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

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.