating the battery at above the melting point of sodium (97.8 °C), in addition to eliminating dendrite formation, could accelerate sluggish cathode reactions and lower cell impedance. This study was focused on understanding the key parameters that affect the performance of the electrodes and their impact on the operation of the molten-Na/air cell in glymes, PYR14TFSI ionic liquid (IL) and polyethylene oxide-based electrolytes. A proper SEI (solid electrolyte interphase) is critical for good battery performance and safety, thus different sodium-SEI precursors were tested. The faradaic efficiency for cycling of molten sodium at 105 °C, was lower than 30% in glymes and up to 95% in both ILs and PEO electrolytes containing certain Na-SEI precursors. The SEI composition was analyzed by XPS. The electrochemical-stability window (ESW) of IL-based and PEO-based was measured. The battery performance and the discharge products will be reported.

FC-1:IL11  Precisely Engineered Colloidal Nanomaterials for Li- and Na-ion Batteries
M.V. KOVALENKO, Institute of Inorganic Chemistry, ETH Zurich, Switzerland and Empa-Swiss Federal Laboratories for Materials Science and Technology, Switzerland

Most of today's applications of Lithium-ion batteries (e-mobility, portable electronics etc.) face growing demands for significantly improved performance: higher energy density, improved cycling performance, safety, flexibility in device integration, etc. For these reasons, there is a great interest in development of nanostructured anode and cathode materials. Colloidal chemical synthesis is very attractive as it offers routine access to materials with the mean crystallite size in the range of 3-20 nm. Non-aqueous synthesis, in particular, allows also inexpensive access to nanocrystals and nanoparticles with very high degree of compositional, morphological and size-uniformity. We will present two examples of highly-monodisperse, sub-20nm nanocrystals: Metallic (Sn. Sb, Ge, etc.) nanocrystals as anode material and metal fluoride nanocrystals as cathode material. These materials were synthesized using inexpensive precursors such as metal chlorides and recyclable, technical grade high-boiling organic solvents such as hydrocarbons, yet enabling narrow size distributions of 3-10%. We will present detailed structural and electrochemical characterization of these nanostructures as perspective electrodes for Li- and Na-ion batteries.

FC-1:L12  Concurrent Formation of LiCoO2 Crystal / Li-B-O Glass Composite Layer onto a Pt Substrate by Glass-Flux-Coating
Y. MIZUNO1, N. ZETTSU1, 2, T. SAKAGUCHI3, T. SAITO3, H. WAGATA1, 2, S. OISHI1, K. TESHIMA1, 2; 1Shinshu University, Nagano, Japan; 2CREST, Japan Science and Technology Agency; 3Toyota Motor Corporation, Japan

All-solid-state lithium-ion rechargeable batteries (LIBs) have been attracted much attention as a power source of electric vehicles and hybrid-electric vehicles because of their large advantages such as high safety, energy density, power density, and long lifetime. A great challenge of all-solid-state LIBs for practical use is reduction of the large charge transfer resistance at the interface between the electrode and electrolyte. One the basis of these backgrounds, we herein propose a new one-step fabrication process for stacking assemblies of LiCoO2 crystal layer/ Li-B-O glass layer on a Pt substrate. The fabrication of LiCoO2 crystal layer using Co metal thin-film and LiNO3 as a solute was performed in Li-B-O glass on the substrate (Glass-flux-coating). The numerous LiCoO2 crystals with a well-developed hexagonal shape were grown directly onto the substrate, and each individual crystals surfaces were fully covered with Li-B-O system glass. Furthermore, the interfaces between the substrate and the LiCoO2 crystal layers were well-connected without impurities formation. Detail of the structural and the LIB characteristics will be reported in the CIMTEC 2014.

FC-1:L13  Polymer-in-ceramic Solid Electrolyte for Li-ion Batteries
G. GOLODNITSKY1, 2, R. BLANGA1, K. FREEDMAN1, E. PELED1, 1School of Chemistry; 2Wolfson Applied Materials Research Center, Tel Aviv University, Tel Aviv, Israel

The method of electrophoretic deposition (EPD) was used to fabricate ion-conducting polymer-in-ceramic electrolytes for the first time. TGA, DSC, XRD, TOFSIMS, ESEM and AC-impedance tests were used for the characterization of the films. We found that the relative content of polyethylene oxide and LiAlO2 in the membrane depends on the type of solvent and composition of the suspension. Films deposited at 50V are smoother, conformal and more uniform than those prepared at 100, 150 and 200V. TOFSIMS positive-ion-species images showed that with increase in concentration of ceramic powder in the suspension, the deposition of PEO occurs predominantly between the LiAlO2 particles. The ionic conductivity of a composite, LiTFSI and LiI electrolyte is 0.4-0.5mS/cm at 30 °C and does not change up to 100 °C. When deposited on a Si anode the membrane conformally follows the contours of the rough electrode surface and provides strong mechanical integrity to the anode, enabling improved capacity of the Li/Si cell. This study paves the way for the application of a new simple EPD approach to the preparation of wide-temperature-range solid lithium-ion conducting electrolytes.

FC-1:L14  Conducting Polymers as Effective Additives for Positive Electrodes in Li-ion Batteries Working at High Rates
P. JIMENEZ1, B. LESTRIEZ1, J.-P. BONNET2, P. BLANCHARD3, J.-C.BADOT4, O. DUBRUNFAUT5, D. GUYOMARD1, J. GAUBICHER1, Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France; 1Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, Nantes, France; 2Lab. réactivité et chimie des solides (LRCS), CNRS UMR7314, Université de Picardie J. Verne, Amiens, France; 3Lab. MOLTECH-Anjou, CNRS UMR6200, Université de Angers, Angers, France; 4Institut de Recherche de Chimie Paris, CNRS UMR 8247, Chimie ParisTech, Paris, France; 5Lab. de Génie Electrique de Paris, CNRS UMR 8507, SUPELEC, Sorbonne; Universités, UPMC Univ Paris 06, Univ Paris-Sud, Gif-sur-Yvette, France

One of the greatest challenges in the current research in lithium-based batteries is reaching the high energy and power density values necessary for applications such as electrical vehicles. The required the scaling up of electrodes brings up severe restraints to the specific capacity obtainable in practice due to limitations to electronic and ionic transport, that have a dramatic effect when a battery is operating at a high current density. To overcome these limitations we put forward the use of conducting polymer additives in a positive electrode, which are able to act as conducting fillers, mechanical reinforcement materials and add some extra capacity to the electrodes.
Here we report successful strategies for incorporation of conducting polymers into positive electrodes improving their performance at high rates. In the case of the low-cost conducting polymer polyaniline (PANI) the excellent properties of a completely deprotonated lithiumdoped state PANI in terms of specific capacity, stability on cycling and rate capability are presented. Different strategies for the introduction of this new PANI material in electrodes of different active materials of interest such as LFP, NMC, or LTO will be presented. Among the most remarkable results we report the coating of bare LFP particles with thin layers of PANI and the electrodes made with them, which clearly surpass the performance at high rates of the commercial carbon coated LFP electrodes.

