Concerted Superionic‐Electron Flow Guides a Sulfur‐Redox Highway in High‐Rate Li–S Batteries

ABSTRACT Designing multifunctional electrocatalysts that simultaneously promote rapid Li + , e − , and polysulfide anion (S x 2− ) transport is critical for achieving high‐rate lithium–sulfur (Li–S) batteries. Herein, C─F hybridization is employed to broaden the Li + migration channels, while embedded Sn particles synergistically accelerate the e − /S x 2− , inducing the solid‐phase conversion pathway to occur earlier at a high voltage plateau. Under ultrafast charge/discharge conditions, the electrode delivers a high reversible capacity of 406 mAh g − 1 . The unique Sn–F interfacial electronic structure remarkably facilitates the charge delocalization of Li 2 S 4 molecules, forming a relaxed interfacial configuration that promotes the reconstruction and cleavage of bridged S─S bonds. Consequently, the apparent rate constant (k s ) for the quasi‐first‐order Li 2 S 4 conversion reaction is increased threefold, enabling Ah‐level pouch cells to achieve reversible cycling at 5 C. This study demonstrates a dynamic modulation strategy of bridging‐bond structures, providing fundamental insights into the “ultrafast ion/electron flow” mechanism and offering development guidance for high‐power Li–S batteries.