Anchoring Atomic Ag in Ordered Oxygen Vacancies for High‐Performance Anode‐Free Lithium Metal Batteries

ABSTRACT The uncontrollable growth of lithium dendrites and the formation of unstable solid electrolyte interphase (SEI) on copper current collectors remain critical challenges for the practical application of anode‐free lithium metal batteries (AFLMB). Here, we propose a facile and effective interface engineering strategy by constructing a three‐dimensional film consisting of lithiophilic nano‐sheets on copper foil (CAC@Cu). In the CAC film, Ag atoms are atomically dispersed and anchored at the oxygen vacancy sites within the CeO 2 lattice, inducing a unique atomic rearrangement that promotes highly ordered oxygen vacancy distribution. The resultant current collector exhibits exceptional lithiophilicity, significantly reducing the lithium nucleation overpotential to 23 mV and enhancing the exchange current density. These properties guide uniform and dense lithium deposition while facilitating the formation of a stable, composite SEI rich in inorganic components. Consequently, the CAC@Cu enables a high average Coulombic efficiency of 99.27% in half‐cells, remarkably stable cycling over 2500 h in symmetric cells, and significantly improved capacity retention in anode‐free LiFePO 4 and NCM811 full cells. This work provides profound insights into the mechanism of metal doping via vacancy anchoring and atomic rearrangement, offering a promising interface‐engineering approach for developing high‐performance, dendrite‐free lithium metal batteries.