Microscopic Dynamics in an Ionic Liquid Augmented with Organic Solvents

Abstract

We present the complex microscopic dynamics of 1-butyl-3-methyl-imidazolium bis(trifluromethylsulfonyl)imide, [Bmim+][TFSI–], ionic liquid mixed with organic solvents to improve its properties for energy storage applications. To probe the microscopic dynamics on different length and time scales, we have used different neutron scattering spectrometers for quasielastic neutron scattering measurements to compare the effects of solvation in several organic solvents with nearly the same dipole moment but broadly varying bulk diffusivity. The ionic liquid–solvent mixtures show a nanoscopic phase separation into an ionic liquid-rich and a solvent-rich phase, as revealed by the model-free dynamic susceptibility data and further corroborated by the cluster histogram analysis of molecular dynamics (MD) simulation. In both phases, we observe a long-range translational mobility of the [Bmim+] cation, which scales with the bulk diffusivities of the organic solvents; this correlation becomes stronger in the solvent-rich phase. Additionally, various localized motion modes of the [Bmim+] cation are observed. A combination of neutron scattering and MD simulations reveals the parameters governing solvent-controlled diffusivity in an ionic liquid, which helps formulate new electrolytes optimized for efficient energy storage devices.