Eutectic Electrolytes Composed of LiN(SO<sub>2</sub>F)<sub>2</sub> and Sulfones for Li-Ion Batteries

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  • Yosuke Ugata
    Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
  • Yichuan Chen
    Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
  • Shohei Sasagawa
    Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
  • Kazuhide Ueno
    Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
  • Masayoshi Watanabe
    Advanced Chemical Energy Research Center, Institute of Advanced Sciences, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan
  • Hiroki Mita
    Murata Manufacturing Co., Ltd., 1-10-1 Higashikotari, Nagaokakyo-shi, Kyoto 617-8555, Japan
  • Jusuke Shimura
    Murata Manufacturing Co., Ltd., 1-10-1 Higashikotari, Nagaokakyo-shi, Kyoto 617-8555, Japan
  • Masayuki Nagamine
    Murata Manufacturing Co., Ltd., 1-10-1 Higashikotari, Nagaokakyo-shi, Kyoto 617-8555, Japan
  • Kaoru Dokko
    Department of Chemistry and Life Science, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, Japan

説明

Sulfones are polar molecules that can be used as thermally stable electrolyte solvents for Li-ion batteries (LIBs). Li salts form stoichiometric solvates with sulfones in the electrolytes. The melting points of the solvates tend to be higher than room temperature, thereby limiting the operating temperature range of the batteries. In this study, the applicability of ternary eutectic mixtures of LiN(SO2F)2 (LiFSA), sulfolane (SL), and dimethyl sulfone (DMS) as LIB electrolytes was assessed. Relative to the binary LiFSA–sulfone electrolytes, the ternary eutectic electrolytes remained liquid over a wide temperature range due to the increased entropy of mixing. Sulfone-bridged Li+–sulfone–Li+ and anion-bridged Li+–FSA––Li+ network structures were formed in the eutectic electrolyte with a composition of [LiFSA]/[SL]/[DMS] = 1/1.5/1.5. Pulsed-field gradient NMR measurements revealed that the Li+ ion dynamically exchanges sulfones and anions and diffuses more rapidly than these ligands, resulting in the relatively high Li+ transference number of the electrolyte. Highly reversible charge–discharge processes of the LiCoO2 and graphite electrodes were attained using the ternary eutectic electrolyte. The rate capability of the Li/LiCoO2 cell in the eutectic electrolyte was comparable to that of the cell in the conventional 1 M LiPF6 in an ethylene carbonate/dimethyl carbonate solution despite its lower ionic conductivity.

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