摘要： Dielectric polymer nanocomposites with high breakdown field and high dielectric constant have drawn significant attention in modern electrical and electronic industries due to their potential applications in dielectric and energy storage systems. The interfaces of the nanomaterials play a significant role in improving the dielectric performance of polymer nanocomposites. In this work, polydopamine (dopa) functionalized TiO2-BaTiO3-TiO2 (TiO2-BT-TiO2@dopa) core@double-shell nanoparticles have been developed as novel nanofillers for high energy density capacitor application. The hierarchically designed nanofillers help in tailoring the interfaces surrounding the polymer matrix as well as act as individual capacitors in which core and outer TiO2 shell functions as capacitor plate because of their high electrical conductivity while the middle BT layer functions as a dielectric medium due to high dielectric constant. Detailed electrical characterizations have revealed that TiO2-BT-TiO2@dopa/PVDF possess maximum relative dielectric permittivity (εr), breakdown strength (Eb), as well as energy densities in comparison to PVDF, TiO2/PVDF, TiO2@dopa/PVDF, TiO2-BT@dopa/PVDF polymer nanocomposites. The εr and energy density of TiO2-BT-TiO2@dopa/PVDF was 12.6 at 1 kHz and 4.4 J cm-3 at 3128 kV cm-1, respectively, which was comparatively much higher than commercially available biaxially oriented polypropylene (BOPP) having εr of 2.2 and the energy density of 1.2 J cm-3 at much higher electric field of 6400 kV cm-1. It is expected that these results will further open new avenues for the design of novel architecture for high-performance polymer nanocomposites-based capacitors having core@multishell nanofillers with tailored interfaces.