Orotic Acid‐Functionalized Solid Electrolyte With Promoted Salt Dissociation for High‐Performance Lithium–Sulfur Batteries

Solid‐state electrolytes (SSEs) offer an effective solution to the polysulfide shuttling and safety issues currently plaguing lithium–sulfur batteries. Among these, PVDF‐HFP‐based SSEs have garnered significant attention due to their excellent electrochemical stability and interfacial wettability. However, PVDF‐HFP electrolytes still face challenges such as poor lithium‐ion conductivity, and the addition of fillers is a mainstream approach to addressing this issue. Nevertheless, traditional fillers still present several problems: inorganic fillers often exhibit poor compatibility with the polymer matrix, while organic fillers tend to aggregate within it. To simultaneously achieve the performance benefits of organic fillers and high dispersion, this study proposes an anion‐anchoring strategy, selecting orotic acid as a small‐molecule filler to prepare a PVDF‐OA electrolyte. By facilitating lithium salt dissociation, orotic acid improves Li ⁺ transport. The resulting PVDF‐OA electrolyte delivers a room‐temperature ionic conductivity of 9.12 × 10 ^{− 4}  S cm ⁻¹ and reaches a Li ⁺ transference number of 0.82. The assembled Li|PVDF‐OA|SPAN battery can stably cycle 300 times at a 1 C rate, with a specific discharge capacity of 883 mAh g ⁻¹ and a capacity retention rate of 93%. This approach provides an economical, effective, and sustainable solution for the commercial development of SSEs.