With fast development of modern industries and electrical systems, polymer dielectrics are urgently demanded to have high discharged energy density (Ud) in elevated temperature. In this paper, novel core-shell poly [2-((3,6,7,10,11-pentakis (hexyloxy) triphenylene-2-yl) oxy) ethyl methacrylate] (PHT) coated barium titanate nanoparticles (BT) (denoted as PHT@BT) are prepared, and then incorporate into polyetherimide (PEI) matrix via solution blending method. Semi-conductive organic shell layer can not only promote the dispersion and compatibility of BT nanoparticles but also construct deep trap. As a result, 0.3 wt% PHT@BT/PEI composites achieve maximal Ud of 7.62 J cm−3 at 641 MV m−1 and room temperature, which is 1.93 times that of pure PEI film (3.93 J cm−3 at 461 MV m−1). Importantly, the Ud of 4.86 J cm−3 is obtained at 150 °C. This work provides superior interfacial modifier for inorganic nanofiller, which is of great significance for the fabrication of polymer-based nanocomposites with superior Ud.
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