目的 研制兼具高储能密度与高放电效率的介电复合薄膜,是推动功率型电子器件向小型化、微型化和轻量化发展的关键。方法 采用静电纺丝法制备具有一维结构的BaZr0.3Ti0.7O3纳米纤维（BZT NF）,并对其表面羟基化改性（记为BZT NF-OH）。利用流延成型工艺制备BZT NF-OH/聚偏氟乙烯（PVDF）复合薄膜,并结合实验表征与有限元模拟,系统考察了羟基修饰的填料对复合体系微观形貌、介电响应及储能性能的调控规律及其内在机理。结果 制备出的BZT NF呈一维纤维形貌,直径分布介于80~240 nm,长度达11.4 μm,分散性良好。表面羟基改性可以改善纤维填料在PVDF基体分散与界面键合。介电性能测试表明,随BZT NF-OH添加量上升,复合电介质薄膜的介电系数显著增大;当填充体积分数为7.5%时,室温下该介电系数达到20.1,损耗相应下降,击穿场强显著提升。储能性能分析表明,在BZT NF-OH为2.5%的填充量（体积分数）下,复合材料储能密度达到8.31 J/cm3,较纯PVDF提高了189%。该性能提升主要归因于羟基化引发的双重效应：一方面促进了BZT NF在PVDF基体中的均匀分散,另一方面优化了界面结合状态。有限元模拟进一步证实,表面羟基化改性有助于均化内部电场分布,抑制局部击穿,从而提升整体耐压能力。结论 表面羟基化改性可有效调控纳米纤维与PVDF界面特性,在较低填料体积分数下实现介电常数与击穿强度的协同提升,显著增强复合材料的储能性能,为高性能电介质电容器的设计与开发提供了可行路径。
Abstract
As essential fundamental electronic components, high-energy-density dielectric capacitors play a critical role in modern industry and defense technology, thanks to their high discharge power, efficient energy utilization, rapid charge-discharge response, excellent cycling durability, and stable performance. However, capacitors currently available on the market still generally suffer from limitations such as relatively low energy storage density, limited output current capability, and short service life, which lead to larger overall device sizes and constrain their further application in compact systems. Developing dielectric composite films featuring simultaneously high stored-energy density and excellent discharge efficiency is crucial for advancing power electronic devices toward miniaturization, downsizing, and lightweight design. In this study, one-dimensional BaZr0.3Ti0.7O3 nanofibers (BZT NFs) were synthesized via the electrospinning technique and incorporated as functional fillers into a PVDF polymer matrix. To improve the dispersion uniformity of the nanofibers in the organic matrix, enhance the interfacial compatibility between the inorganic and organic phases, and further boost the overall performance of the composite system, surface hydroxylation treatment was applied to modify the fibers t (denoted as BZT NF-OH). Subsequently, one-dimensional BZT NF-OH/PVDF dielectric composite films were fabricated through a doctor-blade film-casting process. Combining experimental characterization with theoretical simulations, the influence of surface hydroxylation treatment on the dielectric properties, breakdown strength, and energy storage density of the composites was systematically analyzed.
The as-prepared BZT NFs exhibited well-defined one-dimensional morphology, with diameters ranging from 80 to 240 nm and lengths extending from 11.4 μm, showing excellent dispersibility. Surface hydroxylation significantly enhanced the uniform dispersion of nanofibers within the PVDF matrix and strengthened interfacial adhesion. Dielectric measurements revealed that the incorporation of BZT NF-OH effectively increased the dielectric constant of the composites; at a filler loading of 7.5vol%, the room-temperature dielectric constant reached 20.1, accompanied by reduced dielectric loss. As the filler concentration increased, the breakdown strength of the composite system decreased slightly. This was attributed to the introduction of local defects or micro-voids caused by the incorporation of BZT NF fillers into the PVDF matrix, which led to uneven electric field distribution and consequently a reduction in breakdown strength. Energy storage analysis demonstrated that the composite film with 2.5 vol. % BZT NF-OH achieved a high energy storage density of 8.31 J/cm3, representing a 189% enhancement compared to pristine PVDF. The composite exhibited the optimal efficiency performance. At electric fields below 1 000 kV/cm, the discharge efficiency remained above 84%, even under a high electric field of 3 850 kV/cm, the efficiency could still be maintained above 60%, both significantly superior to those of the pure PVDF. This remarkable improvement was attributed to a dual effect induced by hydroxylation, which improved dispersion homogeneity and optimized interfacial compatibility. Finite element simulations further confirmed that surface hydroxylation promoted a more uniform electric field distribution within the composite, suppressed localized electrical breakdown, and thereby enhanced overall dielectric strength.
In conclusion, surface hydroxylation serves as an effective strategy to tailor the interface between BZT nanofibers and the PVDF matrix, enabling simultaneous enhancement of dielectric constant and breakdown strength at low filler content. This work provides a promising pathway for the design and development of high-performance dielectric capacitors.
关键词
PVDF /
BaZr0.3Ti0.7O3 /
一维纳米纤维 /
复合材料 /
表面羟基化 /
储能性能 /
介电性能
Key words
PVDF /
BaZr0.3Ti0.7O3 /
one-dimensional nanofibers /
composites /
surface hydroxylation /
energy storage performance /
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（202611517001）; 河南省高等学校重点科研项目（26A430004）
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