Nitro‐Functionalized PDOL Gel Electrolytes with Regulated Li + Coordination for Li─S Batteries

Rational design of lithium‐ion coordination architectures within gel polymer electrolytes remains challenging for simultaneously improving ionic transport and interfacial stability in lithium‐sulfur batteries. Herein, we report an in situ copolymerization strategy of 1,3‐dioxolane (DOL) with π ‐conjugated nitroaromatic R‐glycidyl nosylate (R‐GN). The π ‐conjugated structure promotes electron‐density delocalization onto the nitro group, reducing N═O bond polarity compared with conventional nitrate additives. The resulting PDOL@R‐GN electrolyte builds a multidimensional lithium‐ion coordination network through electronic modulation and spatial effects, enabling preferential Li + transport and a high Li + transference number ( = 0.66) at 25°C. It also promotes a gradient solid electrolyte interphase (SEI) with F‐ and N‐rich components, improving interfacial robustness and ionic transport. Pouch‐cell feasibility was demonstrated using a 3 Ah pouch cell, delivering 392 Wh kg −1 under high sulfur loading (8 mg cm −2 ), and lean electrolyte (E/S = 3 g electrolyt e g s −1 ), while retaining 811 mAh g −1 after 40 cycles with an average Coulombic efficiency of 95.0%. This work provides insights into the molecular‐level design of multifunctional electrolytes for high‐energy‐density batteries.