Strong and Tough Cellulose Hydrogels via Solution Annealing and Dual Cross‐Linking

Abstract Strong and tough hydrogels are promising candidates for flexible electronics, biomedical devices, and so on. However, the conflict between improving the mechanical strength and toughness properties of polysaccharide‐based hydrogels remains unsolved. Herein, a strategy is proposed to produce a hierarchically structured cellulose hydrogel that combines solution annealing and dual cross‐linking treatment approaches. The solution annealing considerably increases the hydrophobic stacking and chemical cross‐linking of the cellulose chains, thereby facilitating their subsequent self‐assembly and recrystallization during the chemical and physical cross‐linking processes. The cellulose hydrogels exhibit superposed chemically and physically cross‐linked domains comprising homogeneous nanoporous network structures, which in turn are composed of interconnected cellulose nanofibers and cellulose II crystallite hydrates. These cellulose hydrogels exhibit a high water content of 76–84% and excellent mechanical properties that compare favorably to those of biomacromolecule‐based hydrogels. The prepared hydrogels exhibit a mechanical strength and work of fracture of 21 ± 3 MPa and 2.6 ± 0.4 MJ m⁻³ under compression, and 7.2 ± 0.7 MPa and 5.9 ± 0.6 MJ m⁻³ under tension, respectively. It is anticipated that this strategy will be applicable to other biomacromolecules and crystalline polymers, and that it will enable the construction of other hydrogels exhibiting high mechanical performances.