Evaluating Strategies to Enhance Li Transference in Salt-in-Ionic Liquid Electrolytes: Mixed Anions, Coordinating...

The increased safety of salt-in-ionic liquid electrolytes compared with established carbonate-based systems has promoted intense research in this field, but low conductivities, slow lithium transport, and unfavorable lithium anion correlations still prevent a mass market application. In particular, strong Li-anion correlations lead to dominant vehicular Li transport with the same drift direction for anions and lithium in the electric field. Here, three different strategies and their mutual interplay are evaluated, which could reduce Li-anion coordination, i.e., high salt concentration, a mixed-anion composition, as well as an ether functionalization of the organic cation. To this end, two series of highly concentrated IL-based electrolytes, based on either ethylmethylimidazolium (EMIM) or the ether-functionalized 1-methoxyethyl-1-methylpyrrolidinium (Pyr_12O1) organic cation, and employing mixed bis(fluorosulfonyl)imide/bis(trifluoromethylsulfonyl)imide (FSI/TFSI) anions are investigated. Measurements of conductivities, diffusion coefficients, and electrophoretic mobilities reveal no beneficial effect due to the increased heterogeneity of the FSI/TFSI-based electrolyte matrix, generally showing improved transport properties with increasing FSI share. However, a combination of both the ether-functionalized cation and high FSI content is proven successful, as lithium mobilities are positive, and vehicular transport is overcome by structural Li transport. Our study demonstrates the decisive role of synergy of the different approaches: While the single effect of a high salt concentration, weakly lithium-coordinating anions, or organic cations with lithium-affine functional groups is too weak to prevent vehicular transport, their joint effect can overcome vehicular Li transport, leading to improved Li conduction in ionic liquids.