Large Variations in the Composition of Ionic Liquid–Solvent Mixtures in Nanoscale Confinement

Mixtures of an ionic liquid with an organic solvent are widely used as electrolytes in supercapacitors where they are often confined in porous electrodes with pore widths only slightly larger than the sizes of bare ions or solvent molecules. The composition of the electrolyte inside these pores, which may depend on the pore width and choice of electrolyte, can affect supercapacitor performance but remains poorly understood. Here, we perform all-atom molecular dynamics simulations of solutions of two different ionic liquids in acetonitrile under confinement between graphene sheets forming slit pores of various widths. We observe significant oscillations in the in-pore ionic liquid mole fraction with varying pore widths. Ions are excluded from very narrow pores, while for pore widths that tightly fit a single layer of ions, we observe an in-pore ionic liquid mole fraction over three times greater than that in the bulk. At slightly larger pore widths, we observe for different ionic liquids either a nearly complete exclusion of ions from the pore or a slight depletion of ions, while ion population again increases as pore width further increases. We develop an analytical model that can qualitatively predict the in-pore ionic liquid mole fraction based on the effective molar volumes and the pore wall interaction energies of each species. Our work suggests a new avenue for tuning the ionic liquid mole fraction in nanopores with potentially significant implications for designing systems involving nanoconfined liquid electrolytes such as supercapacitors where in-pore ion population can affect charging dynamics.