Self‐Confined Effects Induced by F─H Bonds Simultaneously Enhance Mechanical Strength, Conductivity, and Self‐Healability of Ionic Elastomers

Abstract Simultaneous enhancement of mechanical strength, ionic conductivity, and self‐healing ability is urgently needed but challenging for solid‐state ionic elastomers because of their inherent contradictions. Herein, an effective and general strategy based on the self‐confined effect induced by fluorine–hydrogen (F─H) bonds is presented to address these challenges. Under self‐confinement, the tensile strength, ionic conductivity, and self‐healing efficiency of a fluorinated solid‐state ionic conductive elastomer (SICE‐FA‐20) are enhanced by 4.2‐, 5.3‐, and 1.2‐fold, respectively, compared to its nonfluorinated counterpart. Notably, the SICE‐FA‐20 achieves record‐high performance across multiple metrics, including tensile strength of 38.5 MPa, fracture energy of 112.5 kJ m − 2 , puncture energy of 642.0 mJ, and self‐healing efficiency of 99.3%, surpassing those of all previously reported solid‐state lithium‐ion conductive elastomers. Furthermore, it shows a high ionic conductivity of 3.82 × 10 −3 S m −1 at 30 °C, remarkable thermal stability, and excellent reprocessability. This approach is expected to inspire new developments in high‐performance functional materials.