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The potential of interactive layers of mixed-conducting oxides for improving the performance of air electrodes of solid oxide cells in the intermediate-temperature range is demonstrated. Active layers of Ce0.9Gd0.1O2−δ (CGO), Ce0.8Pr0.2O2−δ (CPO), and SrFe0.9Mo0.1O3−δ (SFM) with thickness in the range 200–400 nm are deposited on CGO-based electrolyte by spray pyrolysis, followed by deposition of a SFM/CGO composite air electrode by painting. The morphologies and phase composition of the active layers are examined by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy microanalysis. The electrochemical performance of the electrolyte–electrode assemblies is determined by impedance spectroscopy in the range 600–800 °C. Significant improvements in the performance of the electrode process and the geometrically normalized ohmic conductance are observed for the assembly with a CPO active layer with mixed-oxide-ionic–electronic conductivity, especially in the low-temperature range, attributable to extension of the surface path of the electrochemical reactions. The CGO intermediate layer also improves performance but to a lesser degree, most likely due to better ionic-current collection in comparison to the assemblies with either SFM as the active layer or no active layer.

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