Robust, self-healable, recyclable and thermally conductive silicone composite as intelligent thermal interface material

•A robust, self-healable, recyclable and thermally conductive silicone composite is realized by novel asymmetric dynamic crosslinking chain.•This Al2O3/BN/silicone composite has an optimal thermal conductivity of 2.9 W/mK and a tensile strength of 4.7 MPa.•The overall performance of this silicone composite recovers 95% after repeated self-healing, reprocessing and recycling.•Chemical degradation of the composite facilitates the recycling of electronic devices. The facile preparation of robust, thermally conductive, self-healable and recyclable silicone composite is still a major challenge, so an asymmetric dynamic crosslinking chain strategy is proposed herein. Due to the better synergy of dynamic covalent and non-covalent bonds, this crosslinked network designed increases the tensile strength of silicone elastomer by 3 times to 5.1 MPa, compared to traditional symmetric crosslinking structures (1.7 MPa). Moreover, optimizing the size and content of thermally conductive fillers (Al2O3 and BN), the thermal conductivity of silicone composite reaches 2.9 W/mK, vitalizing the rapid heat conduction and dissipation. Moreover, the composite can be repeatedly self-healed and reprocessed, its tensile strength and thermal conductivity recover 95%. The composite can also be recycled into silicone matrix and fillers, and the recycled materials can be remolded into new composite, allowing the recycling of electronic devices. Therefore, this work opens new avenues for intelligent thermal management in electronic devices.