FC-1:IL15  Novel Electrode Materials for Rechargeable Batteries
D. GUYOMARD1, L. ROUÉ2, M. CERBELAUD1, J. GAUBICHER1, N. DUPRÉ1, P. MOREAU1, B. LESTRIEZ1, 1Institut des Matériaux Jean Rouxel (IMN), Université de Nantes, CNRS, Nantes, France; Réseau sur le Stockage Electrochimique de l'Energie (RS2E), FR CNRS 3459, France; 2INRS-Énergie, Matériaux et Télécommunications, Varennes Québec, Canada

An electrode material for a rechargeable battery has to be seen as a complex mixture of a surface-modified electrochemically active material with other non electrochemically active components such as conducting additive and binder, in contact with the current collector. We show that the electrode performance depends on the key integration of the active material within the efficient network of conducting additive and binder, i.e. on the electrode architecture and composition, but also on the adhesion and electric properties of the electrode/current collector interface. Moreover, it is shown that the active material itself needs some surface protection in order to provide long term performance.
On going research at IMN in this field will be reported including new active material synthesis, surface modification of active materials by molecular grafting or electrolyte additives, electrode composition and preparation, and nanotexturation of 2-D and 3-D current collectors. Exemples will be given dealing with LiFePO4 and Li(Ni,Mn)2O4 positive electrodes for Li-ion batteries, NaxFePO4 positive electrode for Na-ion batteries, and Si-based negative electrode for Li-ion batteries.

FC-1:L16  High Cost Performance Cathodes for Large Scale Rechargeable Batteries
S. OKADA, T. KIDERA, N. DIMOV, H. HORI, A. KITAJOU, Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga, Japan 

Iron-based conversion-type cathode for Na is one of the promising candidates for large-scale rechargeable battery. In this presentation, the cathode performances of perovskite-type FeF3, pyrite-type FeS2 and rutile-type FeOF are compared. Among them, the advantage of FeF3 is the highest discharge voltage, because of the strong electronegativity of fluorine. On the other hand, the discharge/charge overpotential is relatively large. Because the strong ionic bond between Fe and F brings low electronic conductivity. In comparison with FeF3, FeS2 has the lower discharge/charge overpotential. However, it is well known that the discharge products such as lithium polysulfides, are soluble to the electrolyte. According to the conversion-type reaction formula as shown in Table 1, the theoretical capacity of FeOF is also attractive. But, it is difficult to synthesize the FeOF single phase. So, the roll-quench method as the quick synthesis route of FeOF is introduced in this presentation. The common disadvantage to these conversion cathodes is the poor cyclability, due to the large volume change. In order to find some solutions of this problem, a discharge/charge reaction mechanism is also examined by XRD, XPS and XANES measurements.

FC-1:L17  Effects of Heat-treating Temperature on the Properties of LiMn1.5Ni0.5O4 Cathode Materials
SHE-HUANG WU, JE-JANG SHIU, Tatung University, Taipei, Taiwan; WEI KONG PANG, N. SHARMA, V.K. PETERSON, Australian Nuclear Science and Technology Organisation, Australia

LiMn1.5Ni0.5O4 samples were prepared via a spray combustion method followed by heat-treatment at temperatures between 600 and 1000 °C for 8 hours in air. Based on the high-resolution NPD data, Fd3 ̅m and P4332 phases are observed dominantly in the samples prepared at 600 and 700 °C, respectively. For samples heat-treated at temperatures higher than 800 °C, Fd3 ̅m phase becomes majority again with detectable LixNi1-xO. Among the prepared samples, 900 °C heated sample shows the most promising cycling performance when they were studied with LiMn1.5Ni0.5O4/Li cells at rates lower than 1C. In order to understand the reasons of the results, in-situ neutron diffraction study with Li4Ti5O12 anode to reveal the structural evolution of LiMn1.5Ni0.5O4 cathodes, dissolution of transition metals upon cycling will also be done in the near future.

FC-1:L18  Hydrothermal Synthesis of Porous Spindle LiFePO4 as High Performance Cathode Material for Lithium Ion Batteries
MEI LIN, BOLEI CHEN, H.L.W. CHAN, JIKANG YUAN, Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong, China

Porous spindle and hexagram-like LiFePO4 (LFP) cathode material was simply synthesized though the hydrothermal method using a copolymer (PEG-PPG-PEG) as the surfactant. The influence of the pH values and reaction time on the morphology of LFP has been briefly investigated. The resulting Hexagram-like LFP microstructures are constructed with three rugby-like plates with 30 µm length, while these micro-plates are cross-linked in an ordered fashion. By adjusting the pH values and reaction time, a novel porous spindle microstructure with 20 µm length were obtained. The presence of copolymer plays an important role in the construction of the hierarchically microstructures. The formation mechanism is proposed based on the results of experiments. In addition, to gain the cell performance of the synthesized LFP, galvanostatic charging-discharging measurement on the as-prepared samples were performed. The hexagram-like LFP/GO shows unexpected electrochemical performance since the hexagram-like LFP have dense and large structure which prevents access for the liquid electrolyte. This work also provides the possibility for further investigation into the shape-dependent electrochemical performance of other materials by optimizing the experimental parameters during hydrothermal synthesis.

FC-1:L19  ESR Study of Electronic Properties, Valence State and Local Crystal Structure of Li-ion Battery Cathode Materials
N.M. SULEIMANOV, Zavoisky Physical Technical Institute of Russian Academy of Sciences, Kazan, Russia; S.R.S. PRABAHARAN, VIT University, Chennai campus, India; D.R. ABDULLIN, Zavoisky Physical Technical Institute of Russian Academy of Sciences, Kazan, Russia; M.S. MICHAEL, Anna University, India

The electronic and ionic transport in cathode materials are two interconnected processes playing a crucial role in Li-ion batteries. Even if the crystal structure is favorable to fast diffusion of Li ions, the poor electronic conductivity will retard the ionic mobility. The electronic conductivity is realized as the jumping of electrons from ion with low valence state to ion with high valence state and a suitable electronic structure is the necessary condition for that. It is also evident that the fundamental knowledge of structural imperfections and their effect on charge transport is needed on atomic scale. In this report recent studies on cathode materials using electron spin resonance method (ESR) are presented. The role of partial substitution of transition elements by Al, Ga and Mg in canonic LiCoO2, LiMn2O4 systems and its effect on the local electronic structure and working parameters will be considered. We will demonstrate how ESR and magnetic susceptibility methods help to shed the light on electronic and crystal structures of LixMn2(MoO4)3 (0 ≤ x ≤ 2) system. The formation of anti-site defects and the mechanism of "healing" of these defects as a result of migration of transition ions to equilibrium positions during the charging process will be discussed.

