Fluoride-Ion Conduction and Wide Electrochemical Stability Window for Ca10-x(HPO4)x(PO4)6-xF2-x (0 ≤ x ≤ 0.6).

F--conducting apatites have unique structural features and thus have emerged as promising electrolytes for next-generation all-solid-state fluoride-ion batteries (FIBs). Structural and morphological analyses indicate that OH- in Ca10-x(HPO4)x(PO4)6-x(OH)2-x (x = 0, 0.1, 0.2, 0.25, 0.3, 0.4, 0.5, and 0.6) are exchanged with F- via chemical fluorination at 150 °C using XeF2. We investigate the F- conductivity of Ca10-x(HPO4)x(PO4)6-xF2-x synthesized with various x values. AC impedance spectroscopy reveals a large increase in ionic conductivity, reaching 5 × 10-5 S cm-1 at 80 °C, with a low activation energy of 0.15 eV for x = 0.3. The material is chemically stable at least up to 1200 °C. Due to the robust crystalline framework containing Ca, the electrochemical stability window (ESW) expands in the active direction, and an extremely high ESW of over 5 V is achieved. Although further increasing the ionic conductivity of this material remains a challenge, its excellent ESW is a unique advantage over existing solid electrolytes in next-generation FIBs, in which safety is a priority during high-voltage operation and in harsh environments.