Fu Jing, Hou Yudong, Zheng Mupeng, Wei Qiaoyi, Zhu Mankang, Yan Hui
College of Materials Science and Engineering, Beijing University of Technology , Beijing 100124, China.
ACS Appl Mater Interfaces. 2015 Nov 11;7(44):24480-91. doi: 10.1021/acsami.5b05344. Epub 2015 Oct 29.
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.
钛酸钡/聚偏氟乙烯(BT/PVDF)是一种在现代电子器件应用中被广泛报道的复合材料。然而,仍然存在一些阻碍介电性能进一步提高的障碍,如界面相容性差和介电常数低。因此,深入研究BT颗粒的尺寸依赖性极化和表面改性对于开发高性能BT/PVDF复合材料具有重要的技术意义。在此,通过调整煅烧温度,采用一种简便的熔盐合成方法制备了不同粒径的BT颗粒。基于粉末X射线衍射Rietveld精修数据,通过理论计算深入研究了BT颗粒的尺寸依赖性自发极化。结果表明,600 nm尺寸的BT颗粒具有较强的极化,这归因于铁电尺寸效应。此外,最佳BT颗粒的表面已用水溶性聚乙烯吡咯烷酮(PVP)试剂进行了改性,包覆颗粒在PVDF基体中呈现出良好的核壳结构和均匀分散性。所得复合材料的介电常数显著提高,特别是,与相同填料浓度下BT/PVDF的文献值相比,制备的含40 vol% BT负载量的复合材料在25 °C、1 kHz下表现出最大介电常数(65)。此外,具有定制结构的复合材料在低电场下的储能密度大幅提高,在储能器件中作为介电材料显示出良好的应用前景。我们的工作表明,在PVDF基体中引入具有最佳尺寸的强极化铁电颗粒并通过PVP构建核壳结构的包覆填料,对于提高复合材料的介电性能是有效的。所展示的方法也可应用于设计和制备其他填充铁电颗粒的聚合物基纳米复合材料,以实现理想的介电性能。