FC-1:IL21  Mesoporous TiO2 as an Alternative Anode for Fast Chargeable Lithium-ion Battery
P. BALAYA, National University of Singapore, Singapore 

It is known that commercial lithium-ion battery uses low potential graphite and is not safe especially at fast charging due to dendrite growth of Li. Currently industries provide fast chargeable battery technology solution using high potential Li4Ti5O12 (1.55V) assuring safety. However, Li4Ti5O12 anode has limited storage capacity (170 mAh/g). Inexpensive TiO2 has relatively high storage capacity (335 mAh/g) with an average Li insertion potential at 1.7V.
In this talk, we present our work on soft-template synthesized mesoporous TiO2 (meso-TiO2). Electrode of meso-TiO2 mixed with 15% carbon shows enhanced storage capacity of 265 and 107 mAh/g at C/5 and 30C respectively and appreciable storage performance without additive carbon. Most importantly, meso-TiO2 exhibits higher tap density (~6 times) than commercial TiO2 powder. Undoped meso-TiO2 with well-integrated nano-grains (15-20 nm) forming 0.5-1 micron particulates favors excellent lithium insertion/extraction unlike isolated grains (25 nm) of commercial TiO2. We discuss the cause for the observed enhanced storage behavior in mesoporous TiO2 in terms of (a) formation of conducting surface layers due to LixTiO2 upon Li insertion and (b) accumulation of electrons at the interfaces in dense packed pristine meso-TiO2.

FC-1:IL22  Superionic Conducting Ceramic Electrolyte Enabling Lithium Metal Anodes and Solid State Batteries
J. SAKAMOTO1, T. THOMPSON1, M. JOHANNES2, A. HUQ3, J. ALLEN4, J. WOLFENSTINE4, I.N. DAVID1, 1Michigan State University, Chemical Engineering and Materials Science Department, East Lansing, MI, USA; 2Naval Research Laboratory/Center for Computational Materials Science, Anacostia, VA, USA; 3 Spallation Neutron Source, Oak Ridge National Laboratory, Oak Ridge, TN, USA; 4Army Research Laboratory, RDRL-SED-C, Adelphi, MD, USA 

Lithium ion battery technology has advanced significantly in the last two decades. However, future energy storage demands will require safer, cheaper and higher performance electrochemical energy storage. While the primary strategy for improving performance has focused on electrode materials, the development of new electrolytes has been overlooked as a potential means to revolutionize electrochemical energy storage. This work explores a new class of ceramic electrolyte based on a ceramic oxide with the garnet structure. The garnet, with the nominal formulation Li7La3Zr2O12 (LLZO), exhibits the unprecedented combination of high ionic conductivity (~1mS/cm at 298 K) and chemical stability against metallic Lithium. This presentation will discuss fundamental and applied aspects involving the development of garnet-based LLZO electrolyte. The purpose of the fundamental activities is to correlate the atomic structure with transport data to hypothesize strategies for further increasing the ionic conductivity. The applied aspects will include DC cycling data to assess the compatibility between metallic Lithium anodes and LLZO.

FC-1:IL24  Reaction Mechanism of High-energy Li-excess NMC Cathode Materials
C. DELMAS1, H. KOGA1, 2, L. CROGUENNEC1, M. MÉNÉTRIER1, S. BELIN3, C. GENEVOIS4, L. BOURGEOIS5, F. WEILL1, 1ICMCB-CNRS, Université de Bordeaux, IPB-ENSCBP, Pessac cedex, France; 2TOYOTA MOTOR EUROPE NV/SA, Zaventem, Belgium; 3Synchrotron Soleil - L'orme des Merisiers Saint Aubin, Gif-sur-Yvette, France; 4GPM, Université de Rouen, Saint Etienne du Rouvray; 5Université de Bordeaux, ISM, Talence, France   

The materials belonging to the (1-x)LiMO2.xLi2MnO3 system (M = Ni, Co) exhibit the largest capacity among all other layered oxides. These materials are overlithiated layered oxides (Li1.(LiyMn1-y-u-tCouNitO2) with a significant amount of lithium in the transition metal site. During the first charge, when all cations are oxidized to the tetravalent state, an overcharge of the cell leads to a structural modification that can be schematically described as a Li2O extraction occurs that cannot explain alone the oxidation process.
In order to clarify the mechanism which is involved during the overcharge a systematic study has been carried using chemical analysis, X-ray and neutron diffraction, in operando XAS, very high-resolution electron microscopy and Raman diffraction. During the high voltage plateau in the first cycle, there is a partial densification on the external part of the particles followed by an oxygen oxidation in the bulk of the lattice without oxygen migration.
This redox process is completely reversible in discharge. The contribution of nickel and cobalt and oxygen reduction leads to the huge specific capacity of this material family.

FC-1:IL25  Lithium-ion Batteries: Cell Design, Production and Performance
S. PASSERINI, Helmholtz Institute Ulm, Karlsruhe Institute of Technology, Ulm, Germany

Along with the worldwide growing importance of energy and the various ways to generate it, energy storage has become more and more essential in order to align its supply and demand with respect to the time and place the energy is provided and required. For such reasons mobile energy storage devices have gathered increasing significance, in particular batteries. The development of lithium-ion batteries has marked a breakthrough in battery technology. Cell design plays an important role in the production, cost and performance of Li-ion batteries. In this presentation the impact of cell and components design on the production cost and cell application will be illustrated.

FC-1:L26  Influence of Electrode Structure on The Performances of Li Ion Battery: From One Dimensional Nanostructured Electrode to Three Dimensional Nanoporous Electrodes
XIN HUANG, HONG YU, QINGYU YAN, HUEY HOON HNG, School of Materials Science and Engineering, Nanyang Technological University, Singapore

The steadily growing market of portable electronic devices has significantly promoted the development of rechargeable lithium ion batteries (LIBs). To fabricate rechargeable LIBs with high capacity and cycling stability, it is required to well design the electrode structures. In this regard, nanotechnology provides the possibility. Reducing the electrode materials to nanoscaled can improve the charge transfer kinetics and increase the fracture strength compared to the bulk counterparts. However, the dimension of electrode materials has significant influence on the improvement that afforded by nanosizing the electrode materials. In the present work, we synthesized tin oxide-based one dimensional (1D), two dimensional (2D) and three dimensional (3D) nanostructured electrode materials by using carbon nanotubes graphene and 3D ordered porous carbon as the electrode framework. Based on morphology characterization and electrochemical measurements, the 3D porous carbon/SnO2 electrode materials exhibit the highest rate capability and very good cycling stability because 3D continuous transport pathway in the 3D porous electrode allows fast ion and electron transport without constrained ambipolar diffusion in any dimension that is impossible in the 1D and 2D electrodes.

