Nanoporous Ni-Ce0.8Gd0.2O1.9-x thin film cermet SOFC anodes prepared by pulsed laser deposition.

Nickel oxide-gadolinia-doped ceria thin films with a ceria composition of 80 at% Ce and 20 at% Gd were grown by pulsed laser deposition on sapphire and SiO2/Si wafers as well as on yttria stabilized zirconia polycrystalline substrates. Upon reduction of the NiO phase in a H2/N2 atmosphere at 600 degrees C, a stable three-phase, 3-D interconnecting microstructure was obtained of metallic Ni, ceramic, and pores. Coarsening and segregation of the Ni to the surface of the film was observed at higher temperatures. The kinetics of this process depend strongly on the microstructures that can be developed in situ during deposition or post-deposition heat treatments. In situ minimization of Ni-coarsening can be achieved at temperatures as low as 500 degrees C when the deposition pressure does not exceed 0.02 mbar. For films deposited at higher pressure and at temperatures below 800 degrees C, coarsening can be minimized post deposition by annealing in air at 1000 degrees C. The films showed very good metallic conductivity and stability upon thermal cycling in a reducing atmosphere. Redox cycles performed at 600 degrees C between air and H2 induced a loss of connectivity of the metallic phase and consequent degradation of the conductivity. After 16 cycles, corresponding to 65 hrs, the conductivity is reduced by one order of magnitude.

Oxidation states of Co and Fe in Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-delta) (x, y = 0.2-0.8) and oxygen desorption in the temperature range 300-1273 K.

Four compositions of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-delta) were studied for phase, oxygen uptake-release, and transition metal (TM) oxidation states after solid state processing and with in situ heating from 300 to 1273 K in air. X-Ray diffraction showed that all compositions except one had the cubic perovskite structure at all temperatures; that with x, y = 0.2 was a mixture as prepared, becoming predominantly cubic at high temperature. Thermogravimetry showed a reversible oxygen absorption-desorption of approximately +/-1% from 700 to 1273 K. X-Ray absorption and Mössbauer spectroscopy showed a majority TM(3+) valence, with at most 40% TM(4+). Up to a temperature of 1073 K, the TM(4+) was reduced to TM(3+). Further heating of the composition with x, y = 0.2 to 1233 K resulted in the reduction of Co(3+) to Co(2+). Results from room temperature measurements confirm the thermally activated carrier hopping mechanism with charge fluctuations, while the high temperature delocalized carrier conductivity occurs with a small amount of TM reduction and without phase change for the initially cubic samples.