Electrode Design for MnO₂-Based Aqueous Electrochemical Capacitors: Influence of Porosity and Mass Loading

The purpose of this study is to highlight the influence of some fabrication parameters, such as mass loading and porosity, which are not really elucidated and standardized during the realization of electrodes for supercapacitors, especially when using metal oxides as electrode materials. Electrode calendering, as one stage during the fabrication of electrodes, was carried out step-by-step on manganese dioxide electrodes to study the decreasing porosity effect on the electrochemical performance of a MnO₂ symmetric device. One other crucial parameter, the mass loading, which has to be understood and well used for realistic supercapacitors, was investigated concurrently. Gravimetric, areal and volumetric capacitances are highlighted, varying the porosity for low-, medium- and large-mass loading. Low-loading leads to the best specific capacitances but is not credible for realistic supercapacitors, except for microdevices. Down 50% porosities after calendering, capacitances are increased and become stable faster, suggesting a faster wettability of the dense electrodes by the electrolyte, especially for high-mass loading. EIS experiments performed on electrodes without and with calendering lead to a significant decrease of the device's time response, especially at high loading. A high-mass loading device seems to work as a power battery, whereas electrode calendaring, which allows decreasing the time response, leads to an electrical behavior closer to that expected for a supercapacitor.