FC-1:L27  The Electrochemical Performances of Li-Oxygen Batteries Based on LiTFSI-Tetraglyme Electrolyte and Unmodified or Au-containing Carbon Cathodes
M. MARINARO, U. RIEK, S. THEIL, L. JÖRISSEN, M. WOHLFAHRT-MEHRENS, Zentrum für Sonnenenergie- und Wasserstoff-Forschung, Baden-Württemberg, Ulm, Germany

Aprotic rechargeable Li­-O2 batteries are considered promising candidates for powering next generations of electrical vehicles. Although the theoretical energy density of Li­-O2 batteries is much higher than that of Li-­ion batteries, many fundamentals and practical issues hinder the development of such technology of batteries.
One of the main challenges is represented by the choice of a suitable electrolyte that allows the formation/dissolution of the desired products (LiO2, Li2O2) during the operation of a typical Li-O2 battery.
Another concern is the sluggish kinetics of the oxygen cathode in aprotic environments. As a consequence, the oxygen reduction (ORR) and oxygen evolution reactions (OER) suffer of high overpotentials ultimately leading to poor rate capability of the aprotic Li-O2 cells.
Trying to overcome the abovementioned issues, we will report during the meeting the latest results obtained from Li-O2 batteries based on LiTFSI-Tetraglyme electrolyte and unmodified or Au-containing carbon cathodes.

FC-1:L28  Mussel-inspired Catechol Batteries
EUN-OK HONG, HAESHIN LEE, Department of Chemistry, KAIST, Daejeon, Republic of Korea

The primary problem of Si anode is due to the dramatic volume expansion and contraction during the Li alloying-dealloying processes, resulting in rapid anode degradation. In this presentation, we synthesized a new catecholic polymer called alginate-catechol (Alg-C) and poly(acrylic acid)-catechol (PAA-C) for mechanical reinforcement of the anode materials (Adv. Mater. 2013, 25, 1571). Catechol is a well-known adhesive chemical moiety found in marine mussels, which plays an important role in interfacial adhesion between the Si nanoparticles. Conjugation of mussel-inspired catechol groups to alginate and PAA backbones results in materials suitable as Si anode binders. The unique wet-resistant adhesion provided by the catechol groups allows the Si nanoparticle electrodes to maintain their structure throughout the repeated volume expansion and shrinkage during lithiation cycling, thus facilitating substantially improved specific capacities and cycle lives. Also, this presentation will shortly discuss about catechol coating on separator membranes to improve power of Li-ion batteries (Adv. Mater. 2011, 27, 3066/ Chem. Mater. 2012, 24, 3481).

FC-1:L28b  Amorphous Silicon Nanoparticles Synthesized by Inductive Coupled Plasma for Secondary Lithium-ion Battery
BOYUN JANG, JOONSOO KIM, JINSOEK LEE, Korean Institute of Energy Research, Deajeon, Korea

Amorphous Silicon (Si) nanoparticles were synthesized by inductive coupled plasma, and their microstructures and electrochemical properties were investigated. As an active material in anode, Si is known to have high theoretical specific capacity of Lithium (Li), which is 4200 mAh/g. The dramatic volumetric change during the Li-insertion and extraction, however, limits its application because this volumetric change results in fracture of anode and failure of battery, eventually. Therefore, there are various researches to compensate this volumetric change and nanoparticles can be one of promising candidates. Amorphous Si phase can play a role of buffer against stress and tension during charge/discharge process. Homogenesous amorphous Si nanoparticles were successively synthesized with average particle sizes of 5 ~ 8 nm when applied plasma power was lower than 100 W. HR-TEM (High resolution- transmitted electron microscopy) analysis revealed that SiOx phase surround the amorphous nanoparticles with the thickness of 1 ~ 2 nm. Conventional half-cell using these nanoparticles as an active material was fabricated and cyclic performance was measured. Even though the first dilithiation capacity was relatively lower than that of crystalline Si, the cyclic performance was enhanced.

FC-1:IL29  Sintering of Monolithic "All-Solid-State" Batteries
L. CASTRO, CEMES, Toulouse, France; A. KUBANSKA, L. TORTET, MADIREL, Marseille, France; R. BOUCHET, LEPMI, Grenoble, France; V. SEZNEC, V. VIALLET, LRCS, Amiens, France; C. JORDY, G. CAILLON, SAFT, Bordeaux, France; M. DOLLÉ, University of Montreal, QC, Canada

The principal challenges to develop bulk-type ceramic batteries are to combine high energy densities and long term stability of the solid/solid interfaces. We recently reported the interest of using the Spark Plasma Sintering (SPS) technique to sinter all inorganic monolithic Li-ion batteries having cycling characteristics approaching their liquid Li-i on counterparts while being safer and faster to be made. Such an achievement is nested in the structural quality of the electrode/electrolyte interfaces, which enable both good charge transfer and mechanical integrity upon cycling. The different steps to obtain all inorganic Li-ion batteries will be detailed starting from the materials selection to the final sintering. The development of composite electrodes, which require many functionalities like a high content in electrochemically active material (AM) to increase the energy density, a good mechanical behavior to allow the easy handling and to insure the cell lifetime and an efficient and homogeneous collecting of electrons (electronic percolator) and ions (electrolyte) in the electrode volume, will be also discussed. Finally, a general discussion on possible enhancements will be addressed.

FC-1:IL30  Novel Monolithic Lithium Cassette as Replaceable Anode/Separator for Li-Air Semi-fuel Cell - A Concept of Plug and Use Galvanic Cell
S.R.S. PRABAHARAN, School of Electronics Engineering, VIT University, Chennai Campus, India; J. KAWAMURA, N. KUWATA, Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Sendai, Japan; M.S. MICHAEL, Chemical Sciences Research Centre, SSN College of Engineering, SSN Nagar, Chennai, India

Currently, various issues pertaining to the electrode/electrolyte interfaces on both sides of anode and cathode have been considered as impediments for the development of Li/Air batteries. An important factor for achieving the high coulombic efficiency is the formation of a protective layer on the highly reactive lithium metal anode. In the present study,we have developed a proof-of-concept air and water stable monolithic electrode/solid electrolyte(Li+) lithium cassette for the first time and demonstrated its stability in aqueous electrolyte. Furthermore,we also have investigated its suitability as removable electrode for Li-air Semi-fuels or the so-called primary cell. The protected lithium anode cassette (PLAC) was fabricated using a combined proprietary PLD techniques using a Li+ solid electrolyte (Ohara Inc., Japan) plate as substrate along with a buffer layer and lithium metal.A four layer structure creates a highly air/water stable monolithic cassette-like appearance. The cassette thus fabricated was tested for its stability against aqueous media in a half cell. The voltammetric analysis of PLAC revealed the typical Li stripping/Deposition reaction in neutral Li+ aqueous medium. The details of PLAC performance as anode in Li/air primary cell will be discussed.

FC-1:L31  High-energy, High-power Lithium-sulfur Batteries
A. MANTHIRAM, YONGZHU FU, YU-SHENG SU, CHENXI ZU, SHENG-HENG CHUNG, Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX, USA 

Lithium-sulfur batteries are appealing as sulfur offers an order of magnitude higher capacity than the conventional insertion-compound cathodes. However, the commercialization of Li-S batteries has been plagued by (i) poor electrochemical utilization arising from the insulating nature of sulfur and the discharge product Li2S and (ii) poor cycle life arising from the dissolution of active material into the electrolyte as polysulfides and the consequent poisoning of the metallic lithium anode. To overcome these difficulties, this presentation will focus on the following strategies: (i) sulfur-carbon nanocomposite cathodes, (ii) novel cell configurations with a microporous carbon paper interlayer between the cathode and the separator, (iii) carbon-dissolved polysulfide cathodes, and (iv) in situ formed Li2S-carbon cathodes. The cells with self-weaving sulfur-MWCNT cathodes or cells with the carbon paper interlayer offer high capacity at high rates with long cycle life. The self-weaving character of the sulfur-MWCNT cathodes offer the advantages of potentially eliminating the toxic NMP solvent and metal current collectors. The carbon interlayer offers the advantages of trapping the mobile polysulfide ions and acting as a pseudo-upper current collector, resulting in superior cell performance.

