Strategic Inorganic‐Rich Hybrid Layer Designs for Superior Charge Transport Kinetics in Stabilizing 3D Lithium Metal Hosts

Abstract Lithium metal anodes (LMAs) are highly promising for high energy density batteries, but their practical application is limited by challenges such as dendrite formation, electrolyte depletion, and low coulombic efficiency (CE) due to the instability of the native solid electrolyte interphase (SEI) layer. Therefore, regulating Li‐ion diffusion and electron transport is crucial for overcoming these issues and enhancing the performance of LMAs. This study introduces an inorganic‐rich hybrid layer‐coated carbon framework (IHL@CF) as a 3D lithiophilic host designed to stabilize and optimize the SEI layer. The IHL@CF features an outer inorganic‐rich hybrid layer (IHL) composed of AgLi alloys and Li ₂ S/LiF, which promotes uniform Li deposition, suppresses dendrite growth, and reinforces SEI stability. The inner hard carbon layer facilitates effective Li‐ion adsorption and intercalation, preserving the mechanical integrity and porosity of the 3D framework. This multilayer structure enables the IHL@CF to achieve long‐term cyclability in symmetrical cells and high capacity retention in full cells. These findings offer valuable insights for designing artificial SEI layer integrated with lithiophilic 3D host, advancing the development of dendrite‐free LMAs.