Lithiophilic V₂CT_x/MoO₃ Hosts with Electronic/Ionic Dual Conductive Gradients for Ultrahigh‐Rate Lithium Metal Anodes

Abstract Lithium (Li) metal is considered as a promising anode material for high‐energy batteries; yet, its practical application is hindered by uncontrolled Li dendrite growth, especially at a high rate. Herein, a dual conductive gradient V₂CT_x/MoO₃ (DG‐V₂CT_x/MoO₃) host that integrates electronic/ionic conductive gradients and lithiophilicity is prepared by layer‐by‐layer assembly for dendrite‐free Li anodes. Gradient LiF deriving from different amount of V₂CT_x endows a good ionic conductive gradient; while, MoO₃ is regarded as a spacer to avoid the restacking of V₂CT_x, increasing space for Li deposition. The dual conductive gradients effectively optimize the current density and Li⁺ flux distribution at the bottom, achieving fast reduction of Li⁺ and a “bottom–up” Li deposition mode. Meanwhile, the lithiophilic V₂CT_x and MoO₃ guide the homogeneous Li growth. As a result, the symmetrical half‐cells based on DG‐V₂CT_x/MoO₃@Li anodes conduct 700 h at 5 mAh cm⁻² and 20 mA cm⁻². The DG‐V₂CT_x/MoO₃@Li||LiFePO₄ full‐cells maintain a capacity retention of 85.4% after 1350 cycles at 2 C. Remarkably, the DG‐V₂CT_x/MoO₃@Li||LiNi_0.6Co_0.2Mn_0.2O₂ full‐cells can run 150 cycles with 80.6% capacity retention even at harsh conditions. The well‐adjusted materials and structures with both dual conductive gradients and lithiophilic properties will bring inspiration for novel material design of other metal batteries.