Multiscale Understanding of Covalently Fixed Sulfur–Polyacrylonitrile Composite as Advanced Cathode for Metal–Sulfur Batteries

Abstract Metal–sulfur batteries (MSBs) provide high specific capacity due to the reversible redox mechanism based on conversion reaction that makes this battery a more promising candidate for next‐generation energy storage systems. Recently, along with elemental sulfur (S₈), sulfurized polyacrylonitrile (SPAN), in which active sulfur moieties are covalently bounded to carbon backbone, has received significant attention as an electrode material. Importantly, SPAN can serve as a universal cathode with minimized metal–polysulfide dissolution because sulfur is immobilized through covalent bonding at the carbon backbone. Considering these unique structural features, SPAN represents a new approach beyond elemental S₈ for MSBs. However, the development of SPAN electrodes is in its infancy stage compared to conventional S₈ cathodes because several issues such as chemical structure, attached sulfur chain lengths, and over‐capacity in the first cycle remain unresolved. In addition, physical, chemical, or specific treatments are required for tuning intrinsic properties such as sulfur loading, porosity, and conductivity, which have a pivotal role in improving battery performance. This review discusses the fundamental and technological discussions on SPAN synthesis, physicochemical properties, and electrochemical performance in MSBs. Further, the essential guidance will provide research directions on SPAN electrodes for potential and industrial applications of MSBs.