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.

Synergized Interface Engineering and Alloying Strategy for In Situ Construction of a Three-Dimensional Lithiophilic Carbon Skeleton: Motivating High-Performance Lithium Metal Batteries

“…The lower overpotential and longer cycling life of LiSn@CN@CC reveal that the introduction of the LiSn alloy and in situ modification of Li 3 N can uniformly guide the Li deposition during cycling, promoting rapid diffusion of Li during stripping/electroplating and achieving stable cycling under a high current density. 35,36 As shown in Figure 3b, Li@CC and Li foil electrodes present a short-circuit phenomenon after 60 h. However, the LiSn@CN@CC electrode exhibits a apparently enhanced cycling performance over 200 h with a low overpotential of 50 mV. Additionally, LiSn@CN@CC anodeassembled symmetric batteries can maintain relatively stable cycling under the stripping/plating capacity of 10.0 mAh cm −2 at 5.0 mA cm −2 , presenting a sharp contrast to Li foil and Li@CC symmetrical batteries (Figure S2 of the Supporting Information).…”

Laser‐Assisted Interfacial Engineering for High‐Performance All‐Solid‐State Batteries

“…Additionally, Hui et al prepared laser-induced Cu 3 Sn/Sn/ SnO 2 interlayers to improve the interfacial stability between the Cu CC and Li metal anode. [118] The laser-deposited Sn/SnO 2 layers can store Li ions and induce homogeneous nucleation of Li. Moreover, the Cu 3 Sn layer improved the adhesion between the interlayer and the Cu foam.…”

Lithium Dredging and Capturing Dual‐Gradient Framework Enabling Step‐Packed Deposition for Dendrite‐Free Lithium Metal Anodes

“…[19] Unfortunately, the intrinsic lithiophobic property of general 3D porous frameworks such as metal foams and carbon skeletons, resulting in a high nucleation barrier, which extremely motivates the growth of Li dendrites. For that, lithiophilic modification by decorating with specific components such as single atoms, [20] metal seeds, [21,22] and compounds, [23,24] has been verified to reduce the lithium nucleation barrier and induce the uniform Li plating. [25] However, under high current density while electrochemical kinetics is dominated by ions diffusion, a large Li + concentration difference will be generated between electrode and separator, and the lithiophilic frameworks will be disabled.…”