掺杂改性PMMA/PVDF共混聚合物基复合介质的储能性能提升

张昌海; 闫炜东; 张统钦; 张天栋; 迟庆国; 刘献礼

doi:10.13801/j.cnki.fhclxb.20220913.004

掺杂改性PMMA/PVDF共混聚合物基复合介质的储能性能提升

doi: 10.13801/j.cnki.fhclxb.20220913.004

1.
哈尔滨理工大学　电气与电子工程学院，哈尔滨 150006
2.
许继电气股份有限公司　柔性输电分公司，高压技术试验中心，许昌 461000
3.
哈尔滨理工大学　机械动力学院，哈尔滨 150006

基金项目: 国家自然科学基金青年科学基金(52007042)；黑龙江省自然科学基金联合引导项目(LH2020 E091)；电子薄膜与集成器件国家重点实验室开放项目(KFJJ201904)

详细信息

通讯作者:
张天栋，博士，副教授，博士生导师，研究方向为聚合物电容器薄膜　E-mail: tdzhang@hrbust.edu.cn

中图分类号: TM211
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出版历程
- 收稿日期: 2022-07-25
- 修回日期: 2022-08-28
- 录用日期: 2022-09-05
- 网络出版日期: 2022-09-14

Improved energy storage performance of PMMA/PVDF blend polymer matrix composites by doping modification

1.
School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150006, China
2.
High Pressure Technology Test Center, Flexible Transmission Branch, Xuji Electric Co., Ltd., Xuchang 461000, China
3.
School of Mechanical Power, Harbin University of Science and Technology, Harbin 150006, China

Funds: National Natural Science Foundation of China Youth Science Foundation (52007042); Natural Science Foundation of Heilongjiang Province (LH2020 E091); Open Project of National Key Laboratory of Electronic Thin Films and Integrated Devices (KFJJ201904)

摘要

摘要: 薄膜电容器在高压输电换流站、新能源汽车电驱动控制器、电磁武器脉冲功率电源等电气工程和电子器件领域具有重要应用。当前薄膜电容器正向着高能量密度、耐电压、耐高温等技术方向发展，对电容薄膜的电气性能提出了更高要求。本文选择铁电聚偏氟乙烯(PVDF)和聚甲基丙烯酸甲酯 (PMMA)共混物作为储能聚合物基体，以具有高介电常数的纳米粒子BaTiO₃ (BT)和具有高电子亲和能的有机分子半导体[6, 6]-苯基C61丁酸甲酯(PCBM)作为掺杂相，综合利用BT的高介电特性以及PCBM的捕获电荷能力，提高复合介质的极化强度与击穿场强，显著改善储能性能。研究表明，单掺杂BT时，掺杂含量为3wt%时复合介质综合性能最优；在此基础上，随着PCBM掺杂含量增大其储能密度和充放电效率提升明显。当PCBM掺杂含量为2wt%时，含有3wt%BT的PMMA/PVDF复合介质具有优异的储能性能，当电场为579.67 kV/mm时，放电能量密度达到15.60 J/cm³且充放电效率为75.30%。本文首次提出基于少量无机高介电协同有机分子半导体功能填料的聚合物薄膜储能性能改性研究，通过加入少量的BT，既避免了因BT含量过高而导致的绝缘性能下降问题，又保证了BT粒子对复合介质介电常数和极化性能的提升。同时，为了进一步改善因低介电常数基体与高介电常数BT颗粒之间的电场畸变所导致的击穿强度下降问题，考虑在复合介质中加入一定量的PCBM，利用PCBM强大的电子亲和能力，在复合介质中构筑深陷阱以捕获和束缚载流子，抑制载流子的迁移，提升复合介质的击穿场强，从而综合提升了复合介质的储能性能，这为开发储能性能优异的聚合物复合介质提供了一种新思路。
- 薄膜电容器 /
- 聚偏氟乙烯 /
- 有机分子半导体 /
- 介电性能 /
- 储能密度
Abstract: Thin film capacitors have important applications in the fields of electrical engineering and electronic devices such as high voltage transmission converter stations, new energy vehicle electric drive controllers, electromagnetic weapon pulse power supply and so on. At present, thin-film capacitors are developing towards the technical direction of high energy density, voltage resistance, high temperature resistance and so on, which put forward higher requirements for the electrical performance of capacitor films. In this study, ferroelectric polyvinylidene fluoride (PVDF) and polymethyl methacrylate (PMMA) blends were selected as the energy storage polymer matrix, and BaTiO₃ (BT) nanoparticles with high dielectric constant and organic molecular semiconductor [6, 6]-phenyl C61 methyl butyrate (PCBM) with high electron affinity were used as the doping phase. The high dielectric properties of BT and the ability of PCBM to capture charge are comprehensively utilized to improve the polarization strength and breakdown field strength of the composite medium and significantly improve the energy storage performance. The results show that when the doping content is 3wt%, the composite media has the best comprehensive performance. On this basis, with the increase of PCBM doping content, its energy storage density and charge-discharge efficiency improved significantly. When PCBM doping content is 2wt%, PMMA/PVDF composite medium containing 3wt%BT has excellent energy storage performance. When the electric field is 579.67 kV/mm, the discharge energy density reaches 15.60 J/cm³ and the charge-discharge efficiency is 75.30%. First proposed in this paper, based on a small amount of inorganic high dielectric organic molecules together semiconductor filler modified polymer film energy storage performance of the function, by adding a small amount of BT particles, avoids insulation performance degradation caused by the high content of BT, and ensures the BT particle on the properties of composite dielectric permittivity and polarization. At the same time, in order to further improve due to the low dielectric constant substrate with high dielectric constant BT particles between the electric field distortion caused by the breakdown strength degradation, consider joining a certain amount of PCBM in a composite medium, use PCBM electron affinity ability, strong in composite medium build deep traps to capture and carrier, inhibit the transfer of carrier.The breakdown field strength of the composite medium is improved, so as to comprehensively improve the energy storage performance of the composite medium, which provides a new idea for the development of polymer composite medium with excellent energy storage performance.
- film capacitor /
- polyvinylidene fluoride /
- organic molecular semiconductor /
- dielectric properties /
- energy storage density

