Closed‐Loop Recyclable Lithium and Sodium Conducting Covalent Adaptable Networks

Abstract Within the past two decades, covalent adaptable networks (CANs) have emerged as a novel class of dynamically crosslinked polymers, combining the benefits of thermosets and thermoplastics. Although some CANs with charged side chains have been reported, CANs with negatively charged backbones remain very limited. The integration of permanent charge into the backbones upon their formation could open up important new applications. Here, we introduce a series of aliphatic spiroborate‐linked ionic covalent adaptable networks (ICANs), representing a new category of dynamic ionomer thermosets. These ICANs were synthesized using a catalyst‐free, scalable, and environment‐friendly method. Incorporating lithium or sodium as counter cations in these networks yielded promising ion conductivity without the need of plasticizers. The dynamic nature of the spiroborate linkages in these materials allows for rapid reprocessing and recycling under moderate conditions. Furthermore, their potential as flexible solid‐state electrolytes is demonstrated in a device that maintained robust conducting performance under extreme physical deformation, coupled with effective self‐healing properties. This research opens new possibilities for future development of dynamic ionomer thermosets and their potential applications in flexible electronic devices.