FC-1:IL33  Supercapattery: Electrochemical Energy Storage beyond Battery and Supercapacitor
G.Z. CHEN, Department of Chemical and Environmental Engineering, and Energy and Sustainability Research Division, Faculty of Engineering, University of Nottingham, Nottingham, UK 

In electricity grid, intermittency comes challenge from not only the user ends, but also the generation sites because of the increasing incorporation of renewables, calling for efficient, durable and affordable storage technologies. The supercapattery as described in this presentation is a recently demonstrated electrochemical energy storage device that combines, and can potentially exceed, the advantages of rechargeable batteries (high energy storage capacity) and supercapacitors (high charge-discharge speed or power). In this presentation, examples are provided to demonstrate the principle, practice and prospect of supercapattery. Particularly, with reference to the author's own research, the performance of supercapattery is correlated to the nanostructured electrode materials (hybrid materials of carbon nanotubes with electronically conducting polymer or transition metal oxides), and device engineering.
(The author thanks the E.ON International Research Initiative (2007-) and the EPSRC (2002-2006) for financial support, and all past and present co-workers, whose names appear in the list of references, for valuable contributions. Responsibility for the content of this publication lies with the author.)

FC-1:L34  A New Fabrication Route for High-quality Crystal Layers of Li4Ti5O12 directly on a Current Collector as well as their All-solid-state Lithium Ion Battery Properties
N. ZETTSU1, 2, H. KOJIMA1, S. NOZAKI1, K. TESHIMA1, 2, 1Shinshu University, Nagano, Japan; 2CREST, Japan Society and Technological Agency

Spinel type Li4Ti5O12 has been identified as an attractive candidate for negative-electrode material of LIB due to its brilliant intercalation-deintercalation reversibility of lithium ions. Because energy density is dependent on the filling amount of active material, we focus on Li4Ti5O12 crystal layer fabrication directly on the current collector by flux-coating method to satisfy above all requirement. The crystal layer of idiomorphic Li4Ti5O12 crystal with well-developed facets was successfully fabricated on the substrates. The Li4Ti5O12 crystal electrodes showed good electrochemical performances without need for an assistant of any additives. This bottom-up growth approach allowed for the formation of well-defined interfaces that between the Li4Ti5O12 crystals and the current collector and those between neighboring Li4Ti5O12 crystals. We believe these well-defined interfaces seem to act as effective charge transportation pathways. We further demonstrated the interface bonding between Li4Ti5O12 (LTO) crystal layer and garnet-type Li7La3Zr2O12 crystal layer by using hot-press technique, and studied their all-solid-state LIB properties.

Session FC-2 - Supercapacitors

FC-2:IL01  Layered Oxides for Pseudocapacitive Energy Storage
X. PETRISSANS, D. GIAUME, P. BARBOUX, Institut de Recherche de Chimie Paris-CNRS UMR7574, Paris, France

Cobalt and vanadium layered oxides have been studied for applications in electrochemical capacitors.
First, a study on composite electrodes formulation was made to maximize the electrochemical performances at at high charge/discharge rates. It appears that carbon percolation and application of a controlled pressure drastically increase the electrode conductivity without collapsing the pore structure.
Nanometric cobalt oxides were synthesized by direct precipitation in alkaline and oxidizing medium has been proposed. The hydrated sodium phase exhibits very good electrochemical properties at high rate in sodium aqueous electrolyte but this phase is metastable towards ionic exchange. Still, the dried phases show a good pseudo-capacitive behavior in either lithium or sodium aqueous electrolytes.
Last, nano-ribbons of vanadium oxide were made thanks to a well known aqueous sol-gel synthesis. These particles were modified by substitution with alkaline ions thanks to a simple ionic exchange or through reduction with iodides, thus forming lamellar bronzes. Because of their good ionic and electronic conductivities the vanadium bronzes show the best electrochemical performances at high charge/discharge rates in either lithium or sodium organic electrolytes.

FC-2:IL03  Electrolytes for Higher Performance Carbon-Based Supercapacitors
HSI-SHENG TENG, H.C. HUANG, M.F. HSUEH, Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan

Electric double layer capacitors (EDLCs) mainly use aqueous and organic liquid electrolytes (LEs). Replacing LEs with gel polymer electrolytes (GPEs) and ionic liquids (ILs) would improve EDLC safety by solving electrolyte leakage and corrosion problems. We used carbons with different pore structures to assess the compatibility of GPEs and ILs with carbon electrodes for high-performance EDLCs.
This work demonstrated that a GPE based on a linear triblock copolymer, PAN-b-PEG-b-PAN, showed superior adjustable mechanical integrity, making the roll-to-roll assembly of GPE-based EDLCs scalable to industrial levels. We found that the PAN chain promotes ion solvation and transport into the carbon interior, and the PEG chain coordinates the solvent molecules to form ion motion channels. The synergistic effect of the PAN and PEG blocks significantly enhanced the performance of the resulting EDLCs.
We used two ILs, EMIm TFSI and MPPy TFSI to assemble EDLCs for high-voltage operation. A hierarchical pore configuration, which allows sequential penetration of ions during the progress of charging, is beneficial for effective energy storage in a wide voltage range. The presence of micropores sustained the stability of carbon electrodes operated at high voltages.

FC-2:L05  Effect of Cation on Diffusion Coefficient of Ionic Liquids at Onion-like Carbon Electrodes
K. VAN AKEN1, J.K. MCDONOUGH1, SONG LI2, GUANG FENG2, S.M. CHATHOTH3, 5, E. MAMONTOV3, P.F. FULVIO4, P.T. CUMMINGS2, SHENG DAI4, Y. GOGOTSI1, 1Department of Materials Science and Engineering & A.J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, PA, USA; 2Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, TN, USA; 3Chemical and Engineering Materials Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN, USA; 4Chemical Science Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA; 5Department of Physics and Materials Science, City University of Hong Kong, Hong Kong, China

While most supercapacitors are limited in their performance by the electrolyte stability, using neat ionic liquids (ILs) can expand the voltage window and temperature range of operation. Three different techniques were used to investigate the characteristics of three ILs in a comprehensive approach for a new field of electrolytes. Exohedral onion-like carbon (OLC) was chosen as the electrode material, allowing the behavior of ILs to be investigated without the influence of the carbon structure. In this study, ILs with bis(trifluoromethylsulfonyl)imide as anion were investigated as the electrolyte in OLC-based electrochemical capacitors. To probe the effect of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests were performed. Diffusion coefficients were measured using electrochemical impedance spectroscopy and correlated with quasielastic neutron scattering and molecular dynamics simulation. The IL with the smaller sized cation had a larger diffusion coefficient, leading to higher capacitance at faster cycling rates. Electrolyte performance was also correlated with increasing temperature.

