Supramolecular‐Reinforced Hard‐Phase Ionogels with Exceptional Mechanical Robustness and Damage Tolerance

Abstract It is a formidable challenge to integrate superior damage tolerance into robust ionogels due to fundamental conflicts between covalent rigidity and dynamic energy dissipation. Herein, an echinoderm‐inspired supramolecular ionogel is engineered with extreme robustness and damage tolerance via synergistic integration of hard‐soft phase‐separated architecture and multi‐scale sacrificial bonding. The molecularly programmed hard segments of polyurethane integrate crystalline domains, high‐density hydrogen bonds, and π–π stacking, which collectively enhance ionogel robustness, while a judiciously selected ionic liquid (IL) reinforced the hard phase via extensive IL‐polymer multiple hydrogen bonds. The crystalline domains synergizing with reversible sacrificial bonds facilitated efficient energy dissipation through dynamic rupture/reformation mechanisms. Consequently, the supramolecular ionogel achieves advanced tensile strength (49.22 MPa), elongation (1721.28%), toughness (424.09 MJ m⁻³), Young's modulus (48.66 MPa) and unprecedented damage tolerance, manifested as tear resistance (387.02 kJ m⁻², 59‐fold that of polyurethane), outstanding puncture energy (1326.8 mJ), and exceptional high‐speed impact resistance (228.74 MJ m⁻³ at strain rate of 20 000 s⁻¹). Notably, the ionogel demonstrated autonomous room‐temperature self‐healing, broad operational temperature adaptability, flame retardancy, and recyclability. Furthermore, a wearable ionogel sensing matrix is developed to simultaneously accomplish real‐time limb motion tracking and precise damage localization, targeting next‐generation intelligent protective equipment to deliver integrated impact protection and flexible sensing.