A Bismuth‐Derived, Inorganic‐Rich Artificial Solid Electrolyte Interphase Enables a Stable and Dendrite‐Free Lithium‐Metal Anode in Rechargeable Batteries

ABSTRACT Rechargeable batteries operated based on lithium‐metal anodes represent a major breakthrough in the field of electrochemical energy storage. However, the Li‐metal batteries (LMBs) are practically hindered by unstable anode chemistry that invites dendrite formation and parasitic reactions, and accounts for rapid battery failure and safety issues. Here we show that a bismuth‐based, inorganic‐rich artificial solid electrolyte interphase (ASEI) helps to effectively stabilize the anode‐electrolyte interface. The interphase is derived from the in situ reaction between Li and Bi(CF ₃ SO ₃ ) ₃ ‐LiNO ₃ salt mixture, and consists of multiple components including Li ₃ Bi, Bi, LiF, and Li ₃ N. The inorganic‐rich ASEI demonstrates high electrolyte wettability, lithiophilicity, and mechanical strength, and a low Li ⁺ diffusion energy barrier, so that it promotes uniform Li plating/stripping while effectively suppressing the dendrite formation and volume variation. By applying ASEI, a Li||Li symmetric battery maintains stable cycling for > 1000 h at an ultra‐high current density of 10 mA cm ⁻² and an areal capacity of 10 mAh cm ⁻² . LMBs that pair the ASEI‐modified Li anode with various layered oxide cathodes exhibit improved cycling and rate performance, and a 10‐Ah Li‐metal pouch cell demonstrates favorable cycling performance at a high specific energy of > 460 Wh kg ⁻¹ , showing promise for the next‐generation electrochemical energy storage.