FC-2:IL07  Modeling Ion Adsorption and Dynamics in Nanoporous Carbon Electrodes
C. PÉAN1, 2, 3, C. MERLET1, 2, B. ROTENBERG1, 2, P. SIMON2, 3M. SALANNE1, 2, 1PHENIX laboratory, Université Pierre et Marie Curie, Paris, France; 2French Research Network on Electrochemical Energy Storage (RS2E), FR CNRS 3459, France; 3CIRIMAT Laboratory, Université Paul Sabatier, Toulouse, France

The recent demonstration that in supercapacitors ions from the electrolyte could enter sub-nanometer pores increasing greatly the capacitance opened the way for valuable improvements of the devices performances. Despite the recent experimental and fundamental studies on that subject, the molecular mechanism at the origin of this capacitance enhancement is still not quite clear. We report here molecular dynamics simulations including two key features: the use of realistic electrode structures comparable with carbide-derived carbons and the polarization of the electrode atoms by the electrolyte. This original design of an electrochemical cell allows us to recover capacitance values in quantitative agreement with experiment and to gain knowledge about the local structure and dynamics of the ionic liquid inside the pores. Then, from the comparison between planar (graphite) and porous electrodes, we propose a new mechanism explaining the capacitance enhancement in nanoporous carbons.
- Merlet, Rotenberg, Madden, Taberna, Simon, Gogotsi and Salanne, Nature Mater., 11, 306 (2012)
- Merlet, Pean, Rotenberg, Madden, Simon and Salanne, J. Phys. Chem. Lett, 4, 264 (2013)

FC-2:IL08  Synthesis and Electrochemical Properties of Graphene-based Composites for Supercapacitors
SANG-HOON PARK, CHANG WOOK LEE, HEE CHANG YOUN, HYUN-KYUNG KIM, SEOK WOO LEE, KWANG-BUM KIM, Laboratory of Energy Conversion and Storage Materials, Department of Material Science and Engineering, Yonsei University, Seoul, Korea

Synthesis of nanostructured materials with well-defined morphology is important to ensure their property performance in various device applications. Electrochemical capacitor (EC) is a high power energy storage device with long cycle life as compared to secondary batteries and fuel cells.
Recently, graphene has been significantly explored as an electrode material for electrochemical energy storage devices owing to its unique properties. One obvious challenge would be to utilize the 2D carbon nanostructure with regard to its large specific surface area and edge sites for the potential application in energy storage devices.
At the same time, metal oxide/graphene nanocomposites are also of considerable interest for EC applications owing to their outstanding properties. These excellent properties of metal oxide/graphene nanocomposites are generated from synergistic combination of graphene with metal oxide on the nanometer scale. Therefore metal oxide/graphene nanocomposites should be synthesized in a way that metal oxide forms only on the surface of graphene on the nanometer scale to improve both high power and high energy properties for ECs applications.
In this study, we report on the synthesis and electrochemical characterization of graphene and metal oxide/graphene nanocomposite.

FC-2:IL09  Improving the Energy Density of Electrochemical Capacitors: From Pseudocapative Electrodes to Hybrid Devices
T. BROUSSE, Institut des Matériaux Jean Rouxel, IMN, UMR-CNRS 6502, Université de Nantes, Réseau RS2E France, Polytech Nantes, Nantes Cedex, France

Electrochemical capacitors (ECs), so-called supercapacitors are energy storage device that combine a high power density with long cycle life. Their main drawback is their moderate energy density that usually hardly exceeds 5 Wh/kg. This limitation becomes even worse when reported as volumetric energy density, a critical parameter in many applications. Despite their low density, the use of carbon based electrode enables to operate the device with organic based electrolytes that enhance the cell voltage up to 2.7V. The optimization of the cell capacitance C using carbon electrodes is a dilemma since high porosity is required to enhance electrode/electrolyte interaction but an increase in porosity often translates in a decrease in the density of carbon electrodes. The use of oxide or nitride based pseudocapacitive materials as electrodes also leads to a dilemma since the cell capacitance is usually enhanced but at the expense of the cell voltage, since most of these alternative electrodes can only be operated in aqueous electrolytes. Subsequently, a tradeoff is often needed in order to balance cell voltage and cell capacitance. This communication will detail some strategies to optimize energy density of ECs.

FC-2:IL10  Economic and Ecological Life Cycle Assessment of New Materials for Supercapacitors and Batteries
M. WEIL1, 2, H. DURA1, M. BAUMANN1, B. ZIMMERMANN1, B. SIMON2, S. ZIEMANN1, G.R. GARCIA2, 1Institute for Technology Assessment and System Analysis (ITAS), Karlsruhe Institute of Technology (KIT), Germany; 2Helmholtz Institute Ulm for Electrochemical Energy Storage (HIU), Karlsruhe Institute of Technology (KIT), Germany

At present lithium based electrochemical storage systems are preferentially used in electric vehicles (full electric vehicles and hybrids). Supercapacitors are considered as alternative energy storage systems in electric vehicles, which are already tested in busses and trams. In comparison to lithium batteries supercapacitors possess practically infinite cycle stability, a high specific power, but unfortunately a relatively low specific energy density. Thus the goal of ongoing research is to develop a new generation of supercapacitors with high specific power and high specific energy. To reach this goal particularly high performance nano materials are developed and tested on cell level. In the presented study the environmental impact (regarding known environmental effects) of the production of supercapacitor cells is investigated by ecological Life Cycle Assessment (LCA). In addition a Life Cycle Costing (LCC) analysis is conducted. Special attention is paid on carboniferous nano materials and the effects of efficiency gains of nano particle production due to scaling up of such processes from laboratory to industrial production scale.

FC-2:L12  Hybrids of 2D-nanomaterials for Supercapacitors/Battery Applications
B. MENDOZA SANCHEZ, J. COELHO, S. O’BRIEN, H. PETTERSSON, V. NICOLOSI, CRANN, Trinity College Dublin, Dublin, Republic of Ireland

Supercapacitors and batteries are energy storage systems, the former offering a high power density and a high degree of cyclability, and the latter being mainly a high energy density device.  Batteries and supercapacitors store energy electrochemically by interaction of an electrode material and an electrolyte. The energy stored is proportional to the surface area of the electrochemically active material and therefore high surface area 2D-nanomaterials are suitable for this application. In this work, we present the manufacture of thin-film supercapacitor/battery electrodes using cost-effective and scalable methods: solvent-exfoliation followed by spray deposition.  A variety of 2D-nanomaterials that can be grouped in two categories, carbon-based and metal oxides, were synthesized, characterized and evaluated. A combination of a carbon-based material and a metal oxide gives place to “hybrid” materials that showed improved performance.
Poster Presentations

FC:P01  Production of Electrolyte Membranes for Sodium-beta Alumina Batteries

The increasing boost towards renewable energy and sustainable mobility have grown the research interest in sodium-beta alumina batteries owing to their high theoretical energy density, high round trip efficiency and good cycle life. These electrochemical devices store electrical energy via sodium ion transport across a β''-Al2O3 solid electrolyte at relative high temperatures (250-350°C). The ceramic membrane acts simultaneously as both the electrolyte and the separator between the anode, molten metallic sodium, and the cathode, molten-sulfur (Na-S battery) or metal halide plus NaAlCl4 (ZEBRA battery). The ceramic electrolyte is a component of crucial importance for sodium-beta alumina batteries. The process needed to produce the electrolytic compartment has a key role to enhance and adapt the batteries performances to the specific requirements for stationary regime applications. Each minimal composition or process deviation strongly influences the final properties of the device. In this work, β"-alumina membranes were produced by die pressing and tape casting. Each process was carefully optimized in order to obtain electrolytic membranes with suitable characteristics. The critical issues and advantages linked to the two shaping processes were underlined and compared.

