Electrocatalytic MOF‐Carbon Bridged Network Accelerates Li+‐Solvents Desolvation for High Li+ Diffusion toward Rapid Sulfur Redox Kinetics

Abstract Lithium‐sulfur batteries are famous for high energy density but prevented by shuttling effect and sluggish electrochemical conversion kinetics due to the high energy barriers of Li + transport across the electrode/electrolyte interface. Herein, the Li + ‐solvents dissociation kinetics is catalyzed and stimulated by designing a carbon bridged metal‐organic framework (MOF@CC), aimed at realizing increased bare Li + transport for the rapid conversion kinetics of sulfur species. Theoretical simulations and spectroscopic results demonstrate that the bridged MOF@CC well grants a special transport channel for accelerating Li + benefited from aggregated anion/cation clusters. Moreover, the CN bridge between ‐NH 2 ligand in MOF and carbon shell enhances electron exchange, and thus promotes polysulfide catalytic efficiency and hinder polysulfide aggregation and accumulation. With the MOF@CC‐modified separators, the assembled Li/S batteries deliver a reversible capability of 1063 mAh g ‐1 at 0.5 C, a capacity retention of 88% after 100 cycles, and a high‐rate performance of 765 mAh g −1 at 5 C. Moreover, the large areal pouch cell with 100 µm Li foil and lean electrolyte is capable of stabilizing 855 mAh g −1 after 70 cycles. These results well demonstrate the efficiency of catalyzing desolvation for fast Li+ transport kinetics and the conversion of polysulfides.