Evaluating oxide nanoparticle exsolution on A-site deficient PrBaCo₂O_6-δ electrodes

Abstract Nanoparticle exsolution is a powerful technique for functionalizing redox oxides in energy applications, particularly at high temperatures. It shows promise for solid oxide fuel cells and electrolyzers. However, exsolution of other chemistries like metal oxides is not well studied, and the mechanism is poorly understood. This work explores oxide exsolution in PrBa_1−x Co₂O_6−δ (x = 0, 0.05, 0.1, 0.15) double perovskites, practiced electrodes in proton ceramic fuel cells and electrolyzers. Oxide exsolution in PrBa_1−x Co₂O_6−δ aimed at boosting the electrocatalytic activity and was evaluated by varying intrinsic materials-related properties, viz. A-site deficiency and external parameters (temperature, under fixed time, and pO₂ = 10⁻⁵ atm conditions). The materials were analyzed with conventional characterization tools and synchrotron-based small-angle x-ray scattering. Unlike metal-nanoparticle exsolution, increasing the A-site deficiency did not enhance the extent of oxide-nanoparticle exsolution, whereas larger nanoparticles were obtained by increasing the exsolution temperature. Combined Raman spectroscopy and electron microscopy analysis revealed that BaCoO₃, Co₃O₄, and amorphous BaCO₃ nanoparticles were formed on the surface of the double perovskites after the reductive treatments. The present results demonstrate the complexity of oxide-nanoparticle exsolution in comparison with metal-nanoparticle exsolution. Further materials screening and mechanistic studies are needed to enhance our understanding of this method for functionalizing proton ceramic electrochemical cells (PCEC) electrodes.