Interfacial “Single‐Atom‐in‐Defects” Catalysts Accelerating Li⁺ Desolvation Kinetics for Long‐Lifespan Lithium‐Metal Batteries

Abstract The lithium‐metal anode is a promising candidate for realizing high‐energy‐density batteries owing to its high capacity and low potential. However, several rate‐limiting kinetic obstacles, such as the desolvation of Li⁺ solvation structure to liberate Li⁺, Li⁰ nucleation, and atom diffusion, cause heterogeneous spatial Li‐ion distribution and fractal plating morphology with dendrite formation, leading to low Coulombic efficiency and depressive electrochemical stability. Herein, differing from pore sieving effect or electrolyte engineering, atomic iron anchors to cation vacancy‐rich Co_1−xS embedded in 3D porous carbon (SAFe/CVRCS@3DPC) is proposed and demonstrated as catalytic kinetic promoters. Numerous free Li ions are electrocatalytically dissociated from the Li⁺ solvation complex structure for uniform lateral diffusion by reducing desolvation and diffusion barriers via SAFe/CVRCS@3DPC, realizing smooth dendrite‐free Li morphologies, as comprehensively understood by combined in situ/ex situ characterizations. Encouraged by SAFe/CVRCS@3DPC catalytic promotor, the modified Li‐metal anodes achieve smooth plating with a long lifespan (1600 h) and high Coulombic efficiency without any dendrite formation. Paired with the LiFePO₄ cathode, the full cell (10.7 mg cm⁻²) stabilizes a capacity retention of 90.3% after 300 cycles at 0.5 C, signifying the feasibility of using interfacial catalysts for modulating Li behaviors toward practical applications.