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.