AABC 2012. LLIBTA Symposium: Large Lithium Ion Battery Technology and Application – Session 1

In this session, we will review the latest advances in Lithium-Ion battery materials intended mostly for automotive and other large-battery applications, including cathodes, anodes, electrolytes, separators and non-active components that promise to support enhanced life or safety, or offer better performance-to-cost ratios.

Prof. Winter's main research interests are in applied electrochemistry, materials electrochemistry and inorganic chemistry and technology. He is the past president of the International Battery Materials Association (IBA), Past Chair of the Division of Electrochemical Energy Storage and Conversion of International Society of Electrochemistry (ISE), and Technical  Editor of the Journal of The Electrochemical Society (ECS). Currently, he is the spokesperson of the LIB2015 Innovation Alliance of the BMBF (Germany Ministry of Education and Research) and a member of the German National Platform E-Mobility (NPE).

1. Advances in Olivine Cathode Materials for Large Lithium-Ion Batteries
   Guoxian Liang, R&D Director, Phostech Lithium, Inc.
   Abstract 

   

   Since the introduction of olivine type lithium metal phosphate cathode materials in 1997 for lithium ion batteries, significant progresses have been made in understanding this chemistry system and in manufacturing lithium metal phosphate materials and batteries. Interest is growing rapidly in using lithium metal phosphate for batteries in energy storage batteries and electric mobility applications. Lithium metal phosphate has very low intrinsic electronic and ionic conductivities, carbon coating on nanao sized particles has been a successful strategy in commercial manufacturing of high performance product to mitigate the low intrinsic conductivity. Therefore, carbon coating, particles size and morphology of primary and secondary particles have great impact on product performance and process-ability. Many different manufacturing processes such as solid state reaction, hydrothermal and sol-gel process have been explored for producing lithium iron phosphate. Each process has its advantages and disadvantages in controlling the material purity, crystal structure, particle size/agglomerate and carbon coating. Sud-Chemie and its subsidiary, Phostech Lithium, continue to develop several synthesis processes to fulfill needs of present & future customers and markets. In this paper, Phostech/Sud-Chemie will present recent development on various products and their applications:

   • PA30, a new advanced Life Power® grade, produced by a solid state reaction,
   • P2 grade, production in Candiac plant, Canada
   • LiMnxFe1-xPO4 high voltage materials

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2. Advances in Materials towards the Realization of Lithium-Ion Cells with Higher Energy Density
   Sujeet Kumar, President & CTO, Envia Systems
   Abstract 

   

   The overwhelming need for low cost and light weight energy storage systems for transportation requires the development of radically new active materials for lithium ion batteries. Envia has developed High Capacity Manganese Rich (HCMR™) cathode with discharge capacity as high as 300 mAh/gm. Envia has manufactured large format cells with specific energy of 240 Wh/kg using this proprietary HCMR™ cathode paired with a graphite anode. Envia has developed a nano-structured silicon-carbon composite anode that exhibits capacity of 1600 mAh/gm. When this anode is paired with HCMR™ cathode, the energy density of the cell improves considerably. By packaging more energy in each cell, amount of active material and the number of cells required for electric drive vehicle applications decreases substantially making widespread adoption of EDVs possible. In this presentation, performance of Envia's high capacity cathode and anode will be examined in large format cells. 

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3. High Performance Overlithiated Layer Oxide (OLO) Cathode Battery
   Hironari Takase, Senior Researcher, Samsung Yokohama Research Institute
   Abstract 

   

   High-voltage cycling performance at elevated temperature of Li-ion battery based on Li-rich layered oxide cathode material, i.e., Li₂MnO₃-LiMO₂ (M=Co, Ni, and Mn. >250mAh/g), was dramatically improved by applying newly-developed electrolyte system with fluorinated ether and fluorinated carbonate solvent. The Li₂MnO₃-LiMO₂ / Graphite cell using the modified electrolyte exhibits over 200mAh/g-cathode even after 200 cycles at 45 °C, under operation voltage range of 4.65 - 2.0V at 1C-charge / 1C-discharge rate (Capacity retention; 87%@200cycle).
   Additionally, less swelling property and its mechanism of the OLO-cathode/Graphite cell will be also discussed at this presentation.

