Effect of composition of (La0.8Sr0.2MnO3-Y2O3-stabilized ZrO2) cathodes: Correlating three-dimensional microstructure and polarization resistance

Composite La0.8Sr0.2MnO3 (LSM)-Y2O3-stabilized ZrO2 (YSZ) cathodes with compositions ranging from 30:70 to 70:30 wt.% LSM:YSZ were studied both electrochemically and microstructurally. Polarization resistance was lowest for the 50wt.% YSZ composition, and increased symmetrically as the composition deviated from this value. Serial-sectioning using focused ion beam-scanning electron microscopy was implemented to reconstruct the three-dimensional cathode microstructure. Various averaged structural parameters were determined versus composition. including phase volume fractions, surface area densities, total triple-phase boundary (TPB) densities, interfacial curvatures, phase tortuosities, and the levels of phase connectivity. Typically >90% of the pore and YSZ networks were found to be intra-connected to the surrounding phase, but the LSM networks showed lower connected fractions, as low as 37.5% for a LSM weight fraction of 30%. The composition dependences of the total TPB density and electrochemically-active TPB density (i.e., TPB's on three fully intra-connected phases) were shown to agree reasonably well with simple sphere-packing structural models. An electrochemical model that accounted for the linear-specific resistance of TPB's, phase intra-connectivity, and oxygen ion transport in the YSZ as influenced by its tortuosity, was found to provide reasonable agreement with the measured polarization resistance versus composition. (C) 2009 Elsevier B.V. All rights reserved.