Low-Temperature Characterization of a Nonaqueous Liquid Electrolyte for Lithium Batteries

被引:2
作者
Hickson, Darby T. [1 ,2 ]
Im, Julia [2 ]
Halat, David M. [2 ]
Karvat, Aakash [2 ]
Reimer, Jeffrey A. [1 ,2 ]
Balsara, Nitash P. [1 ,2 ]
机构
[1] Lawrence Berkeley Natl Lab, Mat Sci Div, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Chem & Biomol Engn, Berkeley, CA 94720 USA
基金
美国国家科学基金会;
关键词
batteries; -; li-ion; energy storage; electrochemical engineering; CARBONATE-FREE ELECTROLYTE; STEADY-STATE CURRENT; ETHYLENE CARBONATE; POLYMER ELECTROLYTES; TRANSFERENCE NUMBERS; TRANSPORT-PROPERTIES; IONIC ASSOCIATION; ESTER COSOLVENTS; LIMITING CURRENT; SOLVENT BLENDS;
D O I
10.1149/1945-7111/ad2d91
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Rechargeable batteries exhibit poor performance at low temperatures due to sluggish ion transport through the electrolytic phase. Ion transport is governed by three transport parameters-conductivity, diffusion coefficient, and the cation transference number with respect to the solvent velocity-and the thermodynamic factor. Understanding how these parameters change with temperature is necessary for designing improved electrolytes. In this work, we combine electrochemical techniques with electrophoretic NMR to determine the temperature dependence of these parameters for a liquid electrolyte, LiTFSI salt dissolved in tetraglyme between -20 and 45 degrees C. At colder temperatures, all species in the electrolyte tend to move more slowly due to increasing viscosity, which translates to a monotonic decrease in conductivity and diffusion coefficient with decreasing temperature. Surprisingly, we find that the field-induced velocity of solvent molecules at a particular salt concentration is a nonmonotonic function of temperature. The cation transference number with respect to the solvent velocity thus exhibits a complex dependence on temperature and salt concentration. The measured thermodynamic and transport properties are used to predict concentration gradients that will form in a lithium-lithium symmetric cell under a constant applied potential as a function of temperature using concentrated solution theory. The calculated steady current at -20 degrees C is lower than that at 45 degrees C by roughly two orders of magnitude.
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页数:10
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