Challenges and Prospects of Electrolyte Design for Lithium‐Sulfurized Polyacrylonitrile Batteries

Abstract Sulfurized polyacrylonitrile (SPAN) is regarded as a promising organic sulphur cathode material for lithium‐sulfur (Li−S) batteries. It undergoes a solid‐solid conversion without forming polysulfide intermediate phases, overcoming the poor electrochemical performance caused by the shuttle effect of elemental S cathodes. However, realizing this unique conversion mechanism requires employing appropriate electrolytes. Furthermore, the direct application of metallic Li as the anode unavoidable introduces a series of issues triggered by Li dendrites in Li‐SPAN batteries, such as low lifespan, short circuits, fire, etc. In this review, we endeavor to encapsulate recent advancements in electrolyte research, with a particular focus on the intrinsic relationship between the solvation structure of the electrolyte and the interfacial chemistry of the Li anode and SPAN electrode, aim to provide insights into the electrolytes design for high performance Li‐SPAN full batteries.