Solvent Effect on the Pore-Size Dependence of an Organic Electrolyte Supercapacitor

Organic electrolytes such as tetraethylammonium tetrafluoroborate dissolved in acetonitrile (TEA-BF4/ACN) are widely used in commercial supercapacitors and academic research, but conflicting experimental results have been reported regarding the dependence of surface-area-normalized capacitance on the pore size. Here we show from a classical density functional theory the dependence of capacitance on the pore size from 0.5 to 3.0 nm for a model TEA-BF4/ACN electrolyte. We find that the capacitance-pore size curve becomes roughly flat after the first peak around the ion diameter, and the peak capacitance is not significantly higher than the large-pore average. We attribute the invariance of capacitance with the pore size to the formation of an electric double-layer structure that consists of counterions and highly organized solvent molecules. This work highlights the role of the solvent molecules in modulating the capacitance and reconciles apparently conflicting experimental reports.