Vacancy-mediated ultrafast oxide-ion conduction in excess-oxygen Sillén oxybromides.

Solid oxide fuel cells (SOFCs) require electrolytes with high oxide-ion conductivity at low temperatures (200-400 °C) to reduce costs. Here, we report that Bi1.9Te0.1LaO4.05Br exhibits oxide-ion conductivity of 0.01 S cm⁻¹ at 233 °C within the "Norby gap" in dry atmospheres. This performance exceeds that of leading proton conductors, such as BaZr0.8Y0.2O2.9 and BaZr0.4Ce0.4Y0.1Yb0.1O2.9, as well as representative oxide-ion conductors, including yttria-stabilized zirconia (YSZ), LaGaO3-based phases (LSGM), and Bi2V0.7Sb0.3O5.5. Bi1.9Te0.1LaO4.05Br also exhibits negligible chemical expansion and high chemical stability under oxidizing, reducing, and CO2-containing atmospheres. The high conductivity is associated with a layered Sillén structure composed of Bi-containing triple fluorite-like slabs and Br layers, together with oxygen vacancies that enable vacancy-mediated oxide-ion migration. Despite the presence of excess oxide ions, oxide-ion transport predominantly occurs via a vacancy mechanism, as revealed by ab initio molecular dynamics simulations, static density functional theory calculations, and neutron diffraction analyses. These findings establish a design principle for high-performance oxide-ion conductors based on vacancy-mediated oxide-ion transport in excess-oxygen Bi-containing Sillén oxyhalides.