LAUSR

Abstract Lithium (Li) has garnered considerable attention as an alternative anodes of next‐generation high‐performance batteries owing to its prominent theoretical specific capacity. However, the commercialization of Li metal anodes (LMAs) is significantly compromised by non‐uniform Li deposition and inferior electrolyte–anode interfaces, particularly at high currents and capacities. Herein, a hierarchical three‐dimentional structure with CoSe2‐nanoparticle‐anchored nitrogen‐doped carbon nanoflake arrays is developed on a carbon fiber cloth (CoSe2–NC@CFC) to regulate the Li nucleation/plating process and stabilize the electrolyte–anode interface. Owing to the enhanced lithiophilicity endowed by CoSe2–NC, in situ‐formed Li2Se and Co nanoparticles during initial Li nucleation, and large void space, CoSe2–NC@CFC can induce homogeneous Li nucleation/plating, optimize the solid electrolyte interface, and mitigate volume change. Consequently, the CoSe2–NC@CFC can accommodate Li with a high areal capacity of up to 40 mAh cm–2. Moreover, the Li/CoSe2–NC@CFC anodes possess outstanding cycling stability and lifespan in symmetric cells, particularly under ultrahigh currents and capacities (1600 h at 10 mA cm−2/10 mAh cm−2 and 5 mA cm−2/20 mAh cm−2). The Li/CoSe2–NC@CFC//LiFePO4 full cell delivers impressive long‐term performance and favorable flexibility. The developed CoSe2–NC@CFC provides insights into the development of advanced Li hosts for flexible and stable LMAs.