Bismuth and Fluorine Dual‐Doping of Lithium Argyrodite toward High‐Performance All‐Solid‐State Lithium Metal Batteries

The chlorine‐rich lithium argyrodite is considered a promising superionic conductor electrolyte, but its practical application is limited due to poor air stability and instability toward lithium metal. In this work, BiF3 is proposed as a multi‐functional dopant for electrolyte modification, and the effects on the ionic conductivity, air stability, critical current density, and electrolyte/Li metal interfacial stability are studied. The results show that the doped electrolyte Li5.54P0.98Bi0.02S4.5Cl1.44F0.06 (LPBiSClF0.06) still maintains a relatively high ionic conductivity of 5.37 mS cm−1. Additionally, the formation of BiS45− unit and LiBiS2 phase provides high air/moisture resistibility. Meanwhile, the critical current density of the Li/LPBiSClF0.06/Li cell is increased two‐fold (2.1 mA cm−2). The in‐situ formation of LiF and Li‐Bi alloy at the lithium metal/electrolyte interface plays a key role in achieving high performance. As a result, the assembled LCO@LNO/LPBiSClF0.06/Li battery retains 78.4% of its capacity after 100 cycles at 0.2C.