Heteronuclear Dual‐Atom Catalysis Boosts Reversible Li 2 S Deposition–Decomposition for Wide‐Temperature Lithium–Sulfur Batteries

ABSTRACT Wide‐temperature operation is essential for practical application of Li─S batteries. Constructing efficient electrocatalysts is an effective strategy to simultaneously alleviate sluggish conversion kinetics at low temperatures and aggravated lithium polysulfide shuttling at high temperatures. Herein, a heteronuclear Cu─Co dual‐atom catalyst‐modified separator (CuCo DACs@PP) was constructed to establish a relay‐catalytic pathway for bidirectional sulfur conversion. Mechanistic studies reveal that Cu sites exhibit stronger π‐bonding orbital overlap with Li 2 S, which lowers the nucleation barrier, while Co sites display pronounced π* antibonding contributions that facilitate Li 2 S activation. The electronically distinct yet spatially coupled Cu and Co sites jointly establish an orbital‐differentiated deposition–decomposition relay pathway, thereby suppressing insulating Li 2 S passivation and maintaining reversible sulfur redox kinetics under thermal perturbation. The CuCo DACs@PP cell operates stably from −20°C to 60°C. This work highlights the potential of atomically dispersed bimetallic catalysts for regulating kinetics over a wide‐temperature range.