Effect of impurities and moisture on lithium bisoxalatoborate (LiBOB) electrolyte performance in lithium-ion cells

Abstract Electrolytes containing LiB(C2O4)2 (LiBOB) salts are of increasing interest for lithium-ion cells for several reasons that include their ability to form a stable solid electrolyte interphase on graphite electrodes. However, cells containing these electrolytes often show inconsistent performance because of impurities in the LiBOB salt. In this work we compare cycling and impedance data from cells containing electrolytes with LiBOB that was obtained commercially and LiBOB purified by a rigorous recrystallization procedure. We relate the difference in performance to a lithium oxalate impurity that may be a residual from the salt manufacturing process. We also examine the reaction of LiBOB with water to determine the effect of salt storage in high-humidity environments. Although LiBOB electrolytes containing trace amounts (∼100 ppm) of moisture appear relatively stable, higher moisture contents (∼1 wt%) lead to observable salt decomposition resulting in the generation of B(C2O4)(OH) and LiB(C2O4)(OH)2 compounds that do not dissolve in typical carbonate solutions and impair lithium-ion cell performance.

[1]  M. Whittingham,et al.  Structural chemistry of new lithium bis(oxalato)borate solvates. , 2004, Acta crystallographica. Section B, Structural science.

[2]  Jeff Dahn,et al.  Comparison of the Thermal Stability of Lithiated Graphite in LiBOB EC/DEC and in LiPF6 EC/DEC , 2003 .

[3]  Kang Xu,et al.  Lithium Bis(oxalato)borate Stabilizes Graphite Anode in Propylene Carbonate , 2002 .

[4]  E. M. Reynolds,et al.  Temperature Dependence of Capacity and Impedance Data from Fresh and Aged High-Power Lithium-Ion Cells , 2006 .

[5]  Doron Aurbach,et al.  Electrode–solution interactions in Li-ion batteries: a short summary and new insights , 2003 .

[6]  Fushen Li,et al.  The Electrochemical Characterization of Lithium Bis(oxalato)borate Synthesized by a Novel Method , 2006 .

[7]  Wu Xu,et al.  Weakly Coordinating Anions, and the Exceptional Conductivity of Their Nonaqueous Solutions , 2001 .

[8]  K. Nechev,et al.  Evaluating LiBOB/Lactone Electrolytes in Large-Format Lithium-Ion Cells Based on Nickelate and Iron Phosphate , 2008 .

[9]  John B. Kerr,et al.  The role of Li-ion battery electrolyte reactivity in performance decline and self-discharge , 2003 .

[10]  M. Wohlfahrt‐Mehrens,et al.  The behaviour of graphite, carbon black, and Li4Ti5O12 in LiBOB-based electrolytes , 2006 .

[11]  Dennis W. Dees,et al.  Application of a lithium-tin reference electrode to determine electrode contributions to impedance rise in high-power lithium-ion cells , 2004 .

[12]  Dennis W. Dees,et al.  Effect of electrolyte composition on initial cycling and impedance characteristics of lithium-ion cells , 2008 .

[13]  Kang Xu,et al.  LiBOB as Salt for Lithium-Ion Batteries:A Possible Solution for High Temperature Operation , 2002 .

[14]  Brett L. Lucht,et al.  Thermal Decomposition of LiPF6-Based Electrolytes for Lithium-Ion Batteries , 2005 .

[15]  H. Schweiger,et al.  NMR Determination of Trace Water in Lithium Salts for Battery Electrolytes , 2005 .

[16]  K. Singh,et al.  Lithium diisopropylamide-mediated ortholithiation and anionic fries rearrangement of aryl carbamates: role of aggregates and mixed aggregates. , 2006, Journal of the American Chemical Society.

[17]  B. Lucht,et al.  Thermal Reactions of LiPF6 with Added LiBOB Electrolyte Stabilization and Generation of , 2007 .

[18]  Kang Xu,et al.  Study of SEI layer formed on graphite anodes in PC/LiBOB electrolyte using IR spectroscopy , 2004 .

[19]  M. Wohlfahrt‐Mehrens,et al.  Film formation in LiBOB-containing electrolytes , 2006 .

[20]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.