Xie Xu, He Zhen-Zhen, Qi Xiao-Dong, Yang Jing-Hui, Lei Yan-Zhou, Wang Yong
School of Materials Science & Engineering , Key Laboratory of Advanced Technologies of Materials (Ministry of Education) , Southwest Jiaotong University , Chengdu , 610031 , China . Email:
Analytical and Testing Center , Southwest Jiaotong University , Chengdu , 610031 , China.
Chem Sci. 2019 Jul 24;10(35):8224-8235. doi: 10.1039/c9sc01965k. eCollection 2019 Sep 21.
Polymer dielectric composites have widespread applications in many fields ranging from energy storage, microelectronic devices, and sensors to power driven systems, and attract much attention of researchers. However, it is still challenging to prepare advanced polymer dielectric composites with a high dielectric constant ('), low dielectric loss (tan ) and simultaneously high breakdown strength ( ). In this work, conductive polypyrrole (PPy) nanoparticles were synthesized in a reaction system containing the common barium titanate (BaTiO, BT) or hydroxylated BaTiO (BTOH) particles, and then the PPy@BT and PPy@BTOH composite particles were incorporated into poly(vinylidene fluoride) (PVDF) to prepare the composites. The morphologies and microstructures of the PPy@BT and PPy@BTOH composite particles and the corresponding PVDF composites were comparatively investigated. The results showed that the PPy@BTOH composite particles had a 'mulberry'-like morphology with a rough surface and the self-assembled structure could be maintained in the PVDF composites, which was apparently different from the PVDF/PPy@BT composites, in which most of the PPy nanoparticles dissociatively dispersed in the PVDF matrix. Electrical conductivity measurements showed that at high particle content (≥20 wt%), the PPy@BTOH composite particles endowed the composites with lower electrical conductivity compared with the PPy@BT composite particles. Dielectric property measurements showed that the 'mulberry'-like PPy@BTOH composite particles endowed the PVDF composites with extremely high ', ultralow tan and high compared with the PVDF/PPy@BT composites with dissociatively dispersed PPy nanoparticles and BaTiO particles. The polarization and loss mechanisms of the composites were then proposed based on the morphologies and the microstructures of the composites. This work provides an alternative way to fabricate functional dielectric particles through trace functional groups inducing polymerization of conductive polymers, and these particles can be used to fabricate advanced dielectric composites.
聚合物介电复合材料在从能量存储、微电子器件、传感器到电力驱动系统等众多领域有着广泛应用,并吸引了研究人员的广泛关注。然而,制备具有高介电常数(ε′)、低介电损耗(tanδ)且同时具有高击穿强度(Eb)的先进聚合物介电复合材料仍然具有挑战性。在本工作中,在含有普通钛酸钡(BaTiO₃,BT)或羟基化钛酸钡(BTOH)颗粒的反应体系中合成了导电聚吡咯(PPy)纳米颗粒,然后将PPy@BT和PPy@BTOH复合颗粒掺入聚偏氟乙烯(PVDF)中制备复合材料。对PPy@BT和PPy@BTOH复合颗粒以及相应的PVDF复合材料的形貌和微观结构进行了对比研究。结果表明,PPy@BTOH复合颗粒具有表面粗糙的“桑葚”状形貌,且自组装结构能够在PVDF复合材料中得以保持,这与PVDF/PPy@BT复合材料明显不同,在PVDF/PPy@BT复合材料中,大多数PPy纳米颗粒以解离状态分散在PVDF基体中。电导率测量表明,在高颗粒含量(≥20 wt%)时,与PPy@BT复合颗粒相比,PPy@BTOH复合颗粒赋予复合材料更低的电导率。介电性能测量表明,与具有解离分散的PPy纳米颗粒和BaTiO₃颗粒的PVDF/PPy@BT复合材料相比,“桑葚”状的PPy@BTOH复合颗粒赋予PVDF复合材料极高的ε′、超低的tanδ和高的Eb。然后基于复合材料的形貌和微观结构提出了复合材料的极化和损耗机制。本工作提供了一种通过微量官能团诱导导电聚合物聚合来制备功能性介电颗粒的替代方法,这些颗粒可用于制备先进的介电复合材料。