Tremendous Stiffness‐Changing Polymer Networks Enabled by Touch‐Induced Crystallization

Abstract Stiffness‐changing polymers are critically needed for intelligent and adaptive applications in soft robotics and wearable electronics; however, they suffer from the requirement of persistent external stimulation. Herein, a stiffness‐changing polymer network impregnated with a supercooled ionic liquid is introduced, which undergoes touch‐induced crystallization from a soft ionogel to a stiff plastic. The network exhibits a remarkable tunability in stiffness change, with the highest value exceeding 190 000 times between the soft and stiff states (3.5 kPa vs 691.1 MPa). This tremendous transition is achieved through the first‐order liquid–solid phase transition of the supercooled ionic liquid, which is highly reversible and isochoric via a heating‐cooling process. Unlike traditional stimuli, only a single touch is needed without sustained stimulation to trigger the stiffening from soft to stiff states. Importantly, the touch‐responsive polymer network can be extended to various types of ionic liquids and monomers, indicating excellent strategic versatility. Moreover, this unique ionogel exhibits switchable adhesiveness and ionic conductivity, effectively demonstrating smart adhesives and ionic switches with enhancements of more than 66 and 5800 times, respectively. This work provides a facile and versatile strategy for designing stable stiffness‐changing polymers, unlocking significant potential applications for next‐generation smart devices.