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.

Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li−S and Li−O 2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li + −solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO 2 CF 3 ) 2 concentration or, more effectively, the addition of LiNO 3 lowers the interaction strength between Li + and solvents, suppressing the graphite exfoliation caused by Li + −solvent co-insertion. Our findings refresh the knowledge of the well-known SEI for graphite stability in metal ion batteries and also provide new guidelines for electrolyte systems to achieve reliable and safe Li−S full batteries.

Solid electrolyte interphase (SEI)-forming agents such as vinylene carbonate, sulfone, and cyclic sulfate are commonly believed to be film-forming additives in lithium-ion batteries that help to enhance graphite anode stability. However, we find that the film-forming effect and the resultant SEI may not be the only reasons for the enhanced graphite stability. This is because the as-formed SEI cannot inhibit Li + −solvent cointercalation once the additive is removed from the electrolyte. Instead, we show that the Li + solvation structure, which is modified by these additives, plays a critical role in achieving reversible Li + (de)intercalation within graphite. This discovery is confirmed in both carbonate and ether-based electrolytes. We show that the problem of graphite exfoliation caused by Li + −solvent cointercalation can be mitigated by adding ethene sulfate to tune the Li + coordination structure. This work brings new insight into the role of additives in electrolytes, expanding the prevailing thinking over the past 2 decades. In addition, this finding can guide the design of more versatile electrolytes for advanced rechargeable metal-ion batteries.