Highly Conductive and Mechanically Robust Cellulose Nanocomposite Hydrogels with Antifreezing and Antidehydration Performances for Flexible Humidity Sensors

Conductive hydrogels are emerging as an appealing material platform for flexible electronic devices owing to their attractive mechanical flexibility and conductive properties. However, the conventional water-based conductive hydrogels tend to inevitably freeze at subzero temperature and suffer from continuous water evaporation under ambient conditions, leading to a decrease in their electrical conductivities and mechanical properties. Thus, it is extremely necessary, but generally challenging, to create an antifreezing and antidehydration conductive gel for maintaining high and stable performances in terms of electrical conductivity and mechanical properties. Herein, we fabricated a cellulose nanofibril (CNF)-reinforced and highly ion-conductive organogel featuring excellent antifreezing and antidehydration performances by immersing it in the CaCl₂/sorbitol solution for solvent displacement. The incorporation of a rigid CNF serving as a dynamic connected bridge provided a hierarchical honeycomb-like cellular structure for the obtained CS-nanocomposite (NC) organogel networks, facilitating significant mechanical reinforcement. The synergy effects of sorbitol and CaCl₂ allowed high-performance integration with excellent antifreezing tolerance, antidehydration ability, and ionic conductivity. Strong hydrogen bonds were formed between water molecules and sorbitol molecules to impede the formation of ice crystals and water evaporation, thereby imparting the CS-NC organogels with extreme-temperature tolerance as low as -50 °C and pre-eminent antidehydration performance with over 90% weight retention. Furthermore, this CS-NC organogel exhibited high humidity sensitivity in a wide humidity detection range (23∼97% relative humidity) because of the ready formation of hydrogen bonds between water molecules and numerous hydrophilic groups in the binary solvent and elaborated polymer chains, which can be assembled as a stretchable humidity sensor to monitor human respiration with a fast response. This work provides a new prospect for fabricating intrinsically stretchable and high-performance humidity sensors using cellulose-based humidity-responsive materials for the emerging wearable applications.