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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.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.
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Keywords:
- capacitors /
- dielectric materials /
- high temperature /
- energy density
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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Tmax与热导率κz和电导率σz的函数关系图; (i) 6种情况下, 最大温度Tmax(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 Tmax inside the film capacitor as function of the thermal conductivity component κz and electrical conductivity component σz. (i) Comparisons of the maximal temperature Tmax (red bar), breakdown strength deterioration factor β (blue bar), and dielectric loss tanδ (black bar) among six circumstances[53].
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].
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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