Binary Mixed Solvent Electrolytes Containing Trifluoropropylene Carbonate for Lithium Secondary Batteries

To improve the safety of the electrolyte used for lithium secondary batteries, binary mixed solvent electrolytes containing trifluoropropylene carbonate (TFPC) as cosolvent have been studied. Chloroethylene carbonate (CIEC), ethylene carbonate, and propylene carbonate were chosen as the other component of the binary mixed solvent for the electrolytes. The solution properties of these electrolytes were characterized using conductivity and nuclear magnetic resonance (NMR) spectroscopy. The chemical shift of CIEC and TFPC did not vary with the mixing ratio due to their similar enthalpies of solvation as derived by molecular orbital simulation. The ClEC/TFPC electrolyte showed higher discharge capacities with lower irreversible capacity loss in both a graphite/Li cell and Li 1+x Mn 2 O 4 /Li cell than other electrolyte systems. Electrochemical impedance spectroscopy measurements were made for cells composed of each electrolyte. The surface of the graphite anode was analyzed using X-ray photoelectron spectroscopy, infrared spectroscopy, and solid 7 Li-NMR spectroscopy.

[1]  A. Dey,et al.  The Electrochemical Decomposition of Propylene Carbonate on Graphite , 1970 .

[2]  G. A. Petersson,et al.  A complete basis set model chemistry. I. The total energies of closed‐shell atoms and hydrides of the first‐row elements , 1988 .

[3]  G. A. Petersson,et al.  A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms , 1991 .

[4]  J. J. Murray,et al.  Electrochemical Intercalation of Lithium into Graphite , 1993 .

[5]  D. Aurbach,et al.  The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries I . Li Metal Anodes , 1995 .

[6]  J. J. Murray,et al.  Use of Chloroethylene Carbonate as an Electrolyte Solvent for a Lithium Ion Battery Containing a Graphitic Anode , 1995 .

[7]  Dominique Guyomard,et al.  High voltage stable liquid electrolytes for Li1+xMn2O4/carbon rocking-chair lithium batteries , 1995 .

[8]  R. Blint.  Binding of Ether and Carbonyl Oxygens to Lithium Ion , 1995 .

[9]  D. Aurbach,et al.  The Study of Electrolyte Solutions Based on Ethylene and Diethyl Carbonates for Rechargeable Li Batteries II . Graphite Electrodes , 1995 .

[10]  Young-Min Choi,et al.  Effects of lithium content on the electrochemical lithium intercalation reaction into LiNiO2 and LiCoO2 electrodes , 1995 .

[11]  M. Yoshio,et al.  Suppression of electrochemical decomposition of propylene carbonate at a graphite anode in lithium-ion cells , 1996 .

[12]  J. J. Murray,et al.  Use of Chloroethylene Carbonate as an Electrolyte Solvent for a Graphite Anode in a Lithium‐Ion Battery , 1996 .

[13]  J. Arai,et al.  Characterization of organic electrolyte systems by nuclear magnetic resonance and molecular orbital simulation: Equilibrium constant and net charge distribution in solvation state , 1997 .

[14]  R. Blint.  Competitive Coordination of Lithium Ion , 1997 .

[15]  Petr Novák,et al.  Insertion Electrode Materials for Rechargeable Lithium Batteries , 1998 .

[16]  M. Ishikawa,et al.  A Raman spectroscopic study of organic electrolyte solutions based on binary solvent systems of ethylene carbonate with low viscosity solvents which dissolve different lithium salts , 1998 .

[17]  M. Ishikawa,et al.  Effects of electrolyte composition on the charge and discharge performances of LiNiO2 positive electrode for lithium ion batteries , 1998 .

[18]  Y. Ein‐Eli,et al.  The Superiority of Asymmetric Alkyl Methyl Carbonates , 1998 .

[19]  Petr Novák,et al.  Chloroethylene carbonate, a solvent for lithium ion cells, evolving CO2 during reduction , 1998 .

[20]  Yasuo Takeda,et al.  7Li-NMR study of carbon fiber and graphite anodes for lithium ion batteries , 1998 .

[21]  P. Novák,et al.  FTIR and DEMS investigations on the electroreduction of chloroethylene carbonate-based electrolyte solutions for lithium-ion cells , 1999 .

[22]  B. Ratnakumar,et al.  Irreversible Capacities of Graphite in Low‐Temperature Electrolytes for Lithium‐Ion Batteries , 1999 .

[23]  J. Arai,et al.  Solvation states and properties of binary mixtures of halogenated cyclic carbonates and a linear carbonate , 1999 .

[24]  K. Kanamura,et al.  Surface Condition Changes in Lithium Metal Deposited in Nonaqueous Electrolyte Containing HF by Dissolution‐Deposition Cycles , 1999 .

[25]  R. Mcmillan,et al.  Fluoroethylene carbonate electrolyte and its use in lithium ion batteries with graphite anodes , 1999 .

[26]  S. Koh,et al.  Induced Surface Reactions and Chemical States: A Kiloelectronvolt Ion Irradiation on Simple Linear Chain Structure Polymers in an O 2 Environment , 1999 .

[27]  Tatsuo Horiba,et al.  Large-scale development of lithium batteries for electric vehicles and electric power storage applications , 1999 .

[28]  D. Billaud,et al.  TEM characterization of the passivating layer formed during the reduction of graphite electrodes in selected electrolytes , 1999 .

[29]  Kang Xu,et al.  Liquid‐Solid Phase Diagrams of Binary Carbonates for Lithium Batteries , 2000 .

[30]  K. Kitaura,et al.  Vibrational Assignments of Lithium Alkyl Carbonate and Lithium Alkoxide in the Infrared Spectra An Ab Initio MO Study , 2000 .

[31]  Matsuhiko Nishizawa,et al.  Kinetic Characterization of Single Particles of LiCoO2 by AC Impedance and Potential Step Methods , 2001 .