Construction of sandwich‐layered polyimide hybrid films containing double core–shell structured fillers for high energy storage density

The inherent low dielectric constant of polyimide (PI) dielectrics restricts their applications to become a component of high energy density film capacitors. In this work, double core–shell structured barium titanate@magnesium oxide@polydopamine (BaTiO3@MgO@PDA) nanoparticles were synthesized successfully and utilized as high dielectric constant functional fillers for PIs, in which the insulating MgO layer meliorated dielectric constant difference between BaTiO3 and PI matrix, and the organic PDA layer improved the compatibility between the inorganic fillers and PI matrices. Then, a series of sandwich‐structured PI‐based hybrid films was prepared through a layer‐by‐layer solution casting method. The middle layer of pure PI with excellent insulating properties effectively suppressed charge injection. With the combination of sandwich structure and the BaTiO3@MgO@PDA nanoparticles, the PI hybrid film containing 15 wt% fillers in the outer layers achieved the maximum breakdown strength of 425.68 kV/mm and the maximum energy density of 5.132 J/cm3, which was 68.3% and 413% higher than those of pure PI film, respectively, meanwhile maintained a low dielectric loss value of 0.0083 at 1 kHz. The introduction of BaTiO3@MgO@PDA enhanced the interfacial polarization due to the high barrier energy between adjacent layers preventing the transfer of electrons and weakening the leakage current in the sandwich‐structured composite film. This work demonstrates that an appropriate combination of high dielectric hybrid fillers and multilayer structure can effectively increase the energy storage density of PI substrate for high‐temperature energy storage applications. Highlights The double core–shell structured BaTiO3@MgO@PDA was synthesized successfully. The sandwich‐structured hybrid films were prepared by layer‐by‐layer method. The energy density of hybrid films reached a high value of 5.132 J/cm3. Dielectric properties of PI‐based composite films.