The optimization of carbon-based supercapacitors is of great technological importance for electrical energy storage. This challenge stresses the relevance of current attempts to increase the surface-related capacitance C/S (F m−2) of carbons. We show that for microporous carbons this property is practically constant for pore widths between 0.7 and 1.8 nm. The study is based on two independent approaches: (i) the effective surface area accessible to the ions, which may differ considerably from the BET-surface and (ii) the volumetric capacitance in the micropores. One obtains 0.094 F m−2 in (C2H5)4NBF4/acetonitrile and approximately 0.100 F m−2 in aqueous H2SO4 after correcting for pseudo-capacitance effects. This pattern is supported by recent modelling which takes into account the solvent. It is also suggested that constant values of the surface based-capacitance may reflect a gradual decrease of the dielectric constant of the electrolytes in smaller micropores due to desolvation.
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Stoeckli et al. (2013) studied this question.
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