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In this work, we report the results from molecular dynamics simulations oflithium salt-ionic liquid electrolytes (ILEs) based either on the symmetricbis[(trifluoromethyl)sulfonyl]imide ($\text{TFSI}^-$) anion or its asymmetricanalog 2,2,2-(trifluoromethyl)sulfonyl-N-cyanoamide ($\text{TFSAM}^-$).Relating lithium's coordination environment to anion mean residence times anddiffusion constants confirms the remarkable transport behaviour of the$\text{TFSAM}^-$-based ILEs that has been observed in recent experiments: Forincreased salt doping, the lithium ions must compete for the more attractivecyano over oxygen coordination and a fragmented landscape of solvationgeometries emerges, in which lithium appears to be less strongly bound. Wepresent a novel, yet statistically straightforward methodology to quantify theextent to which lithium and its solvation shell are dynamically coupled. Bymeans of a Lithium Coupling Factor (LCF) we demonstrate that the shell anionsdo not constitute a stable lithium vehicle, which suggests for this electrolytematerial the commonly termed "vehicular" lithium transport mechanism could bemore aptly pictured as a correlated, flow-like motion of lithium and itsneighbourhood. Our analysis elucidates two separate causes why lithium andshell dynamics progressively decouple with higher salt content: On the onehand, an increased sharing of anions between lithium limits the achievable LCFof individual lithium-anion pairs. On the other hand, weaker bindingconfigurations naturally entail a lower dynamic stability of the lithium-anioncomplex, which is particularly relevant for the $\text{TFSAM}^-$-containingILEs.

physical chemistry chemical physics/pccp. physical chemistry chemical physics

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