Sulfurized polyacrylonitrile (SPAN) is the most promising cathode for next-generation lithium–sulfur (Li–S) batteries due to the much improved stability. However, the molecular structure and reaction mechanism have not yet been fully understood. Herein, we present a new take on the structure and mechanism to interpret the electrochemical behaviors. We find that the thiyl radical is generated after the cleavage of the S–S bond in molecules in the first cycle, and then a conjugative structure can be formed due to electron delocalization of the thiyl radical on the pyridine backbone. The conjugative structure can react with lithium ions through a lithium coupled electron transfer process and form an ion-coordination bond reversibly. This could be the real reason for the superior lithium storage capability, in which the lithium polysulfide may not be formed. This study refreshes current knowledge of SPAN in Li–S batteries. In addition, the structural analysis is applicable to analyze the current organic cathodes in rechargeable batteries and also allows further applications in Al–S batteries to achieve high performance.

Recognizing the Mechanism of Sulfurized Polyacrylonitrile Cathode Materials for Li–S Batteries and beyond in Al–S Batteries