High‐Strength, Minutes‐Timescale Self‐Healable, Recyclable Thermoplastic Ion‐Elastomers Enabled by Chain‐Motion‐Unrestricted Hyperbranched Domains

Abstract High‐performance ion‐conductive elastomers are fundamentally constrained by a critical design trade‐off: intensive crosslinking enhances mechanical robustness but hinders segmental chain dynamics that are essential for reversible characteristics such as self‐healing and recyclability. Herein, a dual‐domain ion‐elastomer that integrates densely crosslinked domains for high mechanical strength with highly mobile hyperbranched domains for dynamic characteristics is synthesized through the ring‐opening polymerization of thioctic acid‐grafted hyperbranched polyethyleneimine, followed by controlled swelling in ion‐conducting deep eutectic solvents. The resulting ion‐elastomer demonstrates multimodal relaxation dynamics. The densely crosslinked domains offer high strength (≈1.15 MPa), exceptional stretchability (>2000%), and high toughness (≈16.6 MJ m −3 ), while the mobile hyperbranched domains enable minutes‐timescale self‐healing and solvent‐free thermoplastic recyclability. The integration of mechanical robustness, environmental durability, and reprocessability enables the ion‐elastomers to be processed into skin‐inspired, shape‐adaptive sensors via extrusion‐based 3D printing, which demonstrate remarkable sensitivity, ultralow detection limit, and high durability. This study presents an innovative molecular design strategy for creating mechanically resilient, self‐healing, and recyclable ion‐elastomers, advancing potentials for sustainable wearable and printable soft electronics.