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三明治结构柔性储能电介质材料研究进展

李雨凡 薛文清 李玉超 战艳虎 谢倩 李艳凯 查俊伟

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三明治结构柔性储能电介质材料研究进展

李雨凡, 薛文清, 李玉超, 战艳虎, 谢倩, 李艳凯, 查俊伟

Research progress of flexible energy storage dielectric materials with sandwiched structure

Li Yu-Fan, Xue Wen-Qing, Li Yu-Chao, Zhan Yan-Hu, Xie Qian, Li Yan-Kai, Zha Jun-Wei
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  • 聚合物电介质材料因其高功率密度、耐击穿、安全柔韧、易加工和自愈性等特点, 被广泛应用于智能电网、新能源汽车、航空航天、国防科技等领域. 其中, 基于三明治结构设计获得具有更高储能密度和储能效率的柔性电介质材料成为近年来聚合物储能电介质领域的研究热点和常用策略. 本文从电介质的材料构成、结构设计以及制备方法等角度综述了基于三明治结构聚合物电介质薄膜在储能密度提升方面的研究进展, 阐述了三明治结构电介质材料性能调控的微观机制和协同增强机理, 并展望了其发展趋势和应用前景.
    Polymer dielectric materials show wide applications in smart power grids, new energy vehicles, aerospace, and national defense technologies due to the ultra-high power density, large breakdown strength, flexibility, easy processing, and self-healing characteristics. With the rapid development of integration, miniaturization and lightweight production of electronic devices, it is required to develop such a storage and transportation dielectric system with larger energy storage density, higher charge and discharge efficiency, good thermostability and being environmentally friendly. However, the contradiction between dielectric constant and breakdown strength of dielectric materials is the key factor and bottleneck to obtain a high performance dielectric material. It is accepted that controlling charge distribution and inhibiting charge carrier injection are important to improve the energy storage characteristics of polymer dielectrics. In recent years, the materials with sandwiched or stacking structures have demonstrated outstanding advantages in inhibiting charge injection and promoting polarization, allowing polymer dielectrics to have increased permittivity and breakdown strength at the same time. Therefore, from the perspectives of material composition, structural design, and preparation methods, this study reviews the research progress of polymer dielectric films with sandwiched structure in improving the energy storage performance. The influence of dielectric polarization, charge distribution, charge injection, interfacial barrier and electrical dendrite growth on the energy storage performance and the synergistic enhancement mechanisms in such sandwich-structured dielectric materials are systematically summarized, showing good development and vast application prospects.In brief, introducing easy polarization, wide-gap and deep-trap nanofillers has greater designability and regulation in the dielectric and breakdown properties. In addition, using the hard layer as the outer layer can reduce charge injection more effectively, resulting in a high breakdown resistance performance that is easy to achieve. The sandwiched structure design also possesses advantages over other methods in maintaining good flexibility and dielectric stability of dielectric materials, thus having become a hot-topic research area in recent years. In the future, it is necessary to combine low conductivity and high thermal conductivity of dielectric polymers to realize high temperature energy storage and efficiency. Researches on recyclable, self-repairing sandwiched insulating films are good for the service life and safety of electronic components and will further expand the application scope of dielectric polymers. Finally, effective evaluation of dielectric with sandwiched structure and energy storage performances through simulation and theoretical modeling is very helpful in revealing the breakdown mechanism and thermal failure mechanism, and also in theoretically guiding the design of polymer dielectric materials.
      通信作者: 李玉超, liyuchao@lcu.edu.cn ; 查俊伟, zhajw@ustb.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 52177020, 52277022)和大学生创新创业训练计划(批准号: CXCY2022184)资助的课题.
      Corresponding author: Li Yu-Chao, liyuchao@lcu.edu.cn ; Zha Jun-Wei, zhajw@ustb.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 52177020, 52277022) and the College Student Innovation and Entrepreneurship Training Program, China (Grant No. CXCY2022184).
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  • 图 1  (a) 介质材料极化储能过程[5]; (b) 介电材料的D-E曲图[6]

    Fig. 1.  Schematic diagram of (a) polarization[5] and (b) D-E loop of dielectric materials[6].

    图 2  BN和TiO2协同提升三明治结构电介质材料储能机理[19]

    Fig. 2.  Synergistic enhancement of energy storage mechanism of sandwich structure composite by BN and TiO2[19].

