Fully Physically Crosslinked PNIPAM Ionogels with High Mechanical Properties and Temperature‐Managed Adhesion Achieved by H₂O/Ionic Liquid Binary Solvents

Abstract Poly(N‐isopropylacrylamide) (PNIPAM) gels change their volume and hydrophilicity in response to temperature stimulus in flexible actuators, flexible sensors, and energy storage management. However, traditional PNIPAM gels exhibit low mechanical properties and poor self‐recovery ability due to weak intermolecular (chain) interactions and necessary covalent crosslinking. Herein, a water/ionic liquid (H₂O/IL) binary solvent system that provides additional hydrogen bonding and hydrophobic interactions as well as can significantly increase the solubility (up to 60 wt.%) of NIPAM is developed. The fully physically crosslinked PNIPAM ionogel is prepared by utilizing the H₂O/IL binary solvent and exhibited excellent mechanical performances, rapid self‐recovery properties, and strong adhesion strength. In addition, the lower critical solution temperature of the PNIPAM ionogel can also be tuned over a wide range (37‐70 °C) by adjusting the IL ratio in the binary solvent. Furthermore, based on the temperature sensitivity and ionic conductivity of the PNIPAM ionogel, applications of PNIPAM ionogels in smart devices, temperature‐managed adhesion, and flexible sensing are demonstrated, respectively. This work improves various performances of PNIPAM gels by using the H₂O/IL binary solvent to adjust non‐covalent interactions and provided new ideas for developing high‐performance temperature‐sensitive gels.