Ultra‐High Conductivity Enhancement of Robust All‐Solid‐State Ion Elastomers via Strain‐Induced Ion Channel Alignment and Temperature‐Activated Ion‐Gated Release

Abstract Despite their potential in ionic electronics, conventional ionic conductors face critical limitations, including modest strain‐modulated conductivity and restricted self‐regulation under temperature variations. Here, a mechanically robust all‐solid‐state ionic elastomer is presented, engineered through molecular design and microphase separation. By in situ integrating polyacrylamide (PAM) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into maleic anhydride‐grafted styrene‐ethylene‐butylene‐styrene (SEBS‐MAH), a hierarchical structure with dynamic non‐covalent interactions (hydrogen bonds, lithium bonds, and cation‐π effects) is achieved. This design yields exceptional mechanical properties, including a tensile strength of 46.4 MPa, strain of 1066%, and toughness of 207.8 MJ m −3 , alongside outstanding recyclability and puncture resistance. Remarkably, strain‐induced alignment of microphase‐separated domains reduces ion transport tortuosity, enabling a 1300 times conductivity enhancement at 1066% strain. Concurrently, temperature‐gated ion release from confined regions triggers a 1600 times conductivity increase at 120 °C. The elastomer maintains high conductivity (>10 −3 S m −1 ) across an ultra‐wide temperature range (−45–120 °C), overcoming the limitations of conventional hydrogels and ionogels. This work pioneers a dual‐stimuli‐responsive strategy for advanced ionic conductors, offering transformative potential in wearable electronics, soft robotics, and adaptive sensors.