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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. -
Keywords:
- flexible /
- sandwich /
- energy storage /
- dielectric /
- research progress
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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]
Figure 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]
Figure 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]
Figure 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]
Figure 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]
Figure 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}} $ tanδ E/(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) 12.06 0.35 599 20.86 60 溶液涂膜 1.3 [20] P(VDF-HFP) (6.5 μm) PMMA (6 μm) 7 0.03 440 20.3 84 溶液浇筑 1.3 [21] PVDF (4 μm) P(VDF-TrFE)-PVDF (70% PVDF, volume percent, 10 μm) 12 0.03 582 23.4 65.5 溶液浇筑 1.5 [26] P(VH-HFP) (3 μm) P(VDF-HFP)-PMMA (25% PMMA, weight percent, 4 μm) 9 0.25 680 28 74 热压、拉伸 1.8 [27] P(VDF-TrFE-CFE) (4 μm) PMMA (13 μm) 5 0.05 399.1 9.7 78 静电纺丝、热压 1.7 [28] P(VDF-TrFE-CFE) (2 μm) PVDF (2 μm) 10.2 0.02 550.9 18.3 60 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) 7 0.05 790 20.1 66 溶液浇筑 2.5 [30] Parylene (1 μm) PI (17 μm) 5.04 0.43 460 4.72 44.8 CVD 2.9 [31] DE-P(VDF-HFP) (30% DE, weight percent, 2.5 μm) PMMA (14.5μm) — — 300 11.8 89 溶液浇筑 1.45 [32] PEI (4.5 μm) P(VDF-TrFE-CFE) (3 μm) ~7 0.03 504 8 81 溶液浇筑 2.6 [33] P(VDF-TrFE-CFE) (3.4 μm) PEI (6.7 μm) ~5 0.01 275 4 80 溶液浇筑 1.3 [33] PVDF (6.5 μm) DE (4 μm) 10.4 0.03 438 20.92 72 溶液浇筑 1.3 [34] PET (2 μm) P(VDF-HFP) (5 μm) 4.5 0.01 583.2 8.2 86.4 溶液浇筑 1.17 [35] Fluorene polyester (7 μm) P(VDF-HFP) (4 μm) 4 0.014 564 8 86.7 溶液浇筑、热压 1.1 [36] PMMA (4 μm) P(VDF-TrFE-CFE) (9 μm) 4.5 0.05 — 7.03 78 溶液浇筑 1.55 [37] PVDF (9 μm) P(VDF-TrFE-CFE) (16 μm) 16 0.03 408 8.7 60 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)11.42 0.03 369.9 10.17 56 溶液浇筑、热压 5 [19] PVDF (3 μm) BT@SiO2@PDA/PVDF (3 μm) 12 0.023 634 15.3 64 溶液浇筑 3.85 [24] BT/PVDF (3%, weight
percent, 4 μm)PVDF (4 μm) 13.3 <0.025 505 15 60 溶液浇筑 1.6 [22] PVDF (4 μm) BT/PVDF (3%, 4 μm) 12.9 <0.025 519.7 19.1 68.6 溶液浇筑 2.3 [22] BT/PVDF (20%, volume
percent, 5 μm)BT/PVDF (1%, volume
percent, 10 μm)17.5 0.05 470 18.8 — 溶液浇筑 4.5 [39] BT/P(VDF-HFP) (10%, weight percent, 5 μm) BNNs (3 μm) 10.99 0.05 414.76 8.37 50 溶液浇筑 2.26 [40] h-BN (70 nm) PVDF (12 μm) ~9.5 0.024 464.7 19.26 52.2 CVD、热压 2.7 [41] BT@HPC/PVDF (1%, weight percent, 5 μm) PVDF (5 μm) 15 0.02 360 10.2 77 旋涂 5.1 [42] h-BN (2 μm) PC (12 μm) 3.15 0.015 — 5.01 80.82 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)7.2 0.041 635.4 24.6 86.3 溶液浇筑 6.15 [44] PVDF (8 μm) BST/PVDF (40%, volume
percent, 14μm)~15 0.025 230.8 7.56 68.59 溶液浇筑、热压 1.89 [45] BST/PVDF (20%, volume
percent, 8 μm)PVDF (8 μm) 17.3 0.025 224.5 10.54 72.02 溶液浇筑、热压 2.63 [45] PMMA (6.6 μm) P(VDF-HPF)/GO (2%, weight percent, 12 μm) 10 0.01 286 10.17 77 溶液浇筑 6.78 [46] BN/PVDF (8 μm) BT/PVDF (8 μm) 12 0.02 370 6.2 55 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)10.5 0.015 453 9.72 — 逐层流延 2.43 [48] BT/PMMA (1%, weight
percent, 5 μm)BT/PMMA(9%, weight
percent, 10 μm)7.15 0.05 501.4 6.08 — 溶液浇筑 4.05 [49] P(VDF-HFP) (5 μm) Ag@BN/PEI (5%, weight
percent, 5 μm)5.9 0.018 510 11 80 热压法 — [50] PVDF (5 μm) NBT@TO/PVDF (6%, weight percent, 10 μm) 12 0.025 304 15.42 66.12 逐层浇筑 3.8 [51] PVDF (10 μm) PPy/TiO2 (30%, weight
percent, 20 μm)16 0.02 99 2.68 66.7 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)16 0.03 350 8.9 — 溶液浇筑、热压 2.3 [53] BN/PVDF (10 %, weigh
percent, 4 μm)BST/PVDF (8%, weigh
percent, 8 μm)12 0.025 588 20.5 60 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. -
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