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An equimolar mixture of lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) 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.
Ueno et al. (Tue,) studied this question.