American Chemical Society, Journal of Physical Chemistry Letters, 13(3), p. 1727-1731, 2012
DOI: 10.1021/jz3004624
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Organic electrolytes such as tetraethylammonium tetrafluoroborate dissolved in acetonitrile (TEA-BF{sub 4}/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-BF{sub 4}/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.