Charge Storage Mechanism of MnO₂ Electrode Used in Aqueous Electrochemical Capacitor

TLDR

Cyclic voltammetry and X‑ray photoelectron spectroscopy were applied to thin MnO₂ films on platinum and thick composite electrodes to probe charge‑storage mechanisms in aqueous electrolyte. Only the thin MnO₂ layer participates in redox, with Mn cycling from +III to +IV and Na⁺ involvement, yet the low Na/Mn ratio indicates proton participation, while the thick composite shows no Mn state change, confirming that only a surface layer stores charge.

Abstract

The charge storage mechanism in MnO2 electrode, used in aqueous electrolyte, was investigated by cyclic voltammetry and X-ray photoelectron spectroscopy. Thin MnO2 films deposited on a platinum substrate and thick MnO2 composite electrodes were used. First, the cyclic voltammetry data established that only a thin layer of MnO2 is involved in the redox process and electrochemically active. Second, the X-ray photoelectron spectroscopy data revealed that the manganese oxidation state was varying from III to IV for the reduced and oxidized forms of thin film electrodes, respectively, during the charge/discharge process. The X-ray photoelectron spectroscopy data also show that Na+ cations from the electrolyte were involved in the charge storage process of MnO2 thin film electrodes. However, the Na/Mn ratio for the reduced electrode was much lower than what was anticipated for charge compensation dominated by Na+, thus suggesting the involvement of protons in the pseudofaradaic mechanism. An important finding of this work is that, unlike thin film electrodes, no change of the manganese oxidation state was detected for a thicker composite electrode because only a very thin layer is involved in the charge storage process.