Polyfunctional and Multisensory Bio‐Ionoelastomers Enabled by Covalent Adaptive Networks With Hierarchically Dynamic Bonding

Abstract Developing versatile ionoelastomers, the alternatives to hydrogels and ionogels, will boost the advancement of high‐performance ionotronic devices. However, meeting the requirements of bio‐derivation, high toughness, high stretchability, autonomous self‐healing ability, high ionic conductivity, reprocessing, and favorable recyclability in a single ionoelastomer remains a challenging endeavor. Herein, a dynamic covalent and supramolecular design, lipoic acid (LA)‐based dynamic covalent ionoelastomer (DCIE), is proposed via melt building covalent adaptive networks with hierarchically dynamic bonding (CAN‐HDB), wherein lithium bonds aid in the dissociation of ions and the integration of dynamic disulfide metathesis, lithium bonds, and binary hydrogen bonds enhances the mechanical performances, self‐healing capability, reprocessing, and recyclability. Therefore, the trade‐off among mechanical versatility, ionic conductivity, self‐healing capability, reprocessing, and recyclability is successfully handled. The obtained DCIE demonstrates remarkable stretchability (1011.7%), high toughness (3877 kJ m −3 ), high ionic conductivity (3.94 × 10 −4 S m −1 ), outstanding self‐healing capability, reprocessing for 3D printing, and desirable recyclability. Significantly, the selective ion transport endows the DCIE with multisensory feature capable of generating continuous electrical signals for high‐quality sensations towards temperature, humidity, and strain. Coupled with the straightforward methodology, abundant availability of LA and HPC, as well as multifunction, the DCIEs present new concept of advanced ionic conductors for developing soft ionotronics.