Catalytic and Dual‐Conductive Matrix Regulating the Kinetic Behaviors of Polysulfides in Flexible Li–S Batteries

The main challenge in developing foldable Li–S batteries (LSB) lies in developing an electrode that is ultraflexible, conductive, and catalytic for dissolved lithium polysulfides (LiPSs). In this paper, lightweight macromolecule graphitic carbon nitride (g‐C₃N₄) film and a conductive polymer (CP) of poly(3,4‐ethylenedioxythiophene) shell are introduced into flexible LSBs by compositing with carbon cloth (CC). In the designed hybrid of CP/g‐C₃N₄@CC, 2D g‐C₃N₄ is used in the form of an effective trapper and functions as a continuous catalytic layer for LiPSs via the formation of pyridinic‐N‐Li bonds. This is revealed by both experimental investigations and theoretical analysis. The sandwich‐like CC and CP simultaneously bring an omnidirectional conductive network for fast interfacial reaction kinetics. With these benefits, the self‐supported CP/g‐C₃N₄@CC forms a powerful interaction system to fully in situ “lock” LiPSs in the commercial CC matrix. Thus, a substantially enhanced electrochemical performance is obtained at a high sulfur loading (4.7 mg cm^–2) even operating in a pouch cell. This work may provide a potential avenue for practical use of high‐performance LSBs toward flexible energy‐storage devices.