Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La_0.6Sr_0.4CoO_3−δ Thin Film Electrodes

Pulsed laser deposited La_0.6Sr_0.4CoO_3−δ (LSC) thin film electrodes on yttria stabilized zirconia (YSZ) single crystals were investigated by impedance spectroscopy, time of flight secondary ion mass spectrometry (ToF-SIMS) and inductively coupled plasma optical emission spectrometry (ICP-OES). Effects caused by different film deposition temperatures, thermal annealing and chemical etching were studied. Correlations between changes in electrode polarization resistance of oxygen reduction and surface composition were found. At high deposition temperatures and after thermal annealing an inhomogeneous cation distribution was detected in the surface-near region, most manifest in a significant Sr enrichment at the surface. An activating effect of chemical etching of LSC is described, which can lower the polarization resistance by orders of magnitude. Chemistry behind this activation and thermal degradation was analyzed by ToF-SIMS and ICP-OES measurements of in-situ etched LSC films. The latter allow quantitative depth resolved compositional analysis with nominally sub nm resolution. High resolution scanning electron microscopy images illustrate the accompanying changes in surface morphology. All measurements suggest that stoichiometric LSC surfaces intrinsically exhibit very high activity towards oxygen reduction.