面向高温介电储能应用的聚合物基电介质材料研究进展

董久锋; 邓星磊; 牛玉娟; 潘子钊; 汪宏

doi:10.7498/aps.69.20201006

摘要

介电储能电容器以其充放电速度快、功率密度高等优点, 在现代电子和电力系统中得到了广泛应用. 目前, 与可再生能源相关的新兴产品, 如混合动力汽车、并网光伏发电和风力发电、井下油气勘探等, 对于介电储能电容器的高温储能性能提出了更高的要求. 本文总结了近年来关于聚合物及其纳米复合电介质材料的高温介电储能研究中的代表性研究进展, 为该领域科研工作者进一步研究提供参考. 首先介绍了电介质材料储能的物理机理, 并对电介质材料的几种电导机制进行了总结和分析; 接下来介绍了目前提高聚合物基电介质材料高温储能性能的几种方法, 包括纳米复合改性和相关的层状结构设计, 以及高分子聚合物的分子结构设计和化学交联处理等; 最后对聚合物基电介质材料在高温储能应用领域中尚待解决的科学技术问题进行了讨论, 并展望了未来可能的研究方向.

关键词:

电容器 /
介电材料 /
高温 /
能量密度

Abstract

Dielectric capacitors are widely used in modern electronic systems and power systems because of their advantages of fast charge discharge speed and high-power density. Nowadays, the new products related to renewable energy, such as hybrid electric vehicles, grid connected photovoltaic power generation and wind turbines, downhole oil, gas exploration, etc., put forward higher requirements for the energy storage capabilities of dielectric capacitors in elevated-temperature. In this review, the research progress of the polymer-based dielectrics for high-temperature capacitor energy storage in recent years is systematically reviewed to offer benefits for further study. Firstly, the physical mechanism of energy storage of dielectric materials is introduced, and several conduction mechanisms of dielectric materials are summarized and analyzed; then, several strategies to improve the high-temperature energy storage performance of polymer dielectrics are presented, including the nanocomposite modification and design of layer-structured polymer composites, and the molecular structure design and chemical crosslinking treatment of dielectric polymer. Finally the scientific and technological problems in the application of dielectric polymer and their nanocomposites for high-temperature capacitor energy storage are discussed, and a possible research direction in the future is prospected.

Keywords:

作者及机构信息

1.
南方科技大学材料科学与工程系, 深圳　518055

2.
西安交通大学电子与信息工程学院, 西安　710049

通信作者: 汪宏, wangh6@sustech.edu.cn

基金项目: 深圳市科技计划(批准号: KQTD20180411143514543, JCYJ20180504165831308)、广东省重点领域研发计划(批准号: 2020B010176001)和深圳市工程研究中心项目(批准号: [2018]1433)资助的课题

Authors and contacts

1.
Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, China

2.
School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Corresponding author: Wang Hong, wangh6@sustech.edu.cn

Funds: Project supported by the Science and Technology Program of Shenzhen, China (Grant Nos. KQTD20180411143514543, JCYJ20180504165831308), the Key Area R&D Program of Guangdong Province, China (Grant No. 2020B010176001), and the DRC Project of Shenzhen, China (Grant No. [2018]1433)

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施引文献

图 1 介电电容器、电化学电容器与电池的能量密度和功率密度的对比图

Fig. 1. Comparison of power density and energy density capabilities of dielectric capacitors, electrochemical capacitors, and batteries.

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图 2 (a) 两个金属电极之间的电介质电容器示意图; (b) 电介质材料的电位移-电场强度关系曲线

Fig. 2. (a) Schematic diagram of dielectric capacitor between two metal electrodes; (b) electric displacement-electric field (D-E) hysteresis loop of a dielectric material.

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图 3 各种电导机制的示意图

Fig. 3. Schematic diagrams of various conduction mechanisms.