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图 1 BaTiO₃ (BT)颗粒的SEM图像

Figure 1. SEM image of BaTiO₃ (BT) particles

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图 2 不同BT含量的聚甲基丙烯酸甲酯 (PMMA)/聚偏氟乙烯(PVDF)-xwt%-BT共混复合薄膜的SEM图像：(a) 1wt%；(b) 2wt%；(c) 3wt%；(d) 4wt%

Figure 2. SEM images of polymethyl methacrylate (PMMA)/polyvinylidene fluoride (PVDF)-xwt%-BT blended composite films with different BT contents: (a) 1wt%; (b) 2wt%; (c) 3wt%; (d) 4wt%

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图 3 PMMA/PVDF-xwt%-BT共混复合薄膜的XRD图像

Figure 3. XRD patterns of PMMA/PVDF-xwt%-BT blended composite films

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图 4 PMMA/PVDF-xwt%-BT共混复合薄膜的FTIR图谱

Figure 4. FTIR spectra of PMMA/PVDF-xwt%-BT blend composite films

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图 5 PMMA/PVDF-xwt%-BT共混复合薄膜的电学性能：(a) 介电常数；(b) 介电损耗；(c) 漏电流密度；(d) 击穿场强

Figure 5. Electrical properties of PMMA/PVDF-xwt%-BT blend composite films: (a) Dielectric constant; (b) Dielectric loss; (c) Leakage current density; (d) Breakdown field strength

P—

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图 6 PMMA/PVDF-xwt%-BT共混复合薄膜的极化性能：(a) 电位移-电场强度(D-E)曲线；(b) 最大极化(D_max)和剩余极化(D_r)的柱状图分布

Figure 6. Polarization properties of PMMA/PVDF-xwt%-BT blend composite films: (a) Electric displacement-electric field intensity (D-E) curves; (b) Histogram distribution of maximum polarization (D_max) and residual polarization (D_r)

