Constructing Binder‐ and Carbon Additive‐Free Organosulfur Cathodes Based on Conducting Thiol‐Polymers through Electropolymerization for Lithium‐Sulfur Batteries

Herein, the concept of constructing binder‐ and carbon additive‐free organosulfur cathode was proved based on thiol‐containing conducting polymer poly(4‐(thiophene‐3‐yl) benzenethiol) (PTBT). The PTBT featured the polythiophene‐structure main chain as a highly conducting framework and the benzenethiol side chain to copolymerize with sulfur and form a crosslinked organosulfur polymer (namely S/PTBT). Meanwhile, it could be in‐situ deposited on the current collector by electro‐polymerization, making it a binder‐free and free‐standing cathode for Li‐S batteries. The S/PTBT cathode exhibited a reversible capacity of around 870 mAh g(−1) at 0.1 C and improved cycling performance compared to the physically mixed cathode (namely S&PTBT). This multifunction cathode eliminated the influence of the additives (carbon/binder), making it suitable to be applied as a model electrode for operando analysis. Operando X‐ray imaging revealed the remarkable effect in the suppression of polysulfides shuttle via introducing covalent bonds, paving the way for the study of the intrinsic mechanisms in Li‐S batteries.