Mixed conduction protonic/electronic ceramic for high temperature electrolysis anode

This thesis validates the concept of mixed electron/proton ceramic conductors to be used as anode materials for intermediate temperature steam electrolyzer. The materials developed are based on cobaltites of alkaline-earth metals and rare earth elements commonly used for their high electronic conductivity in the temperature range of 300-600 C. The stability of each material has been assessed during 350 h in air and moist air. After checking the chemical compatibility with the BaZr0.9Y0.1O3 electrolyte material, eight compositions have been selected: BaCoO3, LaCoO3, Sr0.5La0.5CoO3, Ba0.5La0.5CoO3, GdBaCo2O5, NdBaCo2O5, SmBaCo2O5 and PrBaCo2O5. The thermal evolution of the oxygen stoichiometry of each material was determined by coupling iodo-metric titration and TGA in dry air. TGA in moist air has allowed determining the optimum temperature range for which proton incorporation is possible and maximized. Proton incorporation profiles have been determined on two cobaltites using SIMS and nuclear microanalysis in the ERDA configuration. Deuterium diffusion coefficients have been determined confirming the proton mobility in these materials. Under moist air, NdBaCo2O5 is shown to incorporate rapidly a significant number of protons that spread homogeneously within the material bulk. Anode microstructure optimization has allowed reaching at 450 C and 600 C total resistance values on symmetrical cell highly promising. (author)