LAUSR

Low‐temperature lithium metal batteries (LT‐LMBs) are increasingly desired for higher energy density and longer lifespan. However, due to organic electrolyte solidification, LT‐LMBs are impeded by huge barriers resulting from the hindrance of larger solvation shells with strong ion‐dipole interactions, leading to depressive Li kinetics and severe dendrite formation. Herein, interfacial catalysis by constructing electron delocalization d‐orbital metal oxides toward the ion‐dipole interactions is pioneered to accelerate the larger Li(solvents)x+ dissociation under the low‐temperature environment. Specifically, various kinds of d‐orbital metal oxides (M = Ti, V, Fe, Co) with oxygen defect modulation are systematically screened and investigated for breaking the ion‐dipole interactions, and the prototyped titanium oxide with adjustable electron delocalization behave the best, as confirmed by electrochemical and theoretical experiments. Consequently, optimized Li electrodes withstand environmental robustness from 25 to −50°C, and stabilize long‐term cycling up to 1800 h and high Coulombic efficiency without any short‐circuit under −20°C. The as‐fabricated Li–S full cell enables a high‐capacity retention of 88% at 0.2 C over 200 cycles, and the high‐loading Li‐LiNi0.8Co0.1Mn0.1O2 cell (≈20 mg cm−2) demonstrates excellent capacity retention ≈100% under 0°C, providing a new guideline for adopting a catalytic strategy for achieving advanced LT‐LMBs.