Fast Ion Transport in Li‐Rich Alloy Anode for High‐Energy‐Density All Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state Li batteries (ASSLBs) with solid‐polymer electrolytes are considered promising battery systems to achieve improved safety and high energy density. However, Li dendrite formation at the Li anode under high charging current density/capacity has limited their development. To tackle the issue, Li‐metal alloying has been proposed as an alternative strategy to suppress Li dendrite growth in ASSLBs. One drawback of alloying is the relatively lower operating cell voltages, which will inevitably lower energy density compared to cells with pure Li anode. Herein, a Li‐rich Li 13 In 3 alloy electrode (LiRLIA) is proposed, where the Li 13 In 3 alloy scaffold guides Li nucleation and hinders Li dendrite formation. Meanwhile, the free Li can recover Li's potential and facilitate fast charge transfer kinetics to realize high‐energy‐density ASSLBs. Benefitting from the stronger adsorption energy and lower diffusion energy barrier of Li on a Li 13 In 3 substrate, Li prefers to deposit in the 3D Li 13 In 3 scaffold selectively. Therefore, the Li–Li symmetric cell constructed with LiRLIA can operate at a high current density/capacity of 5 mA cm −2 /5 mAh cm −2 for almost 1000 h.