Chiral LiPS–LiTFSI dimers enabling biomimetic electrocatalysis in lithium||sulfur batteries

Lithium||sulfur batteries promise high energy density but are plagued by sluggish polysulfide conversion under lean-electrolyte conditions. Here we show the formation of chiral LiPS-LiTFSI dimers, fundamentally reshaping the intrinsic chemistry of polysulfides. Building on this finding, we design biomimetic MOF catalysts (MOF-L-His-Cu) in which L-histidine-Cu centers selectively recognize the chiral dimers, accelerating sulfur redox via enzyme-like kinetics. Such MOF-L-His-Cu catalyst achieves 1.84-fold higher activity than its D-enantiomer, enabling lithium||sulfur pouch cells with specific energy of 408 Wh kg−1 (based on the mass of the whole pouch cell deducting the package) at high sulfur loading (12 mg cm−2) and low electrolyte/sulfur ratio (3 μL mg−1). Our findings suggest that chiral coordination could be a previously overlooked factor in lithium||sulfur chemistry. This insight may inform the design of selective electrocatalysts for next-generation energy storage, representing a potential step forward in the field. Lithium||sulfur batteries face slow lithium polysulfide (LiPS) conversion under lean electrolyte condition. Here, authors identify chiral LiPS-LiTFSI dimers and design biomimetic MOF catalysts with L-histidine-Cu for selective recognition and enzyme-like kinetics. The catalyst enables pouch cells with 408 Wh kg−1 (without packaging), underscoring chiral coordination in Li||S chemistry.