目的 开发兼具高储能密度与高放电效率的介电复合薄膜,是应对功率器件向小型化、微型化和轻量化发展的关键途径。方法 采用静电纺丝技术制备形貌均匀的一维Ba0.6Sr0.4TiO3纳米纤维（BST NF）,并通过二辛基磷酸酰氧基钛酸酯偶联剂（NDZ 101）对其进行表面改性（记为BST NF-NDZ）。利用流延成型法制备BST NF-NDZ/聚偏氟乙烯（PVDF）复合薄膜,结合实验表征与有限元模拟,系统研究改性纳米纤维对复合薄膜微观结构、介电性能及储能特性的影响机制。结果 静电纺丝法制备的BST NF直径介于50~350 nm,长度达1.5~11.5 μm,具有良好的一维纳米形貌。钛酸酯偶联剂表面改性显著改善了纳米纤维在PVDF基体中的分散性与界面相容性。介电性能测试表明,随着BST NF-NDZ含量增加,复合薄膜介电常数逐步提升;当填充体积分数为7.5%时,室温介电常数达24.21,同时表现出较低损耗、更高击穿场强、优越的储能密度和放电效率。在BST NF-NDZ为2.5%（体积分数）填充量下,储能密度达到8.53 J/cm³,为纯PVDF薄膜的3.05倍。有限元模拟结果进一步证实,NDZ-101修饰有效调控了复合体系中的局部电场分布,抑制了电场集中效应,从而提升了击穿场强与整体储能性能。结论 利用钛酸酯偶联剂对纳米纤维进行表面改性,可在低填充量下有效调控填料-基体界面特性,协同提升复合薄膜的介电常数与击穿强度,显著增强其储能性能。为高性能聚合物基电介质材料的设计与工程应用提供了一定的实验依据和技术参考。
Abstract
High energy storage density dielectric capacitors, as core electronic components, are widely used in modern industries such as medical equipment and defense technology due to their high discharge power, high energy utilization efficiency, fast charging and discharging capabilities, as well as good cycle stability and operational reliability. However, the lower energy storage density limits further compression of the capacitors in terms of volume and weight, becoming the main bottleneck restricting their development towards miniaturization and lightweighting. To enhance the energy storage performance of polymer based dielectrics, the strategy of introducing high dielectric constant inorganic ceramic fillers into the polymer matrix is commonly adopted to construct polymer based composite dielectrics. However, there are significant differences in physical and chemical properties between high dielectric constant inorganic ceramic fillers and organic polymer matrices, resulting in poor interfacial compatibility and weak bonding between the two. Especially under the high filler content, nanoscale ceramic particles are prone to agglomeration, forming micropores or defects inside the composite material, which can lead to dielectric performance degradation and a decrease in breakdown strength, seriously restricting their practical application in high-frequency and high-performance passive electronic devices. Therefore, how to effectively improve the interfacial properties of inorganic fillers, enhance their dispersion uniformity in polymer matrices, and strengthen the interfacial interactions between ceramics, interfacial layers and polymers has become a key scientific issue and hot research direction in ceramic/polymer composites.
One-dimensional Ba0.6Sr0.4TiO3 nanofibers (BST NF) with uniform morphology were prepared through electrospinning technology, and surface modification was carried out with a dioctyl phosphate oxytitanate coupling agent (NDZ 101) (referred to as BST NF-NDZ). The BST NF-NDZ/polyvinylidene fluoride (PVDF) composite film was prepared by flow casting method, and the effect mechanism of modified nanofibers on the microstructure, dielectric properties, and energy storage performances of the composite films was systematically studied by combining experimental characterization and finite element simulation.
The BST NF prepared by electrospinning method had a diameter of 50-350 nm and a length of 1.5-11.5 μm, exhibiting one-dimensional nanostructure integrity. The surface modification of the titanium ester coupling agent significantly improved the dispersibility and interfacial compatibility of nanofibers in PVDF matrix. The dielectric performance test showed that as the content of BST NF-NDZ increased, the dielectric constant of the composite film gradually increased. When the filling volume fraction was 7.5%, the room temperature dielectric constant reached 24.21, exhibiting lower losses, higher breakdown strength and superior energy storage density and discharge efficiency. At a filling level of 2.5vol.% in BST NF-NDZ, the energy storage density reached 8.53 J/cm3, which was 3.05 times that of the pure PVDF film. The finite element simulation results further confirmed that NDZ-101 modification effectively regulated the local electric field distribution in the composite system, suppressed the electric field concentration effect, and thus improved the breakdown strength and overall energy storage performance. Surface modification of nanofibers with titanium ester coupling agents can effectively regulate the interface characteristics between fillers and the matrix at low filling levels, synergistically improve the dielectric constant and breakdown strength of composite films, and significantly enhance their energy storage performance. This study provides reliable experimental basis and technical support for the design and engineering application of high-performance polymer based dielectric composites.
关键词
复合薄膜 /
储能性能 /
一维纤维填料 /
钛酸酯偶联剂 /
表面改性 /
介电性能
Key words
composites films /
energy storage properties /
one-dimensional nanofibers fillers /
titanate coupling agent /
surface modification /
dielectric properties
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基金
河南省科技攻关计划项目（252102231014,262102231004）; 河南省大学生创新训练计划项目（202511517015）; 河南省高等学校重点科研项目（26A430004）
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