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Abstract Iridium oxide films were formed by potential cycling in neutral phosphate buffer solution (pH = 6.9) and studied by capacitance and photoelectrochemical measurements, and by TEM. The results have revealed p -type semiconductivity of the oxide. The increase of the electric conductivity occurring simultaneously with the colouring of the film is explained by a transition, at the film|electrolyte interface, from a Schottky barrier to an ohmic contact. This transition takes place at the flatband potential, which is close to the potential of the main voltammetric peak. The doping values obtained from the Mott—Schottky approach are related with the porous structure of the film.

Abstract Nanostructured porous MnO2, especially its hydrated amorphous and low crystalline form (MnO2·nH2O), has been one of the most promising material considered for charge storage applications, due to electrochemical similarities with RuO2 and its relative low cost. However, the intrinsic poor conductivity of MnO2 combined with the presence of structural water, which provides high ionic but low electronic conductivity, is a great hindrance for wider application. An effective approach to overcome this drawback involves the deposition of thin MnO2 layers on porous, high surface area metallic scaffolds. The present work addresses this route and provides novel insights thanks to the combination of MnOx·nH2O with custom-made Ni foams, fabricated via one-step electrodeposition using the dynamic hydrogen bubble template (DHBT). The porous Ni foams provide a scaffold with a 3D architecture with optimized pore size and surface. The composite electrode was fabricated by anodic deposition of MnOx·nH2O on the 3D Ni foams. The electrochemical behaviour was tested in 1 M KOH, since there are very few studies addressing the electrochemical behaviour of MnOx·nH2O in alkaline media for electrochemical supercapacitors applications. In addition, thermal treatment (150–250 °C) was performed to evaluate the effect of hydration on the material properties. The results revealed that the as-obtained composites are highly stable, displaying much higher specific capacitances with 73–90% (depending on the mass load) capacitance retention compared to their de-hydrated counterparts. The charge-discharge processes were found to be highly reversible throughout 5000 cycles, maintaining almost 100% columbic efficiency. In conclusion, the MnOx·nH2O@Ni composite electrodes showed a very stable pseudocapacitive behaviour and exceptional cycling performance in 1 M KOH, being therefore a promising alternative charge storage electrode for electrochemical supercapacitors.

Abstract Electrochemical Impedance Spectroscopy (EIS) is a powerful technique to understand the electrode-electrolyte interaction and to evaluate degradation, resistive behaviour and electrochemical activity of energy storage materials used in batteries, pseudocapacitors and supercapacitors among others. However, it can sometimes be misused or under-interpreted. To effectively acquire EIS results, the voltages imposed to the working electrode at which EIS spectra are obtained, shall be critically selected. This work follows a previous study on the EIS response of Nickel-Cobalt hydroxide, and highlights how the Mott-Schottky model can be used as a complementary tool to explain EIS results obtained at different potentials. The Mott-Schottky model is used to understand further the fundamental processes occurring at the electrode-electrolyte interface of nickel-cobalt hydroxide in alkali media and to explain the changes in conductivity of the material that ultimately determine the electrode electrochemical activity. The applicability of the model to assist in the potential selection for EIS studies on other important charge storage materials such as MnOx and MoOx is discussed too.