   Fig.1 Comparative cathode energy density at each charging voltage		Fig.2 Cell swelling reduction at 1st charging (4.6V) by new cathode synthetic method-2
   Fig.3 1C/1C cycle performance at 45 °C of OLO/graphite cell

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4. Advances in Electrolytes for Lithium Ion Batteries: A Mechanistic Understanding
   Brett Lucht, Associate Professor, University of Rhode Island
   Abstract 

   

   There is significant interest in the development of higher energy lithium ion batteries (LIB) for electric vehicles. One method of improving the energy density of lithium ion batteries is to increase the operating voltage of the cells by increasing the working potentials of positive electrode employing for example lithium nickel manganese spinel LiNi_0.5Mn_1.5O₄ or layered mixed metal oxide Li₂MnO₃-LiMO₂ as the active material. However, cycling of lithium-ion cells to high voltages (~5.0 V vs lithium reference electrode, LRE) proceeds with relatively low (99% and less) coulombic efficiency. Among the primary contributors to the poor cycling efficiency are the electrochemical oxidation reactions of the electrolytes at the high positive potentials of positive electrode. We have been conducting a two part investigation of electrolytes for high voltage LiNi_0.5Mn_1.5O₄ and Li₂MnO₃-LiMO₂ cathodes. First, we have been studying the reaction of standard electrolyte (LiPF₆ in EC/EMC) with the surface of the LiNi_0.5Mn_1.5O₄ and Li₂MnO₃-LiMO₂ particles. Second, we have been developing novel additives designed to sacrificially react on the surface of LNMS cathode materials to generate a passivation layer which inhibits further electrolyte oxidation. Our investigation of the reactions of electrolyte with the surface of LiNi_0.5Mn_1.5O₄ cathode materials include electrodes cycled to 4.9 V vs Li, cycled under accelerated aging conditions, and cathode particles stored at elevated temperature (85 °C) in the presence of electrolytes. This will allow us to develop a better understanding of the detrimental electrochemical and thermal reactions of the electrolyte with the cathode surface. Two classes of additives, inorganic and organic, have been investigated which are preferentially oxidized to form a cathode SEI which inhibits the oxidative reactions of the cathode with the electrolyte the cathode particles. Incorporation of the additives has an effect on the capacity retention of the cells when cycled to 4.9 V especially under accelerated aging and improves the cycling efficiency. After cycling and storage experiments an ex-situ analysis of the electrodes or cathode particles was conducted via a combination of SEM, XPS, and FT-IR spectroscopy to determine the relationship between the cathode surface films and of performance differences for different electrolytes. Acknowledgements
   We thank the Batteries for Advanced Transportation Technologies (BATT) Program supported by the U.S. Department of Energy Office of Vehicles Technologies, DOE EPSCoR, and BASF for funding.

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5. Lithium/Air Battery Project
   Winfried Wilcke, Senior Manager Nanoscale Science and Technology, Almaden, IBM Research Division, IBM Group
   Abstract 

   

   The talk will give a summary of the current status and scientific results of the IBM /Battery 500 Lithium/Air battery project. Lithium/Air is a chemistry with the potential for very high specific energy density (Wh/kg). It relies on the use of oxygen (or ideally ambient air) to form a Lithium compound during discharge and the reduction of this compound to lithium metal and gaseous oxygen during recharge. The lithium compound is lithium peroxide for aprotic (non-aqueous)electrolytes and lithium hydroxide for aqueous lithium air batteries, respectively. The IBM results clearly established through laboratory experiments, electrochemical mass spectrometry and supercomputer modeling that commonly used electrolytes for a conventional lithium ion batteries are being destroyed in a lithium air battery and do not work. But several other electrolytes do show clear evidence of supporting charging and recharging, indicating that the choice of electrolytes for these batteries is very critical. The measured charge densities are very high, but the number of charge/discharge cycles is still low and a strong function of the cathode materials used. The effect of common catalysts has been studied and found to be either insubstantial or destructive - catalysts may not play a significant role in Lithium/Air technology. The conductivity properties of lithium peroxide, both in bulk and on the surface, has emerged as a key material property critical for understanding this chemistry. The talk will conclude with an enumeration of the outstanding scientific problems and give an outlook onto the next phase of the project, which will begin to add engineering aspects to the current science. The goal is the construction of a rather large Lithium/air battery in a couple of years.

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