Relationship between the nanoporous texture of activated carbons and their capacitance properties in different electrolytes

A series of activated carbons (ACs) with progressively changing nanotextural characteristics was obtained by heat-treatment of a bituminous coal at temperatures ranging from 520 to 1000 °C, and subsequent activation by KOH at 700 °C or 800 °C. As the pre-treatment temperature increases, the total pore volume VT decreases from 1.28 to 0.30 cm3 g−1, and the BET specific surface area from 3000 to 800 m2 g−1. The specific capacitance determined for each series of ACs using symmetric two electrode cells in 6 mol L−1 KOH varies almost linearly with the BET surface area, suggesting that the charge accumulation is controlled primarily by the surface area development. A further analysis of the electrochemical behaviour in different electrolytic media—aqueous and organic—shows that an adequate pore size is more important than a high surface area in order to obtain high values of capacitance. Theoretical values of volumetric capacitance could be evaluated without considering the size of ions, which is always uncertain in solution, and compared with the experimental data as a function of the pore width. The efficiency of pore filling, i.e., of double layer formation, is optimal when the pore size is around 0.7 nm in aqueous media and 0.8 nm in organic electrolyte. A study of the performance of the positive and negative electrodes during the charge/discharge of the capacitor, reveals an additional pseudo-faradaic contribution due to oxygenated functionalities within the working potential window of the negative electrode. This effect is more pronounced for the ACs series obtained at 700 °C, because of their higher oxygen content.