Abstract
Manganese oxides can undergo an electrochemical activation step that leads to greater capacitances, of which the structural change and mechanism remains poorly understood. Herein we present a wide-ranging study on a manganese oxide synthesised by annealing manganese(II) acetate precursor to 300 °C, which includes in operando monitoring of the structural evolution during the activation process via in situ Raman microscopy. Based on powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron and ex situ Raman microscopy, the as prepared manganese oxide was characterised as hausmannite-Mn3O4 with a minor portion of MnO2. The activation process of converting as-prepared hausmannite-Mn3O4 into amorphous MnO2 (with localised birnessite structure) by electrochemical cycling in 0.5 M Na2SO4 was examined. After activation, the activated MnOx exhibited capacitive performance of 174 F g-1 at a mass loading of 0.71 mg cm-2. The charge storage mechanism is proposed as the redox reaction between Mn(III) and Mn(IV) at outer surface active sites, since the disordered birnessite-MnO2 does not provide an ordered layer structure for cations and/or protons to intercalate.