High‐Performance Fatigue‐Resistant Dual‐ Polyrotaxane Hydrogel Electrolytes for Flexible Aqueous Zinc‐Ion Batteries

Abstract This study presents a novel anti‐fatigue hydrogel electrolyte with a slip‐ring structure for next‐generation flexible wearable energy storage systems. Conventional quasi‐solid aqueous zinc‐ion batteries (ZIBs) with hydrogel electrolytes often suffer from mechanical degradation under repeated stress, limiting practical use. To overcome this, a dual‐Polyrotaxane (DPR)‐polyacrylic acid (PAA) hydrogel with a unique slip‐ring architecture is synthesized, that enhances mechanical durability, self‐healing, and adhesion. The interwoven DPR and PAA networks distribute stress evenly, ensuring high ionic conductivity while preventing zinc dendrites and parasitic reactions for uniform zinc deposition during cycling.When applied to a flexible quasi‐solid‐state Zn‐MnO₂ battery, this hydrogel achieves a specific capacity of 295 mAh g⁻¹ MnO₂ at 0.5C, retains 147 mAh g⁻¹ at 5C, and shows 81.52% capacity retention after 1000 cycles. The battery also demonstrates exceptional stability, with zinc pairs lasting over 1750 h at 5 mA cm⁻ 2 . Furthermore, it maintains reliable operation under mechanical stresses like pressing, folding, and twisting, making it ideal for wearable applications. This work advances hydrogel electrolyte design, offering a durable, high‐performance solution for flexible energy storage systems.