High oxide-ion conductivity through the interstitial oxygen site in Ba7Nb4MoO20-based hexagonal perovskite related oxides

Abstract

Oxide-ion conductors are important in various applications such as solid-oxide fuel cells. Although zirconia-based materials are widely utilized, there remains a strong motivation to discover electrolyte materials with higher conductivity that lowers the working temperature of fuel cells, reducing cost. Oxide-ion conductors with hexagonal perovskite related structures are rare. Herein, we report oxide-ion conductors based on a hexagonal perovskite-related oxide Ba₇Nb₄MoO₂₀. Ba₇Nb_3.9Mo_1.1O_20.05 shows a wide stability range and predominantly oxide-ion conduction in an oxygen partial pressure range from 2 × 10^-26 to 1 atm at 600 °C. Surprisingly, bulk conductivity of Ba₇Nb_3.9Mo_1.1O_20.05, 5.8 × 10^-4 S cm^-1, is remarkably high at 310 °C, and higher than Bi₂O₃- and zirconia-based materials. The high conductivity of Ba₇Nb_3.9Mo_1.1O_20.05 is attributable to the interstitial-O5 oxygen site, providing two-dimensional oxide-ion O1-O5 interstitialcy diffusion through lattice-O1 and interstitial-O5 sites in the oxygen-deficient layer, and low activation energy for oxide-ion conductivity. Present findings demonstrate the ability of hexagonal perovskite related oxides as superior oxide-ion conductors.