FC:P02  Electrochemical Deposition of Ir Catalyst on Carbon Fiber for the Vanadium Air Redox Flow Battery
T. DI NARDO, C. NUNES KIRCHNER, J. GROßE AUSTING, O. OSTERS, L. KOMSIYSKA, NEXT ENERGY . EWE Research Centre for Energy Technology at the University of Oldenburg, Oldenburg, Germany

Vanadium redox flow battery (VRFB) is a promising technology for energy storage of renewable energy sources. However, its actual energy density of about 20 Wh kg-1 can be nearly doubled if the positive half-cell reaction V4+/5+ is replaced by the oxygen evolution (OER)/ oxygen reduction reaction (ORR) resulting in the so called vanadium air redox flow battery (VARFB).[1] However, the presence of catalysts at the positive electrode is crucial for the operation of the VARFB. Electrochemical deposition methods are powerful techniques for controlled modification of relatively inert surfaces such as carbon due to its high selectivity, low operation temperature and low costs.
In this approach Ir-catalyst for the OER was electrochemically deposited on carbon fibers by using different electrochemical techniques. The Ir-electrodeposition occurs at high overvoltages following 3D Volmer-Weber growth mode and is accompanied by hydrogen evolution reaction. After deposition, the Ir-modified fibers were analyzed by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Based on such approach, VARFB positive electrodes were prepared and the performance of battery was investigated.
[1] S. S. Hosseiny et al. Electrochem. Comm. 2011, 13(8), 751.

FC:P03  Synthesis and Properties of LiFePO4/C Cathode Materials prepared from Iron Phosphate Modified by V2O5
MOBINUL ISLAM2, MAN-SOON YOON1, SOON-CHUL UR1, 1Department of Materials Science and Engineering/Research Center for Sustainable Eco-Devices and Materials (ReSEM), Korea National University of Transportation, Chungju, Chungbuk, Republic of Korea; 2Green City Technology Institute, Korea Institute of Science and Technology (KIST), Seoul, Republic of Korea

LiFePO4/C composites are prepared from amorphous FePO4.xH2O and modified by V2O5 by a solid state reaction process. Phase information and morphology of the produced powders have been characterized by XRD and SEM. Effect of V2O5 addition on the carbon coating structure was also characterized using a Raman spectroscopy. Electrochemical performances were evaluated by impedance measurements and galvanostatic charge/discharge tests. V2O5 was shown to manipulate the disordered/graphitized carbon ratio of coated carbon which is related to electrical conductivity of material. The results indicate that surface modification by metal oxide could be an alternative way to improve the comprehensive properties of the cathode materials for lithium ion batteries.

FC:P04  Detecting Aging Phenomena in Electrochemical Storage Devices using High Resolution Computed Tomography
L. KOMSIYSKA, M. LEWERENZ, S. GARNICA, D. LEDWOCH, H. SEEBA, O. OSTERS, NEXT ENERGY . EWE Research Centre for Energy Technology at the University of Oldenburg, Oldenburg, Germany

The morphology of different components within electrochemical energy conversion and storage devices, such as batteries and fuel cells, is one of the key characteristics concerning performance and lifetime. Bearing in mind that generally single components such as electrodes are complex, porous materials, consisting of various compartments, knowledge not only about the surface topography but also the morphology in depth is crucial. High resolution computed tomography (CT) combines a 3D image of the samples and the spatial distribution of quantitative analysis with the resolution of few hundreds of nanometers.
Using this technique the change of the morphometric parameters of electrodes for lithium ion batteries with aging has been examined. Commercially available 2 Ah Li-ion cells were continuously cycled to different state of health (SOH). The electrodes were subsequently analyzed using CT with voxel size of about 400 nm. For a quantitative analysis binarized images were subsequently evaluated to determine quantities like the statistic structure size distribution, porosity, homogeneity and preferential orientation of the sample structure. Using this technique a decrease in the average particle size and an increase in number of particles of LiCoO2 at lower SOH could be observed.

FC:P05  Effect of Process Parameters on the Silicon Nanoparticles Synthesized by Inductive Coupled Plasma
JOON-SOO KIM, BO-YUN JANG, JIN-SEOK LEE, Korea Institute of Energy Research, Daejeon, Korea

To use the anode material for Lithium Ion battery, silicon nanoparticles were synthesized by passing monosilane through the quartz tube wrapped with Inductive Coupled plasma (ICP) coil. Silicon nanoparticles synthesis equipment by Inductive Couple Plasma consisted of gas injection, plasma reaction, cooling and gathering parts. To synthesize the silicon nanoparticles, we have analysed the process conditions such as partial pressure of monosilane, the plasma power, working pressure and Ar flow rate. Properties of silicon nanoparticles were changed by the process conditions such as partial pressure of monosilane, the plasma power, working pressure and Ar flow rate. Partial pressure of monosilane and plasma power determined not only particle size but also crystallinity of nanoparticles. As working pressure increased, the amount of produced nanoparticles linearly increased but working pressure did not determined the particle size. As the amount of Ar, carrier gas, increased, the size was slightly increased. Controlling those parameters, we achieved crystalline and amorphous silicon nanoparticles.

FC:P06  Synthesis and Behaviour of Conductive Polymer-V2O5 based Core Shell Particles for Application as Cathode Material in Lithium Ion Batteries
L. KOMSIYSKA, D. LEDWOCH, E. HAMMER, K. REINKEN, O. OSTERS, NEXT ENERGY . EWE Research Centre for Energy Technology at the University of Oldenburg, Oldenburg, Germany

V2O5 based oxide is a promising compound as cathode material for Li-ion batteries, due to its beneficial properties such as high theoretical capacity (430 mAhg-1), wide voltage range and low costs.[1] However the main drawbacks are the intrinsically low conductivity of 10-3 Scm-1 and the slow lithium intercalation kinetics.[2] Several studies report that via coating the active material particles surface by a conducting polymer can improve the overall battery performance.[3,4] Herein the hydrothermal synthesis and the behavior of V2O5 based core shell particles using different conducting polymers like Polyaniline, Polyanisidine and Polyethoxythiophene is shown.
Synthesis was carried out under hydrothermal conditions at a temperature of 120 °C and a pH value of 3, using the appropriate monomers and ball-milled, commercially available V2O5. The products where characterized by x-ray powder diffraction, scanning electron microscopy and FTIR spectroscopy. The electrochemical performance and stability was analyzed in a 3 electrode assembly using Li as counter and as working electrode.
[1] A.-M. Cao et al. Angew. Chem. Int. Ed. 2005, 44, 4391.
[2] J. Livage Chem. Mater. 1991, 3, 578.
[3] A. Fedorkova et. al. Electrochim. Acta 2010, 55, 943.
[4] C. Wu et al. J.Power Sources 2013, 231, 44.

