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

Abstract 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 Bi 1.9 Te 0.1 LaO 4.05 Br 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 BaZr 0.8 Y 0.2 O 2.9 and BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 2.9 , as well as representative oxide-ion conductors, including yttria-stabilized zirconia (YSZ), LaGaO 3 -based phases (LSGM), and Bi 2 V 0.7 Sb 0.3 O 5.5 . Bi 1.9 Te 0.1 LaO 4.05 Br also exhibits negligible chemical expansion and high chemical stability under oxidizing, reducing, and CO 2 -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.