Integration of Graphene, Nano Sulfur, and Conducting Polymer into Compact, Flexible Lithium–Sulfur Battery Cathodes with Ultrahigh Volumetric Capacity and Superior Cycling Stability for Foldable Devices

Abstract Lithium–sulfur batteries, as one of the most promising next‐generation batteries, attract tremendous attentions due to their high energy density and low cost. However, their practical application is hindered by their short cycling life and low volumetric capacity. Herein, compact, flexible, and free‐standing films with a sandwich structure are designed simply by vacuum filtration, in which nanosulfur is homogenously coated by graphene and poly(3,4‐ethylene‐dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This unique hierarchical structure not only provides a highly conductive network and intimate contacts between nanosulfur and graphene/PEDOT:PSS for effective charge transportation, but also offers synergistic physical restriction and chemical confinement of dissoluble intermediate lithium polysulfides during electrochemical processes. Therefore, these conductive compact films, used directly as cathodes, show the highest reversible volumetric capacity of 1432 Ah L −1 at 0.1 C and 1038 Ah L −1 at 1 C, and excellent cycling stability with a minimal decay rate of 0.04% per cycle over 500 cycles at 1 C. Meanwhile, remarkable rate performance with a high capacity of 701 mAh g −1 at 4 C is also achieved. Soft‐packaged batteries based on this flexible cathode are further fabricated and demonstrate excellent mechanical and electrochemical properties with little capacity decay under folded state, highlighting the practical application of our deliberately designed electrode in a flexible power system.