The role of cations of the electrolyte for the pseudocapacitive behavior of metal oxide electrodes, MnO2 and RuO2

The energy storage process for amorphous hydrated manganese dioxide (MnO2) is suggested as fast faradaic reactions occurring at the solid electrode surface with the reduction from Mn4+ to Mn3+. In order to understand the role of cations of the electrolyte for the MnO2 electrode as a pseudocapacitor in aqueous KCl solution, we monitored the change of the capacitance by varying the concentration of the KCl electrolyte, the cation of the electrolyte, the pH of the solution, and the solvent. The charge storage for the metal oxide electrode such as MnO2 is concluded to involve a fast redox reaction through both potassium ion exchange, MnO2 + δ K+ + δ e- ↔ MnO2-δ(OK)δ and proton exchange, MnO2 + δ H+ + δ e- ↔ MnO2-δ(OH)δ dependent upon the availability of cations in the electrolyte. The contribution of proton to the pseudocapacitive process is not negligible in aqueous solution