Reversible Degradation Phenomenon in PEMWE Cells: An Experimental and Modeling Study

In proton exchange membrane water electrolysis (PEMWE) systems, voltage cycles dropping below a threshold are associated with reversible performance improvements, which remain poorly understood despite being documented in literature. The distinction between reversible and irreversible performance changes is crucial for accurate degradation assessments. One approach in literature to explain this behavior is the oxidation and reduction of iridium. Iridium-based electrocatalyst activity and stability in PEMWE hinge on their oxidation state, influenced by the applied voltage. Yet, full-cell PEMWE dynamic performance remains underexplored, with a focus typically on stability rather than activity. This study systematically investigates reversible performance behavior in PEMWE cells using Ir-black as an anodic catalyst. Results reveal a recovery effect when the low voltage level drops below 1.5 V, with further enhancements observed as the voltage decreases, even with a short holding time of 0.1 s. This reversible recovery is primarily driven by improved anode reaction kinetics, likely due to changing iridium oxidation states, and is supported by alignment between the experimental data and a dynamic model that links iridium oxidation/reduction processes to performance metrics. This model allows distinguishing between reversible and irreversible effects and enables the derivation of optimized operation schemes utilizing the recovery effect.