    图 3  三明治结构 (a) 全有机P(VDF-HFP)-PMMA-P(VDF-HFP)薄膜[21]; (b) 有机/无机PVDF-BT/PVDF-PVDF薄膜[22]; (c) BN, Sr2Nb2O7协同增强PMMA/PVDF电介质薄膜[23]; (d) PI-Al2O3-PI薄膜示意图[25]

    Fig. 3.  Diagram of sandwich structure: (a) All-organic composite film of P(VDF-HFP)-PMMA-P(VDF-HFP) [21], (b) organic/inorganic composite film of PVDF-BT/PVDF-PVDF[22], (c) BN, Sr2Nb2O7 synergistically reinforced PMMA/PVDF dielectric film[23] and (d) PI-Al2O3-PI composite film[25].

    图 4  (a) 对称型A-B-A和B-A-B三明治结构电介质材料示意图; (b) 不同结构电介质材料的储能密度[45]; (c) 相场模拟不同结构复合电介质材料的失效概率与场强关系[59]

    Fig. 4.  (a) Schematics of symmetric A-B-A and B-A-B types of sandwich structure; (b) different energy storage density [45] and (c) failure probability versus electric field [59] of A-B-A and B-A-B types of structure.

    图 5  (a) 五层结构PVDF-SNBT/PVDF-PVDF复合薄膜结构示意图[62]; (b) 对称梯度结构BZCT/PVDF多层膜材料示意图[66]; (c) 非对称梯度结构PEI-PEI/P(VDF-HFP)-P(VDF-HFP)薄膜示意图[67]

    Fig. 5.  Schematic of (a) a five-layer dielectric composite film[62], (b) a symmetrically gradient dielectric film[66] , and (c) an asymmetrically gradient PEI-PEI/P(VDF-HFP)-P(VDF-HFP) film[67].

    图 6  (a) 流延工艺[21]及其(b) PMMA/PVDF-BCZT/PVDF-PMMA/PVDF薄膜扫描电镜图 [68]; (c) 旋涂工艺及其(d) BT@HPC/PVDF-PVDF-BT@HPC/PVDF薄膜扫描电镜图[42]

    Fig. 6.  Sandwich structure composite films prepared by (a) flow casting[21] and (b) representative SEM image of PMMA/PVDF-BCZT/PVDF-PMMA/PVDF dielectric film [68], (c) spin coating process and (d) representative SEM image of BT@HPC/PVDF-PVDF-BT@HPC/PVDF film [42].

    图 7  (a) 热压法制备FPE-P(VDF-HFP)-FPE三明治结构薄膜的制备过程和扫描电镜图[36]; (b) 静电纺丝制备P(VDF-HFP)和BT/P(VDF-HFP)多层膜结构及其扫描电镜图 [71]

    Fig. 7.  (a) Hot-compression molding process of FPE-P(VDF-HFP)-FPE sandwich film and SEM image[36]; (b) electrostatic spinning preparation of P(VDF-HFP) and BT/P(VDF-HFP) multilayer film and its SEM image[71].

