Controlling $\text{Li}^+$ transport in ionic liquid electrolytes through salt content and anion asymmetry: A mechanistic understanding gained from molecular dynamics simulations

Abstract: 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 ($\text{TFSI}^-$) anion or its asymmetric analog 2,2,2-(trifluoromethyl)sulfonyl-N-cyanoamide ($\text{TFSAM}^-$). Relating lithium's coordination environment to anion mean residence times and diffusion constants confirms the remarkable transport behaviour of the $\text{TFSAM}^-$-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 $\text{TFSAM}^-$-containing ILEs.