Development of flexible and freestanding electrode is attracting great attention in lithium–sulfur (Li–S) batteries, but the severe capacity fading caused by the lithium polysulfides (PSs) shuttle effect remains challenging. Herein, a completely new polymeric binder of polyethersulfone is introduced. Not only it enables massive production of flexible/current-free electrode by a novel concept of “phase-inversion” approach but also the resultant polymeric networks can effectively trap the soluble polysulfides within the electrode, owing to the higher hydrophilicity and stronger affinity properties than the routine polyvinylidene fluoride. Coupling with polysulfide-based electrolyte, the Li–S cell shows a higher capacity of 1141 mAh g, a lower polarization of 192 mV, and a more stable capacity retention with 100% Coulombic efficiency over 100 cycles at 0.25C. The advantages of favored binder and electrolyte are further demonstrated in lithium-ion sulfur full battery with lithiated graphite anode, which demonstrates much improved performance than those previously reported. This work not only introduces a novel strategy for flexible freestanding electrodes but also enlightens the importance of coupling electrodes and electrolytes to higher performances for Li–S battery.

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–O2 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(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 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.