    表 1  不同材料构成A-B-A型三明治电介质材料的介电性能

    Table 1.  Dielectric properties of A-B-A type sandwich dielectric materials

    材料构成A层(含量, 厚度)B层(含量, 厚度)A-B-A三明治(25 ℃, 1 kHz)
    $\varepsilon_{\mathrm{r}} $tanδE/(MV·m–1)U/(J·cm–3)η/%制备方法U/U基体文献
    全有机复合PVDF (3 μm)P(VDF-TrFE-CTFE) (3 μm)12.060.3559920.8660溶液涂膜1.3[20]
    P(VDF-HFP) (6.5 μm)PMMA (6 μm)70.0344020.384溶液浇筑1.3[21]
    PVDF (4 μm)P(VDF-TrFE)-PVDF (70% PVDF, volume percent, 10 μm)120.0358223.465.5溶液浇筑1.5[26]
    P(VH-HFP) (3 μm)P(VDF-HFP)-PMMA (25% PMMA, weight percent, 4 μm)90.256802874热压、拉伸1.8[27]
    P(VDF-TrFE-CFE) (4 μm)PMMA (13 μm)50.05399.19.778静电纺丝、热压1.7[28]
    P(VDF-TrFE-CFE) (2 μm)PVDF (2 μm)10.20.02550.918.360溶液涂覆2.44[29]
    PMMA-P(VDF-TrFE-CFE) (20% PMMA, weight percent, 4 μm)DE-P(VDF-TrFE-CFE) (15% DE, weight percent, 4 μm)70.0579020.166溶液浇筑2.5[30]
    Parylene (1 μm)PI (17 μm)5.040.434604.7244.8CVD2.9[31]
    DE-P(VDF-HFP) (30% DE, weight percent, 2.5 μm)PMMA (14.5μm)30011.889溶液浇筑1.45[32]
    PEI (4.5 μm)P(VDF-TrFE-CFE) (3 μm)~70.03504881溶液浇筑2.6[33]
    P(VDF-TrFE-CFE) (3.4 μm)PEI (6.7 μm)~50.01275480溶液浇筑1.3[33]
    PVDF (6.5 μm)DE (4 μm)10.40.0343820.9272溶液浇筑1.3[34]
    PET (2 μm)P(VDF-HFP) (5 μm)4.50.01583.28.286.4溶液浇筑1.17[35]
    Fluorene polyester (7 μm)P(VDF-HFP) (4 μm)40.014564886.7溶液浇筑、热压1.1[36]
    PMMA (4 μm)P(VDF-TrFE-CFE) (9 μm)4.50.057.0378溶液浇筑1.55[37]
    PVDF (9 μm)P(VDF-TrFE-CFE) (16 μm)160.034088.760溶液浇筑、热压2[38]
    有机/无机杂化BN/PVDF (2%, weight
    percent, 4 μm)
    TiO2/PVDF (3%, weight
    percent, 4 μm)
    11.420.03369.910.1756溶液浇筑、热压5[19]
    PVDF (3 μm)BT@SiO2@PDA/PVDF (3 μm)120.02363415.364溶液浇筑3.85[24]
    BT/PVDF (3%, weight
    percent, 4 μm)
    PVDF (4 μm)13.3<0.0255051560溶液浇筑1.6[22]
    PVDF (4 μm)BT/PVDF (3%, 4 μm)12.9<0.025519.719.168.6溶液浇筑2.3[22]
    BT/PVDF (20%, volume
    percent, 5 μm)
    BT/PVDF (1%, volume
    percent, 10 μm)
    17.50.0547018.8溶液浇筑4.5[39]
    BT/P(VDF-HFP) (10%, weight percent, 5 μm)BNNs (3 μm)10.990.05414.768.3750溶液浇筑2.26[40]
    h-BN (70 nm)PVDF (12 μm)~9.50.024464.719.2652.2CVD、热压2.7[41]
    BT@HPC/PVDF (1%, weight percent, 5 μm)PVDF (5 μm)150.0236010.277旋涂5.1[42]
    h-BN (2 μm)PC (12 μm)3.150.0155.0180.82静电纺丝、热压1.16[43]
    P(VDF-CTFE)/PMMA (3 μm)Ag@SrTiO3/P(VDF-CTFE)
    (1.5%, weight percent, 5 μm)
    7.20.041635.424.686.3溶液浇筑6.15[44]
    PVDF (8 μm)BST/PVDF (40%, volume
    percent, 14μm)
    ~150.025230.87.5668.59溶液浇筑、热压1.89[45]
    BST/PVDF (20%, volume
    percent, 8 μm)
    PVDF (8 μm)17.30.025224.510.5472.02溶液浇筑、热压2.63[45]
    PMMA (6.6 μm)P(VDF-HPF)/GO (2%, weight percent, 12 μm)100.0128610.1777溶液浇筑6.78[46]
    BN/PVDF (8 μm)BT/PVDF (8 μm)120.023706.255溶液浇筑1.55[47]
    BT-np/PVDF (10%, volume
    percent, 3.5 μm)
    BT-nf/PVDF (2%, volume
    percent, 5.5 μm)
    10.50.0154539.72逐层流延2.43[48]
    BT/PMMA (1%, weight
    percent, 5 μm)
    BT/PMMA(9%, weight
    percent, 10 μm)
    7.150.05501.46.08溶液浇筑4.05[49]
    P(VDF-HFP) (5 μm)Ag@BN/PEI (5%, weight
    percent, 5 μm)
    5.90.0185101180热压法[50]
    PVDF (5 μm)NBT@TO/PVDF (6%, weight percent, 10 μm)120.02530415.4266.12逐层浇筑3.8[51]
    PVDF (10 μm)PPy/TiO2 (30%, weight
    percent, 20 μm)
    160.02992.6866.7静电纺丝、热压1.1[52]
    BZCT/PVDF (3 l%, volume
    percent, 10 μm)
    Fe3O4@BNNS/PVDF (5%, volume
    percent, 10 μm)
    160.033508.9溶液浇筑、热压2.3[53]
    BN/PVDF (10 %, weigh
    percent, 4 μm)
    BST/PVDF (8%, weigh
    percent, 8 μm)
    120.02558820.560溶液浇筑4[54]
    注: Na0.5Bi0.5TiO3@TiO2=NBT@TO, hollow porous carbon=HPC, BT-np (nf)= BT纳米颗粒(纳米片), Polypyrrole=PPy, 0.5 Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3=BZCT, polyacrylate elastomer=DE.
    下载: 导出CSV
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  • 收稿日期:  2023-04-16
  • 修回日期:  2023-06-24
  • 上网日期:  2024-01-15
  • 刊出日期:  2024-01-20

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