Free volume dependence of dielectric behaviour in sandwich-structured high dielectric performances of poly(vinylidene fluoride) composite films

A dielectric film with a trilayer structure is fabricated to obtain both a high dielectric constant and superior electrical breakdown strength simultaneously. The outer layers of the trilayered composite film are composed of barium titanate (BTO) particles dispersed in poly(vinylidene fluoride) (PVDF) to ensure a relatively high dielectric constant, while the central layer of the composite film consists of exfoliated hexagonal boron nitride nanosheets (BNNS) dispersed in PVDF to provide high electrical breakdown strength. Compared with pristine PVDF, the dielectric constant and breakdown strength are simultaneously enhanced due to the sandwich structure, and the dielectric loss is maintained at a low level. Most important of all, positron annihilation lifetime spectroscopy (PALS) is applied to study the atomic-scale free volume holes of PVDF composite films and the effect of free volume holes on the dielectric constant and breakdown strength. Results show that the size of free volume holes of PVDF increased with the addition of BTO, but it decreased firstly and then increased with the BNNS loading. The correlation between dielectric properties and the size of free volume holes of the PVDF matrix was discussed in each layer. It is illustrated that the experimental dielectric constant of the PVDF/BTO single-layered film is consistent with the theoretical value at a lower BTO loading but smaller than the theoretical value at a higher BTO loading, which is probably ascribed to the increased size of free volume holes. The breakdown strength of the PVDF/BNNS film increased with the introduction of BNNS and the reduced size of free volume holes, which is ascribed to the reduced partial discharge phenomenon. The atomic-scale microstructure analysis based on free volume holes provides valuable ideas and new understanding for the study of the mechanism of the dielectric behaviour of polymer composites.