Abstract

Abstract The electrochemical property of a silicon electrode in a half-cell was investigated using the mixture of monoglyme-based solvents and lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) with 2:1 stoichiometry. The solvents used in this study are monoglyme (G1), 1,2-diethoxyethane (DEE), 1,2-dibutoxyethane (DBE), and 1,2-dimethoxypropane (P-G1). When Li (DEE)2 or Li(P-G1)2 was used, the cell retained ca. 20% capacity at a rate of 3 C, while the other samples showed almost no capacity under the same conditions. Raman spectroscopy measurement revealed that Li+ exists as two forms in the mixture, that is, a solvent shared ion pair (SSIP) [ Li+ ··· solvent ··· TFSA– ] and a contact ion pair (CIP) [ Li+ ··· TFSA– ]. According to the spectroscopic analysis, SSIP is the dominant species for Li (DEE)2 and Li(P-G1)2, and CIP for Li (G1)2 and Li (DBE)2. The order of the rate property was Li(P-G1)2 ∼ Li (DEE)2 > Li (DBE)2 ∼ Li (G1)2, which is almost consistent with the stability of free energy levels of Li+ in the respective monoglymes against CIP Li+ ··· TFSA– evaluated from the Raman spectra.

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