Abstract
We investigate the contribution of pseudocapacitance to the overall capacitance of MnO2 electrodes in pure and alkaline-doped ionic liquids via two spectroscopic methods: step potential electrochemical spectroscopy (SPECS) and in situ Raman spectroscopy. For both characterization methods, thin-film electrodes of birnessite-like amorphous MnO2 were cycled in Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, pure or doped with lithium or sodium. SPECS allows determination of the influence of the electrolyte composition on the electrochemical behavior of the MnO2 electrodes. Pseudocapacitive charge storage can account for over half of the total capacitance with alkaline-doped ionic liquids. In situ Raman spectroscopy provided insight into the reversible ion intercalation in the MnO2 structure, which appears to be controlled by EMIm+ cations. These findings are supported by density functional theory calculations, which further help unveil the charge storage mechanism in birnessite-like amorphous MnO2 thin films operated in pure and alkaline-doped ionic liquids.