Equivalent circuit analysis was undertaken on a mixed conductor electrode/solid oxide electrolyte system. In a limited case where surface reaction is the predominant rate-controlling process, the equivalent circuit was simplified to parallel connection of a resistor (surface reaction resistance) and a capacitor (chemical capacitance due to oxygen nonstoichiometry). Equilibrium oxygen vacancy concentration was correlated with the chemical capacitance. The model was applied to a dense film of La0.6Sr0.4CoO3−δ deposited on a sintered plate of Ce0.9Gd0.1O1.95 by a laser ablation method. Frequency response of the electrochemical impedance was measured under dc bias at 873-1073 K in O2­normalAr gas mixtures. The observed capacitance was extremely large, e.g., around 0.1 to 1 Fcm−2 for the 1.5 μm thick film. The oxygen vacancy concentration in the film was calculated from the capacitance and compared with the literature data measured by thermogravimetry. The film was found to show smaller oxygen nonstoichiometry. The enthalpy for oxygen vacancy formation in the film was about 40 kJ mol −1 larger than the bulk. © 2002 The Electrochemical Society. All rights reserved.

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Proton transport properties across the grain boundary of barium zirconate based proton conductors were studied in accordance with the space charge concept. The analysis is performed at temperatures lower than 200 C using a Mott-Schottky model. The barrier height of Y-and Gd-doped barium zirconate is in the range of 0.29 to 0.57 V, which higher than that of oxygen ionic conductors. The barrier height of the space charge layer shows a dependence on the dopant type and concentration. The dependence correlates with the enrichment of the dopant at the grain boundary. The results suggest that the enrichment of the dopant decreases the barrier height and is effective to improve proton transport properties across the grain boundary.

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