Supramolecular Association of a Block Copolymer via Strong Hydrogen Bonding to Form Self-Healable Ionogels

The drive to enhance the operational durability and reliability of stretchable and wearable electronic and electrochemical devices has led to the exploration of self-healing materials that can recover from both physical and functional failures. In the present study, we fabricated a self-healable solid polymer electrolyte, referred to as an ionogel, using reversible hydrogen bonding between the ureidopyrimidone units of a block copolymer (BCP) network swollen in an ionic liquid (IL). The BCP consisted of poly(styrene-b-(methyl acrylate-r-ureidopyrimidone methacrylate)) [poly(S-b-(MA-r-UPyMA)], with the IL-phobic polystyrene forming micellar cores that were interconnected via intercorona hydrogen bonding between the ureidopyrimidone units. By precisely regulating the molecular weight and the composition of the hydrogen-bondable motifs, the mechanical, electrical, and self-healing characteristics of the ionogel were systematically evaluated. The resulting ionogel samples exhibited suitable stretchability, ionic conductivity, and room-temperature self-healability due to reversible hydrogen bonding. To highlight the applicability of the self-healing ionogel as a high-capacitance gate insulator, an electrolyte-gated transistor (EGT) was fabricated using a poly(3-hexylthiophene-2,5-diyl) semiconductor, and the performance of the EGT was fully recovered from a complete cut without any external stimuli.