Solvent effects on Li ion transference number and dynamic ion correlations in glyme- and sulfolane-based molten Li...

The Li⁺ transference number of electrolytes is one of the key factors contributing to the enhancement in the charge-discharge performance of Li secondary batteries. However, a design principle to achieve a high Li⁺ transference number has not been established for liquid electrolytes. To understand the factors governing the Li⁺ transference number t_Li, we investigated the influence of the ion-solvent interactions, Li ion coordination, and correlations of ion motions on the Li⁺ transference number in glyme (Gn, n = 1-4)- and sulfolane (SL)-based molten Li salt solvate electrolytes with lithium bis(trifluoromethansulfonyl)amide (LiTFSA). For the 1 : 1 tetraglyme-LiTFSA molten complex, [Li(G4)][TFSA], the Li⁺ transference number estimated using the potentiostatic polarisation method (t = 0.028) was considerably lower than that estimated using the self-diffusion coefficient data with pulsed filed gradient (PFG)-NMR (t = 0.52). The dynamic ion correlations (i.e., cation-cation, anion-anion, and cation-anion cross-correlations) were determined from the experimental data on the basis of Roling and Bedrov's concentrated solution theory, and the results suggest that the strongly negative cross-correlations of the ion motions (especially for cation-cation motions) are responsible for the extremely low t of [Li(G4)][TFSA]. In contrast, t is larger than t in the SL-based electrolytes. The high t of the SL-based electrolytes was ascribed to the substantially weaker anti-correlations of cation-cation and cation-anion motions. Whereas the translational motions of the long-lived [Li(glyme)]⁺ and [TFSA]^- dominate the ionic conduction for [Li(G4)][TFSA], Li ion hopping/exchange conduction was reported to be prevalent in the SL-based electrolytes. The unique Li ion conduction mechanism is considered to contribute to the less correlated cation-cation and cation-anion motions in SL-based electrolytes.