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Henderson – NCSU V.D.6 Nonfluorinated (or Partially Fluorinated) Anions for Lithium Salts and Ionic Liquids (NCSU) 5. 5th International Conference on Polymer Batteries and Fuel Cells (ICPB-5), Argonne National Laboratory, Chicago, IL, Aug 1-5, 2011―Scrutinizing Liquid and Solid Polymer Electrolyte Solvation via Phase Diagrams and Crystalline Solvate Structures. 6. ACS/MARM-2011―New Technologies for Ion Lithium Batteries II, College Park, MD, May 23, 2011―Ionic Liquid-Based Electrolytes for Lithium Batteries: Linking Structure with Physical Properties 7. DOE Annual Merit Review & Evaluation Meeting―Hydrogen Program and Vehicle Technologies Program, Crystal City, VA, May 9 12, 2011―Inexpensive, Nonfluorinated (or Partially Fluorinated) Anions for Lithium Salts and Ionic Liquids for Lithium Battery Electrolytes. 8. Symposium on Scalable Energy Storage Beyond Li-Ion: Materials Perspectives, Oak Ridge National Laboratory, Oak Ridge, TN, Oct 7-8, 2010―Ionic Liquids, Lithium Salts, Solvents and Water: Phase Behavior and Molecular Interactions. Figure V - 159: Ion coordination in the crystal structures of (AN)3:LiDFOB and (AN)1:LiDFOB (Li-purple, O-red, N-blue, B-tan, F- green). Figure V - 160: Ion coordination in the crystal structures of (ADN):LiDFOB (Li-purple, O-red, N-blue, B-tan, F-green). FY 2011 Publications/Presentations 1. Allen. J. L.; Boyle, P. D.; Henderson, W. A. "Lithium difluoro(oxalato)borate tetramethylene sulfone disolvate" Acta Crystallogr. 2011, E67, m533. 2. Allen, J. L.; Boyle, P. D.; Henderson, W. A. "Poly[diacetonitrile[μ 3 -difluoro-(oxalato)borato] sodium" Acta Crystallogr. 2011, E67, m678. 3. Allen, J. L.; Han, S.-D.; Boyle, P. D.; Henderson, W. A. "Crystal structure and physical properties of lithium difluoro(oxalato)borate (LiDFOB or LiBF 2 Ox)" J. Power Sources 2011, 196, 9737. 4. MIT, Boston, MA, Oct 14, 2011―Molecular Insight into the Electrolyte Heart that Beats Life into Lithium Batteries—Tuning Stability, Conductivity, Crystallization…and Other Vitals. FY 2011 Annual Progress Report 615 Energy Storage R&D
V.D.7 Development of Electrolytes for Lithium-ion Batteries (URI) Brett L. Lucht (Project Manager) University of Rhode Island Department of Chemistry 51 Lower College Rd., Pastore Phone: (401) 874-5071; Fax: (401) 874-5072 E-mail: blucht@chm.uri.edu Start Date: April 1, 2009 Projected End Date: March 31, 2014 Objectives · Investigate cathode film forming additives for high voltage (> 4.5 V) cathode materials. · Investigate properties of LiPF 4 C 2 O 4 /carbonate electrolytes at low temperature after accelerated aging. · Investigate incorporation of electrolyte solid electrolyte interphase (SEI) forming additives for Sibased anodes. · Investigate the surface of cathodes and anodes cycled with novel electrolytes, with or without additives, to develop a mechanistic understanding of interface formation and degradation. Technical Barriers This project addresses the following technical barriers from the Batteries for Advanced Transportation Technologies Research, Development Plan regarding electrolytes. · Improve cell performance, life and cost · Improve calendar Life · Expand survival temperature range Technical Targets · Cell performance, life, cost: Calendar life: 40°C, 15 yrs · Survival Temp Range: -46 to +66°C · Unassisted Operating & Charging Temperature Range, -30 to + 52°C. Accomplishments · Development of cathode film forming additives that improve the performance of high voltage cathodes. · Development of a thorough understanding of the source of poor first cycle efficiency for LiPF 4 (C 2 O 4 ) electrolytes on graphite anodes. · Investigation of the low temperature performance of LiPF 4 (C 2 O 4 )/PC electrolytes after accelerated aging. · Investigation of novel electrolytes additives to improve performance of Si-based anodes. Introduction While commercial lithium-ion batteries (LIBs) perform well for most home electronic applications, currently available LIB technology does not satisfy some of the performance goals for Plug-in Hybrid Electric Vehicles (PHEV). In particular, currently available LIB technology does not meet the 15 year calendar life requirement set by the United States Advanced Battery Consortium (USABC). The most extensively used LIB electrolytes are composed of LiPF 6 dissolved in organic carbonates. However, LiPF 6 based electrolytes have poor thermal stability and performance when cycled to high voltage (> 4.5 V vs Li). Significant energy fading occurs after several years at room temperature and over only a few months at the moderately elevated survival temperature of 66°C required by the USABC. While there are several different factors that limit the thermal stability, calendar life and voltage window of LIBs, the reactions of