Strengthened d-p Orbital Hybridization through Asymmetric Coordination Engineering of Single-Atom Catalysts for...

Although single-atom catalysts (SACs) have been largely explored in lithium-sulfur (Li-S) batteries, the commonly reported nonpolar transition metal-N₄ coordinations only demonstrate inferior adsorption and catalytic activity toward shuttled lithium polysulfides (LiPSs). Herein, single Fe atoms with asymmetric coordination configurations of Fe-N₃C₂-C were precisely designed and synthesized as efficient immobilizer and catalyst for LiPSs. The experimental and theoretical results elucidate that the asymmetrically coordinated Fe-N₃C₂-C moieties not only enhance the LiPSs anchoring capability by the formation of extra π-bonds originating from S p orbital and Fe d/d orbital hybridization but also boost the redox kinetics of LiPSs with reduced Li₂S precipitation/decomposition barrier, leading to suppressed shuttle effect. Consequently, the Li-S batteries assembled with Fe-N₃C₂-C exhibit high areal capacity and cycling stability even under high sulfur loading and lean electrolyte conditions. This work highlights the important role of coordination symmetry of SACs for promoting the practical application of Li-S batteries.