Unbreakable Hydrogels with Self‐Recoverable 10 200% Stretchability

Design of tough hydrogels maintaining structural integrity under multivariable mechanical loads remains hugely challenging because the anticipated characteristics such as stretchability, strength, toughness, and fracture resistance can hardly be compatible. Herein, a simple but robust hydrogel network formed by copolymerization of divinyl benzene with acrylamide in micellar solutions for ultra-high fracture resistance and self-recoverable stretchability is proposed. The network provides dynamic association of hydrophobic domains and homogeneous crosslinking of hydrophilic chains, which shows step-by-step deformation process. The dynamic associations allow recoverable small deformations, then the homogeneous crosslinking ensures reversible unfolding and alignment of polymer chains to self-strengthen for ultra-large deformations without crack propagations. The resultant hydrogels exhibit comprehensive unbreakable feature with self-recoverable ultra-high stretchability (100% recovery from 10 200% strain), superior fracture resistance (toughness > 26 kJ m^-2 ), and anticrack propagation and fatigue (fatigue threshold: ≈2.5 kJ m^-2 ). Even the prenotched hydrogels can undergo tens cyclic loads at 10 200% strain and thousands cyclic loads at 200% strain without noticeable changes in mechanical performance. The robust network prepared from homogeneous hydrophobic crosslinking provides a facile approach and a new mechanism to explore tough hydrogels with superior antifracture and extreme self-recoverable deformability for diverse applications.