Although ion-hopping is believed to be a significant mode of transport for small ions in liquid high concentration electrolytes (HCE), its bulk signatures over sufficiently long time intervals are yet to be shown. We computationally establish the long and short time imprints of hopping in HCEs using LiBF4-in-sulfolane mixtures as models. The high viscosity of this electrolyte leads to significant dynamic heterogeneity in Li-ion transport. Li-ions exhibit a preference to transit to previously occupied Li-ion-sites, bridged through anion or solvent molecules. Hopping in the liquid matrix was found to be an activated process, whose free energy barrier and transition state structure have been determined. Evidence for nanoscale compositional heterogeneity at high salt concentrations is also presented. The simulations shed light on the composition, stiffness, and lifetime of the solvation shell of Li ions. The understanding of HCEs gleaned from this study will spearhead the choice, engineering and applicability of this class of electrolytes.
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