Coordinatively Stiffen and Toughen Hydrogels with Adaptable Crystal‐Domain Cross‐Linking

Abstract Conventional hydrogels usually suffer from the inherent conflict between stiffness and toughness, severely hampering their applications as load‐bearing materials. Herein, an adaptable crystal‐domain cross‐linking design is reported to overcome this inherent trade‐off for hydrogels by taking full advantage of both deformation‐resisting and energy‐dissipating capacities of cross‐linking points. Through solvent exchange to homogenize the polymer network, followed by salting out to foster crystallization, a class of sal‐exogels with high number densities of uniform crystalline domains embedded in homogeneous networks is constructed. During the deformation, those adaptive crystalline domains initially survive to arrest deformation, while later gradually disentangle to efficiently dissipate energy, crucial to the realization of the desirable compatibility between stiffness and toughness. The resultant sal‐exogel achieves coordinatively enhanced stiffness (52.3 ± 2.7 MPa) and toughness (120.7 ± 11.7 kJ m −2 ), reconciling the challenging trade‐off between them. This finding provides a practical and universal route to design stiff and tough hydrogels and has a profound impact on many applications requiring hydrogels with such combined mechanical properties.