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图 7 PMMA/PVDF-xwt%-BT共混复合薄膜的储能性能：(a) 储能密度(U_e)和储能效率(η)变化规律；(b) 储能密度和储能效率的柱状图分布

Figure 7. Energy storage performance of PMMA/PVDF-xwt%-BT blend composite film: (a) Changing rule of energy storage density (U_e) and energy storage efficiency (η); (b) Histogram distribution of energy storage density and energy storage efficiency

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图 8 PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的SEM截面图像：(a) 1wt%PCBM；(b) 1.5wt%PCBM；(c) 2wt%PCBM；(d) 2.5wt%PCBM

Figure 8. SEM cross sections of PMMA-ywt%PCBM@PVDF-3wt%BT composite films: (a) 1wt%PCBM; (b) 1.5wt%PCBM; (c) 2wt%PCBM; (d) 2.5wt% PCBM

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图 9 PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的XRD图谱

Figure 9. XRD patterns of PMMA-ywt%PCBM@PVDF-3wt%BT blend composite films

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图 10 PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的FTIR图谱

Figure 10. FTIR spectra of PMMA-ywt%PCBM@PVDF-3wt%BT blend composite films

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图 11 PMMA-xwt.%PCBM@PVDF-3wt.% BT共混复合薄膜的电学性能：(a)介电常数, (b) 介电损耗, (c) 漏电流密度, (d) 击穿场强

Figure 11. Electrical properties of pmma-xwt.%PCBM@PVDF-3wt.% BT blend composite films :(a) dielectric constant, (b) dielectric loss, (c) leakage current density, (d) breakdown field strength

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图 12 PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的极化性能：(a) D-E曲线；(b) D_max和D_r的柱状图分布

Figure 12. Polarization properties of PMMA-ywt%PCBM@PVDF-3wt%BT blend composite films: (a) D-E curves; (b) Histogram distribution of D_max and D_r

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图 13 PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的储能性能：(a) 储能密度和储能效率变化规律；(b) 储能密度和储能效率的柱状图分布

Figure 13. Energy storage performance of PMMA-ywt%PCBM@PVDF-3wt%BT blend composite films: (a) Energy storage density and energy storage efficiency; (b) Histogram distribution of energy storage density and energy storage efficiency

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表 1 具有不同BT含量的PMMA/PVDF-xwt%-BT共混复合薄膜的电学性能参数

Table 1. Electrical properties of PMMA/PVDF-xwt%-BT blended composite films with different BT contents 100 Hz

Sample	ε	tanδ	E_b/(kV·mm⁻¹)	β
PMMA/PVDF	5.50	0.0586	593.39	12.55
PMMA/PVDF-1wt%-BT	5.80	0.0531	554.76	12.04
PMMA/PVDF-2wt%-BT	6.00	0.0543	522.67	10.20
PMMA/PVDF-3wt%-BT	6.37	0.0584	511.96	11.51
PMMA/PVDF-4wt%-BT	6.90	0.0601	434.52	9.84
Notes: ε—Dielectric constant; tanδ—Dielectric loss; E_b—Breakdown electric field; β—Shape parameter.

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表 2 不同PCBM含量的PMMA-ywt%PCBM@PVDF-3wt%BT共混复合薄膜的电学性能参数

Table 2. Electrical properties of PMMA-ywt%PCBM@PVDF-3wt%BT blends with different PCBM contents 100 Hz

Sample	ε	tanδ	E_b/(kV·mm⁻¹)	β
PMMA/PVDF-3wt%-BT	6.37	0.0584	511.96	11.51
PMMA-1wt%PCBM@PVDF-3wt%BT	6.57	0.0620	531.70	10.98
PMMA-1.5wt%PCBM@PVDF-3wt%BT	6.78	0.0585	563.83	10.02
PMMA-2wt%PCBM@PVDF-3wt%BT	7.06	0.0546	579.67	11.17
PMMA-2.5wt%PCBM@PVDF-3wt%BT	7.29	0.0653	490.94	10.99

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