Stable all-solid-state lithium metal batteries enabled by ultrathin LiF/Li3Sb hybrid interface layer

•A simple and scalable spray painting method is used to treat commercial Li foils (∼100 μm) to get the ultrathin LiF/Li3Sb hybrid interface layer modified Li anode (SbF3@Li).•The assembled all-solid-state symmetric SbF3@Li cell can cycle stably at a high current density of 0.6 mA·cm–2 for 0.2 mAh·cm–2 and show an extended cycle life over 300 h at 0.2 mA·cm–2 for 0.2 mAh·cm–2, while the LiFePo4|PEO-LLZTO|SbF3@Li cell maintained a high average coulombic efficiency of 99.4% and good capacity retention of 94.5% after 200 cycles.•The in-situ optical microscopy is used to observe the interface of SbF3@Li/PEO-LLZTO during Li deposition directly at room temperature.•The enhanced electrochemical performance and stability of SbF3@Li can be ascribed to the uniform deposition of Li on the surface and bottom of the hybrid interface layer.