Solvate Cation Migration and Ion Correlations in Solvate Ionic Liquids.

Lithium salt-glyme mixtures are interesting candidates as electrolytes for battery applications. Depending on the type of glyme or anion and the salt concentration, they either show ionic liquid-like behavior with stable lithium-glyme complex cations or concentrated salt solution-like behavior. Here, we apply electrophoretic NMR (eNMR) to elucidate transport mechanisms by observing the migration of the molecular species in an electric field. We investigate two solvate ionic liquids, i.e., lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and lithium tetrafluoroborate (LiBF), in tetraglyme (G4) at different glyme-salt molar ratios . A field-induced migration of neutral glyme molecules is directly observed, which is due to stable solvate-Li complex formation. Transference numbers, effective charges, and ionicities are derived from electrophoretic mobilities and self-diffusion coefficients, respectively, for the nuclei H, Li, and F. The effective charges are the highest at the equimolar mixture, = 1, they differ strongly for lithium and anion, and they show large differences between both systems. These findings are qualitatively interpreted in a speciation model, suggesting anionic clusters and solvate cations as the species dominating charge transport. The resulting effective charges can only be explained taking into account ion-ion anticorrelations in the framework of the Onsager formalism, where anticorrelations between the solvate cation and the anionic complexes arise due to momentum conservation. The contributions to the anticorrelation are most dominant at high salt concentrations and in the system with the LiBF anion due to its lower mass and ability to form larger asymmetric clusters with Li. Thus, in either system, also the lithium transference number is influenced to a different extent by ion-ion anticorrelations.