Influence of Solvent on Ion Aggregation and Transport in PY₁₅TFSI Ionic Liquid–Aprotic Solvent Mixtures

Molecular dynamics (MD) simulations using a many-body polarizable APPLE&P force field have been performed on mixtures of the <i>N</i>-methyl-<i>N</i>-pentylpyrrolidinium bis­(trifluoromethanesulfonyl)­imide (PY₁₅TFSI) ionic liquid (IL) with three molecular solvents: propylene carbonate (PC), dimethyl carbonate (DMC), and acetonitrile (AN). The MD simulations predict density, viscosity, and ionic conductivity values that agree well with the experimental results. In the solvent-rich regime, the ionic conductivity of the PY₁₅TFSI–AN mixtures was found to be significantly higher than the conductivity of the corresponding −PC and −DMC mixtures, despite the similar viscosity values obtained from both the MD simulations and experiments for the −DMC and −AN mixtures. The significantly lower conductivity of the PY₁₅TFSI–DMC mixtures, as compared to those for PY₁₅TFSI–AN, in the solvent-rich regime was attributed to the more extensive ion aggregation observed for the −DMC mixtures. The PY₁₅TFSI–DMC mixtures present an interesting case where the addition of the organic solvent to the IL results in an increase in the cation–anion correlations, in contrast to what is found for the mixtures with PC and AN, where ion motion became increasingly uncorrelated with addition of solvent. A combination of pfg-NMR and conductivity measurements confirmed the MD simulation predictions. Further insight into the molecular interactions and properties was also obtained using the MD simulations by examining the solvent distribution in the IL–solvent mixtures and the mixture excess properties