Anchoring Active Li Metal in Oriented Channel by In Situ Formed Nucleation Sites Enabling Durable Lithium‐Metal Batteries

Abstract Lithium metal is the ultimate anode material for pursuing the increased energy density of rechargeable batteries. However, fatal dendrites growth and huge volume change seriously hinder the practical application of lithium metal batteries (LMBs). In this work, a lithium host that preinstalled CoSe nanoparticles on vertical carbon vascular tissues (VCVT/CoSe) is designed and fabricated to resolve these issues, which provides sufficient Li plating space with a robust framework, enabling dendrite‐free Li deposition. Their inherent N sites coupled with the in situ formed lithiophilic Co sites loaded at the interface of VCVT not only anchor the initial Li nucleation seeds but also accelerate the Li⁺ transport kinetics. Meanwhile, the Li₂Se originated from the CoSe conversion contributes to constructing a stable solid‐electrolyte interphase with high ionic conductivity. This optimized Li/VCVT/CoSe composite anode exhibits a prominent long‐term cycling stability over 3000 h with a high areal capacity of 10 mAh cm⁻². When paired with a commercial nickel‐rich LiNi_0.83Co_0.12Mn_0.05O₂ cathode, the full‐cell presents substantially enhanced cycling performance with 81.7% capacity retention after 300 cycles at 0.2 C. Thus, this work reveals the critical role of guiding Li deposition behavior to maintain homogeneous Li morphology and pave the way to stable LMBs.