Electrochemical, top-down nanostructured pseudocapacitive electrodes for enhanced specific capacitance and cycling efficiency

Stabilization of the electroactive redox centers on ideally polarisable conductive electrodes is a critical challenge for realizing stable, high performing pseudocapacitive energy storage devices. Here, we report a top-down, electrochemical nanostructuring route based on voltammetric cycling to stabilize β-MnO₂ on a single walled carbon nanotube (CNT) scaffold from a MnMoO₄ precursor. Such in situ nanostructuring results in controlled disintegration of an ∼8 μm almond like structure to form ∼29 nm β-MnO₂ resulting in a 59% increase in the specific surface area and a 31% increase in the porosity of the pseudocapacitive electrode. Consequently, the specific capacitance and areal capacitance increase by ∼75% and ∼40%, respectively. Such controlled, top-down nanostructuring is confirmed through binding energy changes to Mo 3d, C 1s, O 1s and Mn 2p respectively in XPS. Furthermore, Raman spectral mapping confirms the sequential nanostructuring initiating from the interface of CNTs with MnMoO₄ and proceeding outwards. Thus, the process yields the final CNT/β-MnO₂ electrode that is electrically conductive, facilitates rapid charge transfer, and has increased capacitance and longer stability. Furthermore, the charge-transfer resistance and equivalent resistance are significantly lower compared to conventional activated carbon based electrodes.