Interfacial Reconstruction of Li ⁺ Solvation Shell for Fast Diffusion Kinetics in Low‐Temperature Dendrite‐Free Li Metal Battery Enabled by Atomic Catalysts

Low‐temperature lithium‐metal batteries (LT‐LMBs) are increasingly pursued for higher energy density and extended cycle life, yet suffer from severely depressed interfacial Li + desolvation/diffusion kinetics due to the enlarged solvation structures as well as organic electrolyte solidification, ultimately inducing much higher barriers to overcome. Herein, the interfacial structure of the Li + solvation shell has been remodeled for fast diffusion kinetics in low‐temperature surroundings via an atomic catalyst. Briefly, the interfacial electron‐delocalization catalysis engineered by anchoring single‐atomic Zn into defect‐rich vanadium trioxide (SAZn@DRVO) was developed to expedite the Li + desolvation/diffusion kinetics under a low‐temperature environment, achieving stable operation even at −50°C. As verified by coupled microscopic imaging, chemical valence‐ and electronic‐state analyses, and electrochemical validation, the optimal SAZn@DRVO‐Li electrode delivers long‐cycling stability up to 1200 h at −10°C. Even when increasing the plating capacity to 5 mAh cm −2 , it retains robust dendrite‐free cycling stability for 400 h at 2 mA cm −2 . Even down to −50°C, a stable ultralow overpotential below 550 mV is achieved without short circuit. The optimal full cell delivers a high‐capacity retention of ∼100% after 120 cycles at 0.2C under −20°C, highlighting the feasibility of atom‐level catalysis for the development of durable LT‐LMBs.