A Tough Monolithic‐Integrated Triboelectric Bioplastic Enabled by Dynamic Covalent Chemistry

Abstract Electronic waste is a growing threat to the global environment and human health, raising particular concerns. Triboelectric devices synthesized from sustainable and degradable materials are a promising electronic alternative, but the mechanical mismatch at the interface between the polymer substrate and the electrodes remains unresolved in practical applications. This study uses the sulfhydryl silanization reaction and the chemical selectivity and site specificity of the thiol–disulfide exchange reaction in dynamic covalent chemistry to prepare a tough monolithic‐integrated triboelectric bioplastic. The stress is dissipated by covalent bond adaptation to the interface interaction, which makes the polymer dielectric layer to the conductive layer have a good interface adhesion effect (220.55 kPa). The interfacial interlocking of the polymer substrate with the conductive layer gives the triboelectric bioplastic excellent tensile strength (87.4 MPa) and fracture toughness (33.3 MJ m −3 ). Even when subjected to a tension force of 10 000 times its weight, it still maintains a stable triboelectric output with no visible cracks. This study provides new insights into the design of reliable and environmentally friendly self‐powered devices, which is significant for the development of flexible wearable electronics.