Enormous-stiffness-changing polymer networks by glass transition mediated microphase separation.

The rapid development of flexible electronics and soft robotics has an urgent demand for materials with wide-range switchable stiffness. Here, we report a polymer network that can isochorically and reversibly switch between soft ionogel and rigid plastic accompanied by a gigantic stiffness change from about 600 Pa to 85 MPa. This transition is realized by introducing polymer vitrification to regulate the liquid-liquid phase separation, namely the Berghmans' point in the phase diagram of binary gel systems. Regulating the Lewis acid-base interactions between polymer and ionic liquids, the stiffness-changing ratio of polymer network can be tuned from 10 to more than 10. These wide-range stiffness-changing ionogels show excellent shape adaptability and reconfigurability, which can enhance the interfacial adhesion between ionogel and electrode by an order of magnitude and reduce interfacial impedance by 75%.