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Hole-Proton Mixed Conduction of Perovskite-Oxide Thin Film with Oxygen Vacancies and Lattice Distortion for SOFC Electrode

Tuesday, 25 July 2017
Grand Ballroom East (The Diplomat Beach Resort)
T. Higuchi, S. Furuichi, W. Namiki, M. Takayanagi (Tokyo University of Science), M. Minohara (High Energy Accelerator Research Organizaton), K. Horiba, H. Kumigashira (High Energy Accelerator Research Organization), and T. Tsuchiya (NIMS)
Acceptor-doped BaPrO3 bulk ceramic is a proton conducting material in the intermediate-temperature (IMT) region from 300 to 700 °C. In particular, the electrical conductivity at 500 °C of Gd3+- or Yb3+-doped BaPrO3 is ~1.0×101 Scm1 in wet atmosphere. Furthermore, the occurrence of electron (or hole)–ion mixed conduction, which is expected as the electrode material of a solid state fuel cell (SOFC) using an oxide proton conductor, has also been proposed in the IMT region of Yb3+-doped BaPrO3.

In this study, in-plane-oriented BaPrO3−δ thin film with mixed valence states has been prepared on an Al2O3(0001) substrate by RF magnetron sputtering. With increasing crystallization temperature (Tsub), the lattice constant decreases and the orientation changes from the a-axis to the b-axis. The thin film prepared above Tsub = 800 °C exhibits a higher proton conductivity than bulk ceramics. The conductivity below 400 °C decreases with oxygen gas partial pressure, indicating the existence of hole-ion mixed conduction. The valence band consists of O 2p states hybridized with the Pr4+ (4f0) and Pr3+ (4f1L) states, which are closely related to the mixed conduction. The energy difference between the top of the valence band and the Fermi level corresponds to the activation energy of holes for the total conductivity below 400 °C.