As a key material for capacitors, high-performance polymer dielectric films still exhibit the problem of low energy storage density, which cannot meet the requirements of high-power and high-temperature conditions. Here, a sandwich-structured composite film with inner layer doped TiO2-BCB (titanium dioxide – benzocyclobutene) and outer layer doped BN-BCB (boron nitride – benzocyclobutene) nanoparticles was prepared, which exhibits reduced dielectric loss, leakage current and enhanced dielectric constant (ε) and breakdown strength (Eb). Diels-Alder reaction and radical polymerization reactions are utilized to form the entire cross-linked sandwich structure. Moreover, the thermal-induced crosslinked structure replaces the traditional multilayer structure established by Van der Waals forces, thus improving the dielectric and mechanical qualities of the film. Specifically, the sandwich structure composites achieved a large discharge energy density (4.0 J/cm3) and high charge-discharge efficiency (84%) at 150 °C and 450 MV/m, and the dielectric dissipation factor is less than 0.005. These results demonstrated that designing a cross-linked network in multilayer nanocomposite structure is a feasible method to improve the high-temperature energy storage performance of these films.
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