Tris(2,2,2-trifluoroethyl) phosphite as a co-solvent for nonflammable electrolytes in Li-ion batteries

被引:163
作者
Zhang, SS [1 ]
Xu, K [1 ]
Jow, TR [1 ]
机构
[1] USA, Res Lab, Sensors & Electron Devices Directorate, Adelphi, MD 20783 USA
关键词
Li-ion battery; nonflammable electrolyte; phosphite; phosphate; fire retardant;
D O I
10.1016/S0378-7753(02)00537-2
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this work, we used tris(2,2,2-trifluoroethyl) phosphite (TTFP), in which the oxidization number of phosphorus was three (III), to formulate nonflammable electrolytes of the Li-ion batteries. Using 1 m (mole solute per kilogram solvent) LiPF6 3:3:4 (w) propylene carbonate (PC)/ethylene carbonate (EC)/ethyl methyl carbonate (EMC) electrolyte as a baseline, the effect of TTFP on the flammability and conductivity of the electrolytes, as well as the cell performance was evaluated. It is observed that the addition of TTFP can substantially reduce flammability of the electrolytes at a small expense in the ionic conductivity. When the TTFP content reaches 15 wt.% versus the solvent, the electrolyte becomes nonflammable. In Li/graphite half-cell, TTFP not only suppresses PC decomposition and graphite exfoliation but also increases Coulombic efficiency (CE) of the lithiation and delithiation cycle. In Li/cathode (a lithium nickel-based mixed oxide cathode) half-cell, TTFP has negligible adverse impact on the cycling performance when the cells are cycled between 2.7 and 4.2 V. In graphite/cathode Li-ion cell using PC-based electrolytes, TTFP can improve cycling performance, especially at high temperature (60 degreesC), since its presence favors the formation of solid electrolyte interface (SEI) film on the graphite electrode and increases thermal stability of LiPF6-based electrolytes. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:166 / 172
页数:7
相关论文
共 31 条
[1]   An ionic conductivity and spectroscopy study of ionic transport mechanism in fire-retardant polyacrylonitrile-based gel electrolytes for Li polymer batteries [J].
Akashi, H ;
Tanaka, K ;
Sekai, K .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (03) :881-887
[2]   A novel fire-retardant polyacrylonitrile-based gel electrolyte for lithium batteries [J].
Akashi, H ;
Sekai, K ;
Tanaka, K .
ELECTROCHIMICA ACTA, 1998, 43 (10-11) :1193-1197
[3]  
AKASHI H, 1997, Patent No. 5658686
[4]   Chemical composition and morphology of the elevated temperature SEI on graphite [J].
Andersson, AM ;
Edström, K .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 2001, 148 (10) :A1100-A1109
[5]   Capacity fade mechanisms and side reactions in lithium-ion batteries [J].
Arora, P ;
White, RE ;
Doyle, M .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (10) :3647-3667
[6]   Thermal analysis of lithium-ion batteries [J].
Chen, YF ;
Evans, JW .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1996, 143 (09) :2708-2712
[7]   RECHARGEABLE LI1+XMN2O4/CARBON CELLS WITH A NEW ELECTROLYTE-COMPOSITION - POTENTIOSTATIC STUDIES AND APPLICATION TO PRACTICAL CELLS [J].
GUYOMARD, D ;
TARASCON, JM .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1993, 140 (11) :3071-3081
[8]   Electrochemical-calorimetric studies of lithium-ion cells [J].
Hong, JS ;
Maleki, H ;
Al Hallaj, S ;
Redey, L ;
Selman, JR .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1998, 145 (05) :1489-1501
[9]   Capacity loss of lithium manganese oxide spinel in LiPF6/ethylene carbonate-dimethyl carbonate electrolytes [J].
Huang, HT ;
Vincent, CA ;
Bruce, PG .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (02) :481-485
[10]  
Lee CW, 2000, ELECTROCHEM SOLID ST, V3, P63