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$^{−2}$. ... mehrEven 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.