Topology Fortified Anodes Powered High‐Energy All‐Solid‐State Lithium Batteries

Abstract Despite its high theoretical capacity and the lowest electrode potential, the lithium metal (Li°) anode possesses significant volume changes and narrow external pressure tolerance upon cycling, hindering its commercial applications in all‐solid‐state lithium batteries (ASSLBs). Herein, the concept of topology fortified anode (TFA) materials is introduced, featuring a 3D lithiophilic Li 5 B 4 skeleton combined with an ingeniously optimized fraction of electroactive lithium phase, along with broadened external pressure tolerance to synergistically enhance the electrochemical performance of ASSLBs. The unique topological design of the TFA materials empowers them with robust mechanical stability and fast lithium diffusivity, achieving near‐zero volume changes along with a fivefold improvement in external pressure tolerance compared to Li°. An archetypal TFA‐based symmetric cell demonstrates 3.6‐fold higher critical current density than its Li°‐based counterpart, sustaining stable cycling for >6,000 h at 2 mAh cm −2 . When paired with a high‐capacity of FeS 2 cathode, the archetypal TFA‐based full cells achieve 62% active lithium utilization (9.5 mAh cm −2 ), and ≈70% capacity retention after 800 cycles at a high current density of 3.07 mA cm −2 . The findings provide a revolutionary design approach for high‐energy anodes in ASSLBs, advancing not only their development but also battery technologies beyond lithium chemistry.