Elucidating the interplay of local and mesoscale ion dynamics and transport properties in aprotic ionic liquids

Ion dynamics and charge transport in 1-methyl-3-octylimidazolium ionic liquids with chloride, bromide, tetrafluoroborate, tricyanomethanide, hexafluorophosphate, triflate, tetrachloroaluminate, bis(trifluoromethylsulfonyl)imide, and heptachlorodialuminate anions are investigated by broadband dielectric spectroscopy, rheology, viscometry, and differential scanning calorimetry. A detailed analysis reveals an anion and temperature-dependent separation of characteristic molecular relaxation rates extracted from various representations of the dielectric spectra. The separation in rates extracted from the electric modulus and conductivity formalisms is interpreted as an experimental signature of significant heterogeneity in the local ion dynamics associated with the structural glass transition, viscosity, and dc ion conductivity. It is further found that the degree of dynamic heterogeneity correlates with the strengths of slow dielectric and mechanical relaxations previously attributed to the dynamics of mesoscale solvophobic aggregates. Increasing local dynamic heterogeneity correlates with an increase in the strength of the slow, aggregate dielectric relaxation and a decrease in the strength of the slow, aggregate mechanical relaxation. Accordingly, increasing local dynamic heterogeneity, brought about by change in temperature and/or cation/anion chemical structure, correlates with an increase in the static dielectric permittivities and a decrease in the contribution of aggregate dynamics to the zero-shear viscosities. The established correlation provides a new ability to distinguish between the influence of mesoscale aggregate shape/morphology versus local and mesoscale ion dynamics on the transport properties of ionic liquids.