the electrolyte with the surface of the electrode materials are frequently reported to be the most important. Approach Test cells were constructed with novel electrolyte formulations and ex situ analysis of the surfaces of cathodes and anodes was conducted to develop a mechanistic understanding of interface formation and degradation. Cathode film forming additives for high voltage (> 4.5 V) cathode materials were studied to improve cycling performance at high potential. An investigation of the properties of the thermally stable highly conductive salt, LiPF 4 C 2 O 4 , in carbonate solvents was conducted to better understand the novel salt. The electrode surface films for cells cycled with LiPF 4 (C 2 O 4 ) electrolyte were investigated to determine source of performance differences compared to LiPF 6 . Incorporation of electrolyte SEI forming additives was studied to improve the performance of Si-based Alloy anodes. Energy Storage R&D 616 FY 2011 Annual Progress Report
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V. FOCUSED FUNDAMENTAL RESEARCH Int
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V.A Introduction Duong - DOE, Srini
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V.B Cathode Development V.B.1 First
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V.B.1 First Principles Calculations
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V.B.1 First Principles Calculations
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V.B.2 Cell Analysis, High-energy De
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V.B.3 Olivines and Substituted Laye
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V.B.4 Stabilized Spinels and Nano O
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V.B.4 Stabilized Spinels and Nano O
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V.B.5 The Synthesis and Characteriz
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V.B.5 Synthesis & Characterization
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V.B.6 Cell Analysis-Interfacial Pro
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V.B.6 Cell Analysis-Interfacial Pro
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V.B.7 Role of Surface Chemistry on
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V.B.8 Characterization of New Catho
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V.B.8 Characterization of New Catho
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V.B.9 Layered Cathode Materials (AN
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V.B.10 Development of High Energy C
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V.B.10 Development of High Energy C
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V.B.11 Crystal Studies on High-ener
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V.B.12 Developing Materials for Lit
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V.B.13 Studies on the Local SOC and
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V.B.13 Studies on the Local SOC and
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V.B.14 New Cathode Projects (LBNL)
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V.C.1 Nanoscale Composite Hetero-st
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V.C.1 Nanoscale Composite Hetero-st
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V.C.2 Interfacial Processes - Diagn
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V.C.3 Search for New Anode Material
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V.C.4 Nano-structured Materials as
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V.C.4 Nano-structured Materials as
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V.C.5 Development of High Capacity
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V.C.5 Development of High Capacity
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V.C.6 Advanced Binder for Electrode
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V.C.6 Advanced Binder for Electrode
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V.C.7 Three-Dimensional Anode Archi
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ARGONNE2_CDJ403T me Pro ile V.C.7 T
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Page 117 and 118: V.C.12 Silicon Clathrates for Anode
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Page 121 and 122: V.C.13 Wiring Up Silicon Nanopartic
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Page 137 and 138: V.D.3 Molecular Dynamics Simulation
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V.F.2 Novel In Situ Diagnostics Too
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V.F.2 Novel In Situ Diagnostics Too
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V.G Integrated Lab-Industry Researc
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