Discovery of a Rare-Earth-Free Oxide-Ion Conductor CaGaO by Screening through Bond Valence-Based Energy Calculations, Synthesis, and Characterization of Structural and Transport Properties.

In this work, we have discovered CaGaO as a rare-earth-free oxide-ion conductor by a combined technique of bond valence (BV)-based energy calculations, synthesis, and characterization of structural and transport properties. Here, the energy barriers for oxide-ion migration () of 217 Ga-containing oxides were calculated by the BV method to screen the candidate materials of oxide-ion conductors. We chose the orthorhombic calcium gallate CaGaO as a candidate of oxide-ion conductors, because CaGaO had a relatively low . CaGaO was synthesized by a solid-state-reaction method. Rietveld analyses of time-of-flight neutron and synchrotron X-ray powder diffraction data of CaGaO indicated an orthorhombic 2 layered crystal structure consisting of Ca and (GaO) units where the (GaO) units form the two-dimensional (2D) corner-sharing GaO tetrahedral network. The electromotive force measurements with an oxygen concentration cell showed that the transport numbers of the oxide ion were 0.69 at 1073 K and 0.84 at 973 K in CaGaO, which indicates that the major carrier of CaGaO is the oxide ion. The oxide-ion conductivity was estimated to be 1.03(8) × 10 S cm at 1073 K. The total electrical conductivity and impedance spectroscopy measurements of this CaGaO sample indicated that the bulk conductivity was much higher than the grain-boundary conductivity and that the total conductivity was equivalent to the bulk conductivity. The bond valence-based energy landscape calculated using the refined crystal parameters of CaGaO indicated 2D oxide-ion diffusion in the layered tetrahedral network [(GaO) unit]. It was found that the structural and transport properties of CaGaO are similar to those of LaSrGaO melilite.