Analysis of H2O-induced surface degradation in SrCoO3-derivatives and its impact on redox kinetics

Abstract

Substituted SrCoO₃ perovskites have been proposed as promising mixed ionic electronic conductors for a range of applications including intermediate temperature solid oxide fuel cells (IT-SOFCs), electrolysers and thermochemical water splitting reactors for H₂ production. In this work we investigate the effect of sample exposure to water in substituted SrCoO₃ powders and thin films and correlate it with the degradation of oxygen mobility and kinetics. SrCo_0.95Sb_0.05O_3−δ (SCS) thin films have been deposited on different single crystal substrates by pulsed laser deposition (PLD). After water cleaning and post annealing at 300 °C, the sample surface presented an increase of the SrO-surface species as observed by ex situ X-ray Photoemission Spectroscopy (XPS) analysis. This increase in SrO at the sample surface has also been confirmed by the Low Energy Ion Scattering (LEIS) technique on both SCS thin film and powder. Thermochemical water splitting experiments on SCS and SrCo_0.95Mo_0.05O_3−δ (SCM) powder revealed a phase degradation under water oxidising conditions at high temperature with the formation of the trigonal phase Sr₆Co₅O₁₅. Transmission Electron Microscopy (TEM) analysis of SCS powder treated with water suggests that this phase degradation could already superficially start at Room Temperature (RT). By isotope exchange depth profile experiments on SCS thin films, we were able to quantify the oxygen diffusivity in this SCS surface decomposed layer (D* = 5.1 × 10⁻¹⁷ cm² s⁻¹ at 400 °C). In the specific case of bulk powder, the effect of water superficial decomposition translates into a lower oxidation and reduction kinetics as demonstrated by comparative thermogravimetric analysis (TGA) studies.