A Universal Strategy to Mitigate Microphase Separation via Cellulose Nanocrystal Hydration in Fabricating Strong, Tough, and Fatigue‐Resistant Hydrogels

Abstract As a common natural phenomenon, phase separation is exploited for the development of high‐performance hydrogels. Using supersaturated salt to create microphase‐separated hydrogels with strengthened mechanical properties has gained widespread attention. However, such strengthened hydrogel loses its intrinsic flexibility, making the phase separation strategy unsuitable for the fabrication of stretchable and tough hydrogels. Here, a phase‐engineering design strategy is introduced to produce stretchable yet tough hydrogels using supersaturated NaAc salt, by leveraging the hydration effect of cellulose nanocrystal (CNC) to mitigate microphase separation. The CNC‐mitigated microphase‐separated hydrogel presents unprecedented mechanical properties, for example, tensile strength of 1.8 MPa with a fracture strain of 4730%, toughness of 43.1 MJ m⁻³, fracture energy of 75.4 kJ m⁻², and fatigue threshold up to 3884.7 J m⁻². Furthermore, this approach is universal in synthesizing various microphase separation‐enhanced polymer gels, including polyacrylic acid, poly(acrylic acid‐co‐acrylamide), gelatin, and alginate. These advancements provide insights into the incorporation of CNC‐mediated microphase separation structures in hydrogels, which will foster the future development of high‐performance soft materials.