Li+ Solvation and Ionic Transport in Lithium Solvate Ionic Liquids Diluted by Molecular Solvents

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• 作者：Kazuhide Ueno ; Junichi Murai ; Kohei Ikeda ; Seiji Tsuzuki ; Mizuho Tsuchiya ; Ryoichi Tatara ; Toshihiko Mandai ; Yasuhiro Umebayashi ; Kaoru Dokko ; Masayoshi Watanabe
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：July 28, 2016
• 年：2016
• 卷：120
• 期：29
• 页码：15792-15802
• 全文大小：684K
• 年卷期：0
• ISSN：1932-7455

文摘

An equimolar mixture of lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]) and either triglyme (G3) or tetraglyme (G4) yielded stable molten complexes: [Li(G3)][TFSA] and [Li(G4)][TFSA]. These are known as solvate ionic liquids (SILs). Glyme-based SILs have thermal and electrochemical properties favorable for use as lithium-conducting electrolytes in lithium batteries. However, their intrinsically high viscosities and low ionic conductivities prevent practical application. Therefore, we diluted SILs with molecular solvents in order to enhance their ionic conductivities. To determine the stabilities of the complex cations in diluted SILs, their conductivity and viscosity, the self-diffusion coefficients, and Raman spectra were measured. [Li(G3)]⁺ and [Li(G4)]⁺ were stable in nonpolar solvents, that is, toluene, diethyl carbonate, and a hydrofluoroether (HFE); however, ligand exchange took place between glyme and solvent when polar solvents, that is, water and propylene carbonate, were used. In acetonitrile (AN) mixed solvent complex cations [Li(G3)(AN)]⁺ and [Li(G4)(AN)]⁺ were formed. [Li(G4)][TFSA] was more conductive than [Li(G3)][TFSA] when diluted with nonpolar solvents due to the greater ionic dissociativity in [Li(G4)][TFSA] mixtures. In view of the stability of the Li–glyme complex cations, the enhanced ionic conductivities, and the intrinsic electrochemical stabilities of the diluting solvents, [Li(G4)][TFSA] diluted by toluene or HFE, can be a candidate for an alternative battery electrolyte.