Disulfide‐Assisted Organic Polysulfide Cathode Design Enables Improved Kinetics in Lithium‐Sulfur Batteries

Lithium‐sulfur batteries (LSBs) is fundamentally limited by the “shuttle effect” and poor kinetics. To address these challenges, this study proposes an approach through developing a novel organic polysulfide composite cathode with high sulfur loading. By implementing a radical reaction between elemental sulfur and a disulfide of tetramethylthiuram disulfide (TMTD), linear organic polysulfides (TMTD‐S) containing over 70 wt% sulfur are successfully synthesized. This kind of material features a covalently bonded R‐Sn‐R (R=C 2 H 6 N(S)) backbone. Further compounding with the conductive carbon (ECP600JD) and integrating into a paper‐based electrode help to improve the electrode's conductivity and optimized ion transport pathways. The obtained TMTD‐24S@ECP600JD cathode demonstrates a capacity retention rate of 79.1% after 250 cycles at 0.2C, far superior to traditional S@ECP600JD materials (14.1%). By increasing the sulfur content in TMTD, higher sulfur‐content linear organic polysulfides are also obtained. Among them, the TMTD‐54S@ECP600JD with 88 wt% sulfur content exhibits the best electrochemical performance and the highest lithium‐ion diffusion coefficient, delivering an initial discharge capacity of 941 mAh g −1 at 0.2C, with a capacity retention rate of 82.1% after 200 cycles. Even at a high rate of 2C, it still maintained a high specific capacity of 638.3 mAh g −1 , making it a potential material for high‐performance Li‐S batteries.