Kinetic analysis of the self-discharge of the NiOOH OER active phase in KOH electrolyte: insights from in-situ Raman and UV–Vis reflectance spectroscopies

Abstract

NiOOH has been established as the active phase of NiO-based electrocatalysts in the alkaline Oxygen Evolution Reaction (OER). Here, we investigate the self-discharge behavior of NiOOH electrodes under open circuit potential (OCP) conditions in 1 M KOH electrolyte by monitoring phase changes via in-situ Raman and UV–Vis reflectance spectroscopies and performing kinetic analyses on the OCP and spectroscopic data. Our findings reveal a linear phase change from NiOOH to Ni(OH)₂ over time, indicative of a 0^th-order reduction reaction. Contrarily, the OCP evolution associated with this phase reduction displayed a combination of linear and exponential decay patterns as a result of various kinetics, including Faradaic processes and diffusion-controlled mechanisms, influencing the self-discharge potential over 1.25 V (vs RHE). An additional linear region at lower potentials (<1.25 V (vs RHE)) suggests that charge redistribution due to the phase change from α-Ni(OH)₂ to β-Ni(OH)₂ dominates the self-discharge, a behavior confirmed by in-situ UV–Vis reflectance spectroscopy. These findings highlight the effectiveness of combining in-situ Raman and UV–Vis spectroscopy with electrochemical data for real-time monitoring of electrochemical processes, here potential-dependent electrocatalyst phase changes, leading to a more detailed and accurate understanding of the dynamic behavior, phase change kinetics, and self-discharge behaviors of solid electrocatalysts that can guide the design of more efficient and durable energy storage and conversion materials.