Electrochemistry
Online ISSN : 2186-2451
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78 巻 , 4 号
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  • Etsuro IWAMA, Fumitaka SHIMODATE, Yusuke OKI, Katsuhiko NAOI
    78 巻 (2010) 4 号 p. 266-272
    公開日: 2012/03/26
    ジャーナル フリー
    New hydrofluoroethers (HFEs), 2-trifluoromethyl-3-methoxy-perfluoro-pentane (TMMP) and 2-(trifluoro-2-fluoro-3-difluoropropoxy)-3-difluoro-4-fluoro-5-trifluoropentane (TPTP) were investigated as nonflammable electrolyte solvents for lithium ion batteries. Activation energies (ΔGdep) for desolvation of lithium ion (Li+) and lithium-solvation number (Ns) were evaluated for 1 M LiBETI/EC+DEC electrolytes with and without TMMP or TPTP in order to understand the mechanism of rate-capability improvement. The ΔGdep for the carbonate-mixed electrolyte (0.01–2 M of LiBETI/EC+DEC (50:50 in volume)) increased from 45.7 to 98.3 kJ mol−1 with a decrease in the LiBETI concentration. In comparison, ΔGdep was found lower (ΔGdep≈35 kJ mol−1) for TPTP-mixed electrolytes (LiBETI/EC+DEC+TPTP (5:45:50)) and much lower (ΔGdep≈25 kJ mol−1) for TMMP-mixed electrolytes (LiBETI/EC+DEC+TMMP (5:45:50)). Adding 60 vol% TPTP in EC+DMC (50:50) reduced both NEC and NDMC by 40%, exemplified by Raman spectroscopy with different concentrations of LiBETI (0.05–1.5 M) and DFT calculation. Thus, the rate-capability improvement by adding TMMP or TPTP is exerted by both enhancements of the intercalation kinetics and Li+ diffusion at the LiCoO2 interface, where HFEs preferentially exist by their affinity with the hydrophilic LiCoO2 cathode surface.
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