Inorganic Ionic Oligomers Induced Organic‐Inorganic Synergistic Toughening Enabling Mechanical Robust and Recyclable Nanocomposite Hydrogels

Abstract Mechanical robust hydrogels are ideal for applications in energy, environment, biomedicine, and structural engineering materials fields. However, high strength and high toughness are usually in conflict with each other, and simultaneously achieving both of them within a hydrogel has been challenging. Herein an organic‐inorganic synergistic toughening strategy is reported via in‐situ inorganic ionic polymerization of calcium phosphate oligomers within polymer composite networks composed of polyvinyl alcohol chains and aramid nanofibers. The composite hydrogels are provided with a prestress‐induced hierarchically fibrous structure through the assembly, which resulted in the mechanical strength and toughness up to 24.15 ± 1.12 MPa and 15.68 ± 1.78 MJ m⁻³, respectively, surpassing most toughened hydrogels. Through lamination and crosslinking, bulk hydrogels with controllable mechanical anisotropy and significant energy absorption/dissipation ability are produced. Moreover, the recycling and regeneration of the hydrogels are easily realized owing to the physically crosslinked network and acid‐induced dissolution of the inorganic units of the hydrogels, which lays a foundation for the sustainable large‐scale production and application of the hydrogels. This study provides an alternative approach for the development of mechanical robust and recyclable nanocomposite hydrogels for various applications including soft body armor, flexible electronics, soft robotics, etc.