Acylsemicarbazide-based dynamic networks coupling ion transport and reprocessability in all-solid-state ionic elastomers

All-solid-state ionic conductive elastomers are attractive for soft ionotronics, but their development is often limited by the difficulty of reconciling ion transport, mechanical stability, and reprocessability in a liquid-free polymer network. Herein, a series of LiTFSI-containing acylsemicarbazide-based elastomers was developed by integrating dynamic covalent linkages, dense hydrogen-bonding interactions, and ion-associated coordination within a unified network. The acylsemicarbazide units acted as both thermally exchangeable motifs and reinforcing interaction centers, whereas the ether-rich soft segments provided coordination sites for lithium-ion solvation and migration. More importantly, LiTFSI functioned not only as an ionic source, but also as a regulator of the network state by altering local coordination, segmental mobility, and effective network constraints. As a result, the elastomers showed high optical transparency, tunable tensile strengths from 11.3 to 1.3 MPa, elongations at break up to 1050%, and ionic conductivities up to 3.60 × 10 −3 mS cm −1 at 20 °C. The optimized composition exhibited balanced mechanical compliance and stable electromechanical responses in both capacitive and resistive sensing modes, enabling reproducible detection of deformation, human motion, and temperature variation. The ASC-containing networks exhibited pronounced thermally activated stress relaxation and could be reprocessed while retaining ionic conductivity and sensing functionality. This work provides a network-state regulation strategy for designing reprocessable all-solid-state ionic elastomers in which ion transport, mechanical response, and dynamic rearrangement are coupled within the same molecular framework.