Operando Characterization of Protonic Ceramic Electrochemical Cells: Revealing Proton Defect Chemistry, Electrode Reconstruction and Interface Evolution

Protonic ceramic electrochemical cells (PCECs), including protonic ceramic fuel cells, electrolysis cells and reversible cells, have attracted increasing attention as efficient solid-state devices for electricity generation, hydrogen production and chemical conversion at intermediate temperatures. Recent advances in electrolyte thinning, electrode nanostructuring and interface engineering have enabled remarkable device performance, including reversible operation at 500–650 °C, operation below 450 °C, and expanded fuel flexibility toward hydrogen, ammonia and methane-containing feeds. However, the working-state mechanisms governing their performance and durability remain insufficiently understood. In particular, proton incorporation, surface hydration, proton exchange, proton-coupled oxygen reduction/evolution, electrode reconstruction and buried interface degradation are highly dynamic processes that cannot be fully resolved by ex situ or post-mortem characterization. Operando characterization provides a powerful route to bridge this knowledge gap by directly correlating structural, chemical and electrochemical evolution under realistic temperature, steam, gas atmosphere and electrochemical bias. In this review, we summarize recent progress in operando and in situ characterization of PCECs, with emphasis on vibrational spectroscopy, X-ray-based techniques, neutron methods, electron microscopy and electrochemical diagnostics. We discuss how operando DRIFTS and H/D isotope exchange reveal voltage-dependent proton exchange kinetics, how operando Raman captures oxygen-electrode surface reconstruction, how X-ray and neutron methods probe redox chemistry and proton dynamics, and how EIS/DRT analysis links structural changes to reaction resistance. We further highlight current challenges, including limited access to buried interfaces, difficulty in quantifying protonic defects, insufficient multimodal correlation and the lack of standardized operando cell configurations. Finally, we propose future directions based on isotope-resolved spectroscopy, multimodal operando platforms, AI-assisted spectral/impedance analysis and theory-guided interpretation. This review aims to establish a working-state mechanistic framework for rationally designing durable, high-performance PCECs.