Energy storage film is one of the most important energy storage materials, while the performance of commercial energy storage films currently cannot meet the growing industrial requirements. Hence, this work presents a h-BN/PVDF/h-BN sandwich composite structure film prepared by laminating a large area of ultrathin hexagonal boron nitride (h-BN) and polyvinylidene fluoride (PVDF), the existence of which was confirmed by using an optical microscope and elemental composition analysis based on scanning electron microscopy and X-ray diffraction. This film has an ultrahigh dielectric strength of 464.7 kV/mm and a discharged energy density of up to 19.256 J/cm3, which is much larger than the commercial energy storage film biaxially oriented polypropylene (BOPP) (<2.5 J/cm3). Although the thickness of the h-BN film is only 70 nm compared with that of PVDF (about 12 μm), the dielectric strength of the sandwich-structured film presents a great increase. It is because of the excellent insulation performance of the h-BN film that helps to resist the electron injection and migration under high electric field, and then suppress the formation and growth of the breakdown path, leading to an improvement of the charge–discharge efficiency.
Dielectrics with improved energy density have long-standing demand for miniature and lightweight energy storage capacitors for electrical and electronic systems. Recently, polyvinylidene fluoride (PVDF)-based ferroelectric polymers have shown attractive energy storage performance, such as high dielectric permittivity and high breakdown strength, and are regarded as one of the most promising candidates. However, the non-negligible energy loss and inferior temperature stability of PVDF-based polymers deteriorated the energy storage performance or even the thermal runaway, which could be ascribed to vulnerable amorphous regions at elevated temperatures. Herein, a new strategy was proposed to achieve high energy density and high temperature stability simultaneously of PVDF/PMMA blends by in situ polymerization. The rigidity of the amorphous region was ideally strengthened by in situ polymerization of methyl methacrylate (MMA) monomers in a PVDF matrix to obtain PVDF/PMMA blends. The atomic force microscopic study of the microstructure of etched films showed the ultra-homogenous distribution of PMMA with high glass transition temperature in the PVDF matrix. Consequently, the temperature variation was remarkably decreased, while the high polarization response was maintained. Accordingly, the high energy density of ∼8 J/cm3 with ∼80% efficiency was achieved between 30 and 90 °C in PVDF/PMMA films with 39–62% PMMA content, outperforming most of the dielectric polymers. Our work could provide a general solution to substantially optimize the temperature stability of dielectric polymers for energy storage applications and other associated functions.