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图 4 (a) PI-STO纳米复合膜制备的电容器示意图; 当电场强度为200 kV/mm, 400 K温度条件下工作时, 由(b) 纯PI, (c) 垂直纳米纤维, (d) 垂直纳米片, (e) 随机纳米颗粒, (f) 平行纳米纤维, (g) 平行纳米片填充的纳米复合薄膜制备的不同电容器的稳态温度分布; (h) 薄膜电容器内的最大温度T_max与热导率κ_z和电导率σ_z的函数关系图; (i) 6种情况下, 最大温度T_max(红色条)、击穿强度劣化因子β (蓝色条)和介电损耗tanδ (黑色条)的性能比较^[53]

Fig. 4. (a) Schematic illustration of a real capacitor made by winding the PI-STO nanocomposite film. When working under an applied electric field of 200 kV/mm and a surrounding temperature of 400 K, the steady-state temperature distributions in different capacitors made by film nanocomposites filled by (b) pure polymer, (c) vertical nanofibers, (d) vertical nanosheets, (e) random nanoparticles, (f) parallel nanofibers, and (g) parallel nanosheets. (h) Maximal temperature T_max inside the film capacitor as function of the thermal conductivity component κ_z and electrical conductivity component σ_z. (i) Comparisons of the maximal temperature T_max (red bar), breakdown strength deterioration factor β (blue bar), and dielectric loss tanδ (black bar) among six circumstances^[53].

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图 5 (a) 在25 ℃和1 kHz下, PI纳米复合材料的介电常数和损耗随填料含量的变化; PI和PI纳米复合材料在150 ℃下的(b) Weibull击穿强度和(c)储能性能; (d) 150 ℃下, 模拟电流密度分布随Al₂O₃, HfO₂和TiO₂填料含量和外加电场的变化^[59]

Fig. 5. (a) Dielectric constant and loss of the PI nanocomposites as a function of filler content at 25 ℃ and 1 kHz; (b) Weibull breakdown strength and (c) energy density performance of PI and the PI nanocomposites measured at 150 ℃; (d) simulated current density distribution as a function of Al₂O₃, HfO₂, and TiO₂ filler content and the applied electric field at 150 ℃^[59].

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图 6 (a) 蜘蛛丝和蜘蛛丝的显微结构; (b) BN-BCB@DPAES复合材料的工艺图^[76]

Fig. 6. (a) Spider silk and the hierarchical microscopic structure of the spider silk; (b) schematic of preparation process of BN-BCB@DPAES films^[76].

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图 7 (a) Roll-to-roll PECVD示意图; (b) 聚合物表层沉积SiO₂的断面扫描电子显微镜图; (c) 聚合物表层沉积SiO₂的断面能量色散X射线图谱; (d) 在120 ℃下, BOPP薄膜表层沉积180 nm 厚度的SiO₂前后的储能密度和储能效率对比; (e) 在150 ℃下, 储能效率大于90%时, 各种电介质聚合物薄膜表层沉积SiO₂前后的最大放电能量密度^[93]

Fig. 7. (a) Schematic of the roll-to-roll PECVD; (b) cross-sectional scanning electron microscope image of the coating layer on polymer film; (c) element concentration from energy dispersive X-ray spectroscopy scanned across the coating layer deposited on polymer film; (d) charge-discharge efficiency and discharged energy density of BOPP and BOPP-SiO₂ films with 180 nm coating layer on each side of the polymer measured at 120 ℃; (e) maximum discharged energy density of the various dielectric films before and after coating achieved at above 90% charge-discharge efficiency measured at 150 ℃^[93].

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图 8 (a) 芳香族聚脲、聚硫脲和聚芳醚脲的结构式; (b)砜基化聚苯醚和砜基化自具微孔聚合物的结构式

Fig. 8. (a) Chemical structures of ArPU, ArPTU and PEEU; (b) chemical structures of SO₂-PPO₂₅, and SO₂-PIM.

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