Nanosecond Pulsed Laser‐Assisted Deposition to Construct a 3D Quasi‐Gradient Lithiophilic Skeleton for Stable Lithium Metal Anodes

Abstract The continuous growth of Li dendrites and volumetric deformation of Li severely impede the commercial application of Li metal anodes. To regulate Li stripping/plating, electrodeposition or magnetron sputtering is extensively utilized to fabricate lithiophilic‐metal deposited 3D Li hosts. However, the binding force between lithiophilic‐metal and host is weak, inevitably leading to numerous cracks/defects of lithiophilic‐surface‐layer during Li plating/stripping. Herein, a quasi‐gradient (Cu‐Cu₃Sn‐Sn‐SnO₂) 3D skeleton consisting of hierarchical Sn/SnO₂ composite metallurgically bonded to copper foam through Cu₃Sn alloy (LAD‐SSC@CF) is designed, and prepared in one‐step by a nanosecond‐pulsed‐laser‐assisted deposition strategy. The homogeneous Li nucleation sites provided by Li₂₂Sn₅ formed by the reaction of Sn/SnO₂ with Li can inhibit Li dendrites growth. Meanwhile, the porous space and strong bonding of Cu₃Sn layer avoid structural deterioration of anodes. Consequently, a symmetric cell based on LAD‐SSC@CF@Li exhibits an outstanding cycling stability of 1500 h at 1 mA cm⁻². In particular, a full cell with LiFePO₄ cathode provides good capacity retention of 81.3% at 5 C after 600 cycles. Moreover, the successful preparation of other composite materials (In, Zn, Sn‐Bi, etc.) loading on various substrates (Kapton film, ceramic, copper foil, etc.) demonstrates the versatility of pulsed‐laser‐assisted deposition strategy for preparing battery materials.