Tailoring Solvation Structure via Soft‐Hard Segment Synergy in Gel Polymer Electrolytes Enables Dendrite‐Free Sodium Batteries with Ultra‐Long Cycling

(NVP) cell demonstrates excellent rate durability, sustaining 12 000 and 20 000 cycles at 5C and 10C, respectively, with nearly 100% Coulombic efficiency. Furthermore, a 29-layer pouch cell with NVP cathode and hard carbon (HC) anode delivers a high capacity approaching 1.0 Ah. This study demonstrates that designing polymer segments capable of regulating solvation structure and directing interfacial fluorination offers a promising strategy for high-performance GPEs for Na batteries.