Investigation of Water Impacts on Surface Properties and Performance of Air‐Electrode in Reversible Protonic Ceramic Cells

Abstract Water, being abundant and readily accessible, gains widespread usage as proton source in many catalysis and energy conversion technologies, including applications like reversible protonic ceramic cells (R‐PCCs). Revealing the influence of water on the electrode surface and reaction kinetics is critical for further improving their electrochemical performance. Herein, a hydrophilic air‐electrode PrBa 0.875 Cs 0.125 Co 2 O 5+δ is developed for R‐PCC, which demonstrates a remarkable peak power density of 1058 mW cm −2 in fuel cell mode and a current density of 1354 mA cm −2 under 1.3 V in electrolyzing steam at 650 °C. For the first time on R‐PCC, surface protons' behavior in response to external voltages is captured using in situ FTIR characterizations. Further, it is shown that contrary to the bulk proton uptake process that is thought to follow hydrogenation reactions and lead to cation reductions. The air‐electrode presents enriched surface protons occurring through oxidizing surface cations, as confirmed by depth‐profiling XPS results. H/D isotope exchange experiments and subsequent electrochemical characterization analyses reveal that the presence of protons enhances surface reactions. This study fills the knowledge gap between water‐containing atmospheres and electrochemical performance by providing insights into the surface properties of the material. These new findings provide guidance for future electrode design and optimization.