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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The preferential site for oxygen isotope exchange was investigated on layered films of La 2−x Sr x CoO 4 ͑x = 0.5,1.0͒/La 0.6 Sr 0.4 CoO 3 prepared by pulsed laser deposition ͑PLD͒ on a polycrystalline Ce 0.9 Gd 0.1 O 1.95 . An isotope exchange experiment was performed at 773 K in 18 O-enriched oxygen of 0.2 ϫ 10 5 Pa. Three-dimensional imaging of secondary ion mass spectrometry ͑SIMS͒ was carried out to visualize the isotope distribution. The SIMS images suggested that there are fast oxygenincorporation paths along the hetero-phase interface of La 2−x Sr x CoO 4 /La 0.6 Sr 0.4 CoO 3 . The results have reproduced our former findings on the fast oxygen surface exchange with La 2−x Sr x CoO 4 /La 0.6 Sr 0.4 CoO 3 composite polycrystals.

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