FC:P07  A Study on the Electrochemical Properties for Idiomorphic Crystals of Spinel-type Li+-conductive Oxides
S. KOMINE1, Y. SATO1, S. SUZUKI1, K. KAMI1, N. ZETTSU2, 3, K. TESHIMA2, 3, 1DENSO CORPORATION, Agui-cho, Chita-gun, Aichi, Japan; 2Shinshu University, Nagano, Japan; 3CREST, Japan Society and Technological Agency

Spinel type Li-ion conductive oxides have been identified as attractive candidates for positive-electrode materials of lithium ion batteries (LIBs) due to their brilliant intercalation-deintercalation reversibility of lithium ions with small volume change. Currently. Teshima et al demonstrated growth of idiomorphic crystals of spinel-type manganese oxides by flux method as well as characterization of their electrochemical properties. Battery testing showed that the flux-grown crystals have a high charge storage capacity at high power operation, which is better than commercially available powders.
In this study, we systematically performed micro-structured analysis of the spinel-type crystals coupled with their electrochemical properties in order to gain a deeper understanding of how the flux growth condition affects to its crystal properties and electrochemical properties.
We assembled coin-type cell (CR2032) in order to study the electrochemical properties of the spinel-type crystals as cathode active materials for LIBs. We found their electrochemical properties were strongly dependent on both macroscopic and microscopic differences in their crystallographic characteristics.

FC:P13  Electrochemical Performance of Magnetic Nanoparticles Encapsulated in Hollow Carbon Nanofibers
M.C. GIMENEZ-LOPEZ, C. HERREROS LUCAS, A.N. KHLOBYSTOV, School of Chemistry, Nottingham University, University Park Nottingham, UK

We have developed an effective methodology for the integration of preformed magnetic nanoparticles (NPs) into the internal cavity of carbon nanofibers (NFs), yielding to different hybrid nanostructures exhibiting different magnetic and electrochemical behaviors. The arrangement of NPs is precisely controlled by the internal structure of the host NF. Non-covalent interactions, which are responsible for the efficient encapsulation of guest-NPs into NFs, in principle could allow NPs to stay mobile within the NFs and reversibly align along an applied magnetic field. This new class of hybrid nanomaterial has enable the development of supercapacitors and facilitate harnessing of the synergistic effects of carbon host-nanofibers combined with the magnetic properties of guest-NP, which are important for the emerging area of spintronic devices. The encapsulation of magnetic NPs into NFs described in this study opens up a number of exciting opportunities for applications requiring the precise control of position and orientation of guest-NPs, for example, nano- electronics and nanocatalysis.

FC:P14  Direct Growth of Polyaniline Chains from Nitrogen Site of N-doped Carbon Nanotubes for High Performance Supercapacitor
JOONWON LIM, HAQ UL ATTA, SANG OUK KIM, Korea Advanced Institute of Science and Technology, Daejeon, South Korea

Polymer grafting from graphitic carbon materials has been pursued for several decades. Unfortunately, currently available methods mostly rely on the harsh chemical treatment of graphitic carbons which causes severe degradation of chemical structure and material properties. A straightforward growth of polyaniline chain from the nitrogen (N)-doped sites of carbon nanotubes (CNTs) is presented. N-doping sites along the CNT wall nucleate the polymerization of aniline, which generates seamless hybrids consisting of polyaniline directly grafted onto the CNT walls. The resultant materials exhibit excellent synergistic electrochemical performance, and can be employed for charge collectors of supercapacitors. This approach introduces an efficient route to hybrid systems consisting of conducting polymers directly grafted from graphitic dopant sites.

FC:P16  V2O5 Nanostrips Grown over Graphene Oxide for High Performance Electrochemical Capacitor
V. SAHU, S. GROVER, G. SINGH, R. KISHORE, Sharma University of Delhi, Department of Chemistry, Delhi, India

Supercapacitors are under extensive research as an auxiliary energy supplement when used with rechargeable batteries. Having the favorable properties of capacitor as well as rechargeable batteries, it stores high energy and delivers high power in a short span of time. Depending upon the mechanism of charge storage, supercapacitor can be divided into two categories: electrical double layer capacitor (EDLC) and redox/faradic capacitor. Various forms of carbon like activated carbon, carbon nanotube, graphene etc. are used as EDLC materials whereas metal oxide and conducting polymer are served as redox material. We have synthesized a vanadium oxide (V2O5) strips with sharp edges grown over Graphene oxide (GO) for electrochemical capacitor electrode material. Among various transitions metal oxide V2O5 shows variable oxidation states (V-II) which further results in wide potential window. The reasons for using GO as a substrate for V2O5 growth are: it acts as a conducting filler, reduce dissolution of V2O5, enhances cycling life and electrolyte accessible area. The V2O5/GO composite shows high specific capacitance (525 F/g) in comparison to bare V2O5 (105 F/g). Galvanostatic charge-discharge also improved significantly with very low IR drop and nearly equal charge-discharge time.

FC:P17  Ruthenium Oxide Nanoplates and Their High Performance in Lithium Ion Batteries
A. NAVULLA, G. STEVENS, L. MEDA, Department of Chemistry, Xavier University of Louisiana, New Orleans, LA, USA

Synthesis and understanding of materials with improved properties are critical in the development of high capacity electrochemical cells for application in lithium ion batteries. Nanostructured materials, specially 2D nanoplates, have shown exceptional storage capability. We have prepared nanostructured columnar self-assembled ruthenium oxide (RuO2) nanoplates directly on stainless steel current collectors using low pressure chemical vapor deposition (LPCVD). The as-prepared materials were examined by powder X-ray diffraction and indexed to the standard rutile crystal structure. Nanoplates ranging from 50 to 80 nm were self-assembled into columns as high as 230 nm thick as seen under field-emission scanning electron microscope. Galvanostatic charge-discharge experiments versus Li/Li+ in the range of 4 to 0.1 V have demonstrated that these nanoplates are reversible at extremely high capacity (~1150 mAh g-1, 5.70Li per mol of RuO2). The capacity retention was 100% from the first to second cycle and 87% after 25 cycles. In addition, we will discuss The synthesis of 2D alpha-Fe2O3 and cubic-MnO nanoplates by LPCVD and their electrochemical properties. The excellent capacity retention of these materials is attributed to the growth process and their unique nanostructure.

Cimtec 2014

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