Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and...

As protonic ceramic electrolysis cells emerge for efficient H₂ production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr_0.9Y_0.1O_3-δ) and a redox-active mixed ionic electronic conductor (Ce_0.9Pr_0.1O_2-δ), that may enable rapid proton surface exchange at the solid-gas interface and transport along the solid-solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k_H, k_O) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400-500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.