In Situ Characterization of Ceria Oxidation States in High-Temperature Electrochemical Cells with Ambient Pressure XPS

Abstract

Ambient pressure X-ray photoelectron spectroscopy (XPS) is used to measure near-surface oxidation states and local electric potentials of thin-film ceria electrodes operating in solid oxide electrochemical cells for H2O electrolysis and H2 oxidation. Ceria electrodes which are 300 nm thick are deposited on YSZ electrolyte supports with porous Pt counter electrodes for single-chamber tests in H2/H2O mixtures. Between 635 and 740 °C, equilibrium (zero-bias) near-surface oxidation states between 70 and 85% Ce3+ confirm increased surface reducibility relative to bulk ceria. Positive cell biases drive H2O electrolysis on ceria and further increase the percentage of Ce3+ on the surface over 100 μm from an Au current collector, signifying broad regions of electrochemical activity due to mixed ionic-electronic conductivity of ceria. Negative biases to drive H2 oxidation decrease the percentage of Ce3+ from equilibrium values but with higher electrode impedances relative to H2O electrolysis. Additional tests indicate that increasing H2-to-H2O ratios enhances ceria activity for electrolysis.