Simulating Cyclic Voltammetry at Porous Electrodes Considering Faradaic and non-Faradaic Currents

Cyclic voltammetry (CV) is a commonly employed electroanalytical technique for characterizing the impact of electrode modification in electrochemical energy devices. Previous methods aimed to describe CV responses using models that relied on pore-scale data and assumed geometrical structures. In this study, we have developed a simpler and more efficient approach to model CV responses in porous electrodes by incorporating the Bruggeman correlation to account for the effects of porosity and tortuosity. Additionally, our developed model has been integrated with an equivalent circuit to simulate non-Faradaic currents using a constant phase element (CPE). The model's validity has been confirmed through comparisons with previous studies that assumed different geometrical structures, showing a reasonable level of agreement. Consequently, this developed model can be employed to simulate CV responses in porous electrodes without the need for detailed pore-scale information or assumed geometrical structures. Furthermore, we conducted a thorough investigation into the effects of various system parameters, including active surface area, reaction rate constant, porosity, Bruggeman exponent, and electrode thickness, to gain insights into how these parameters influence CV curves. This alternative approach to using CV responses for characterizing porous electrodes offers valuable opportunities for researchers to enhance their understanding of how to interpret CV curves in the context of porous electrode applications.