Humidity‐Induced Degradation Mapping of Pt ₃ Co ORR Catalyst for PEFC by In‐Operando Electrochemistry and Ex Situ SAXS

Understanding the degradation mechanisms of Pt-alloy catalysts is crucial for enhancing their durability. This study investigates the impact of relative humidity on Pt and Pt₃Co catalysts using potential-cycling-based accelerated stress tests. Two conditions are investigated: 100% relative humidity on both sides, and a gradient with 30% at the anode and over 100% at the cathode. Pt₃Co demonstrates sensitivity, with 77% performance loss and reductions in electrocatalyst surface area. Results demonstrate a 30% decrease in potential loss for Pt catalysts and a 77% increase for Pt₃Co catalysts, indicating significant performance degradation in high humidity conditions, with Pt₃Co exhibiting greater sensitivity. Measurements of electrochemically active surface area reinforce these findings. Resistance analysis using electrochemical impedance spectroscopy using equivalent circuit modeling reveals a threefold increase in Pt₃Co MEAs' cathode charge transfer resistance and mass transport resistance during accelerated stress tests. Local current distribution analysis highlights differences between Pt catalyst and Pt₃Co, with the latter displaying dealloying effects. Small-angle X-ray scattering reveals changes in particle and cluster sizes, indicating structural changes. Scanning electron microscopy highlights catalyst and membrane thickness variations, suggesting heterogeneity in Pt₃Co. Under humidity gradients, Ostwald ripening plays a significant role in altering the catalyst's Pt₃Co structure and subsequently impacting its performance.