Physicochemical properties of La0.5Ba0.5Co1-xFexO3-δ (0≤x≤1) as positrode for proton ceramic electrochemical cells

We report on essential properties of materials in the series La_0.5Ba_0.5Co_1-xFe_xO_3-δ as positrodes for proton ceramic electrochemical cells (PCECs). The unit cell and thermochemical expansion coefficient (TCEC) of these cubic perovskites decrease with iron content x, the TCEC of La_0.5Ba_0.5FeO_3-δ going as low as 11·10^-6 1/K. The materials behave as LaMO₃ perovskites with small band gaps and Ba acting as acceptors compensated by electron holes and oxygen vacancies. The electrical properties are dominated by p-type conduction with high large polaron mobilities for the Co-rich compositions at low temperatures, shifting towards small polaron mobilities with increasing Fe content. X-ray absorption spectroscopy (XAS) shows that Co is in a high spin state and takes on the main part of the cation oxidation state changes, and that hole states are in orbitals overlapping with the O 2p states, confirming the large polaronic behaviour, while holes on Fe are more localised at the cation. Hydration is more pronounced in inert atmospheres, as hydration of oxygen vacancies is easier than hydrogenation and increases with Fe content, in line with the commonly accepted finding that delocalization of holes disfavours protonation. Fe-rich compositions benefit from lower TCEC and higher hydration and hence expected proton permeability, at the cost of lower electronic conductivity. The surfaces are hydrophobic irrespective of Fe content, suggesting weak chemisorption of the underlaying water layer, possibly giving relatively many available surface sites for oxygen adsorption, but limited surface proton conductance – both of importance to positrodes for operando PCECs.