Controlling Li + transport in ionic liquid electrolytes through salt content and anion asymmetry: a mechanistic understanding gained from molecular dynamics simulations.

In this work, we report the results from molecular dynamics simulations of lithium salt-ionic liquid electrolytes (ILEs) based either on the symmetric bis[(trifluoromethyl)sulfonyl]imide (TFSI - ) anion or its asymmetric analogue 2,2,2-(trifluoromethyl)sulfonyl- N -cyanoamide (TFSAM - ). Relating lithium's coordination environment to anion mean residence times and diffusion constants confirms the remarkable transport behaviour of the TFSAM - -based ILEs that has been observed in recent experiments: for increased salt doping, the lithium ions must compete for the more attractive cyano over oxygen coordination and a fragmented landscape of solvation geometries emerges, in which lithium appears to be less strongly bound. We present a novel, yet statistically straightforward methodology to quantify the extent to which lithium and its solvation shell are dynamically coupled. By means of a Lithium Coupling Factor (LCF) we demonstrate that the shell anions do not constitute a stable lithium vehicle, which suggests for this electrolyte material the commonly termed "vehicular" lithium transport mechanism could be more aptly pictured as a correlated, flow-like motion of lithium and its neighbourhood. Our analysis elucidates two separate causes why lithium and shell dynamics progressively decouple with higher salt content: on the one hand, an increased sharing of anions between lithium limits the achievable LCF of individual lithium-anion pairs. On the other hand, weaker binding configurations naturally entail a lower dynamic stability of the lithium-anion complex, which is particularly relevant for the TFSAM - -containing ILEs.