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Dense silver (Ag) cathodes with defined triple phase boundary (TPB between the interface of electrolyte, electrode, and gas) lengths (LTPB) and electrode areas (AELT) were fabricated by photolithography and E-beam evaporation over a proton conducting BaZr0.4Ce0.4Y0.1Yb0.1O3−δ (BZCYYb4411) electrolyte. A bi-layer lift-off resist method appears to be more versatile than a single layer lift-off resist method for successful patterned cathode fabrication. The electrochemical behaviors of the patterned Ag cathodes over the BZCYYb4411 electrolyte were tested by electrochemical impedance spectroscopy (EIS) at different temperatures in atmospheres with different concentrations of O2 and H2O. The results were processed using Distribution of Relaxation Times (DRT) and reaction order analyses and also fitted to equivalent circuits. The directions for future work on patterned electrodes with different LTPB and AELT and theoretical calculations to gain further insights into the kinetics and mechanism of the cathode oxygen reduction reaction (ORR) over proton conducting electrolytes are pointed out. 

BaCo0.4Fe0.4Zr0.1Y0.1O3−σ (BCFZY) is a proton, oxygen-ion, and electron-hole conducting cathode material for intermediate temperature solid oxide fuel cells. Its electrode reaction mechanism in air with moisture is not well understood. In this study, three types of symmetrical cells with the same BCFZY cathode were fabricated over three related proton conducting electrolytes: BaZr0.8−xCexY0.1Yb0.1O3−δ (x = 0.1, 0.4, and 0.7). The cathode shows similar performance over three different electrolytes in dry air but different responses to moisture introduction. The differences are hypothesized to relate to the mutual diffusion at the cathode/electrolyte interface. Such a hypothesis is supported by different techniques such as XRD Rietveld refinement of BCFZY cathode in mixtures with different electrolytes after firing, energy-dispersive X-ray spectroscopy (EDS) line scanning for element concentration distribution at the cathode/electrolyte interface, as well as electrochemical test for a related BaCoFeO-type cathode with Zr replaced by Ce.