BaTiO3/polyvinylidene fluoride (BT/PVDF) is the extensive reported composite material for application in modern electric devices. However, there still exists some obstacles prohibiting the further improvement of dielectric performance, such as poor interfacial compatibility and low dielectric constant. Therefore, in depth study of the size dependent polarization and surface modification of BT particle is of technological importance in developing high performance BT/PVDF composites. Here, a facile molten-salt synthetic method has been applied to prepare different grain sized BT particles through tailoring the calcination temperature. The size dependent spontaneous polarizationof BT particle was thoroughly investigated by theoretical calculation based on powder X-ray diffraction Rietveld refinement data. The results revealed that 600 nm sized BT particles possess the strong polarization, ascribing to the ferroelectric size effect. Furthermore, the surface of optimal BT particles has been modified by water-soluble polyvinylprrolidone (PVP) agent, and the coated particles exhibited fine core-shell structure and homogeneous dispersion in the PVDF matrix. The dielectric constant of the resulted composites increased significantly, especially, the prepared composite with 40 vol % BT loading exhibited the largest dielectric constant (65, 25 °C, 1 kHz) compared with the literature values of BT/PVDF at the same concentration of filler. Moreover, the energy storage density of the composites with tailored structure was largely enhanced at the low electric field, showing promising application as dielectric material in energy storage device. Our work suggested that introduction of strong polarized ferroelectric particles with optimal size and construction of core-shell structured coated fillers by PVP in the PVDF matrix are efficacious in improving dielectric performance of composites. The demonstrated approach can also be applied to the design and preparation of other polymers-based nanocomposites filled with ferroelectric particles to achieve desirable dielectric properties.

FeTiNbO6 (denoted as FTN) is a recently discovered giant dielectric material with high Curie temperature (550 K). In this work, well dispersive FTN particles with mean particle size about 500 nm were synthesized by the improved solid-state reaction method. Using FTN particles as fillers and poly(vinylidene fluoride) (denoted as PVDF) polymer as matrix, multi-volume ratio (0%–60%) homogeneous ceramic/polymer composites have been prepared through a hot-pressing technology. At the same filling content, the FTN/PVDF composites display higher dielectric permittivity compared to the normal reported BaTiO3/PVDF composites, even larger than that of PVDF based composites using giant dielectric CaCu3Ti4O12 as filler. Especially, for 40 vol. % FTN/PVDF composites, the dielectric permittivity is as high as 181 measured at 100 Hz and 25 °C. Through the theoretical analysis correlated with structure evolution observation, it is deduced that the high dielectric performance originates from the combined effect of a variety of factors, such as giant dielectric semiconducting FTN particles, the micro-capacitor structure, and percolation phenomenon at appropriate volume fraction of FTN. Moreover, FTN/PVDF composites present strong dielectric relaxation behavior, which results from the superposition of the dielectric relaxation between PVDF and FTN. These flexible, easy processing FTN/PVDF composites with large dielectric permittivity values could find applications as new generational embedded capacitors.