高储能密度铁电聚合物纳米复合材料研究进展

沈忠慧; 江彦达; 李宝文; 张鑫

doi:10.7498/aps.69.20201209

摘要

介电电容器具有超高功率密度、低损耗以及高工作电压等优点, 是广泛应用于电子电力系统的关键储能器件. 铁电聚合物是发展高储能密度电介质薄膜材料的理想选择, 而基于铁电聚合物的纳米复合材料则兼具了聚合物的高击穿场强、柔性、易加工等特点以及陶瓷的高介电性能, 是近年来电介质储能材料研究的前沿与热点. 本文首先介绍了铁电聚合物材料的制备、铁电性能以及极化特性的调控方法, 随后总结了铁电聚合物纳米复合材料中纳米填料、复合结构以及界面三个关键调控策略对复合材料介电与储能性能的影响, 并探讨了基于相场方法的纳米复合材料中介电与储能特性的微观机制研究, 最后对高储能密度铁电聚合物纳米复合材料现存问题以及未来发展方向进行了总结与展望.

关键词:

Abstract

Electrostatic capacitors based on dielectrics delivering an ultrahigh power density, low loss and high operating voltage, are widely used in energy storage devices for modern electronic and electrical systems. Dielectric polymers, especially ferroelectric polymers, are preferable for an energy storage medium in film capacitors due to their superiority in ultrahigh breakdown strength, low mass density, flexibility, and easy fabrication process. Ferroelectric polymer nanocomposites combining the advantageous properties of ferroelectric polymer matrix and high dielectric constant of ceramic fillers, show great potential applications in achieving superior energy storage performances and have aroused substantial academic interest. This review focuses on the recent research progress of high-energy-density ferroelectric polymer nanocomposites. First, the synthesis and properties of PVDF-based ferroelectric polymers are introduced. Second, the effects of nanofillers, composite structures and interfaces on the dielectric and energy storage properties of ferroelectric polymer nanocomposites are summarized. Third, the underline mechanism of dielectric and energy storage behaviors in ferroelectric nanocomposites are discussed in the aspect of phase-field simulation. Last, the existing challenges and future directions of ferroelectric polymer nanocomposites with high energy storage density are summarized and prospected.

Keywords:

作者及机构信息

1.
武汉理工大学, 材料复合新技术国家重点实验室, 智能材料与器件研究中心, 武汉　430070

2.
武汉理工大学材料科学与工程国际化示范学院, 武汉　430070

通信作者: 张鑫, zhang-xin@whut.edu.cn

基金项目: 国家自然科学基金(批准号: 51802237, 52072280, 41180991)、中国科学技术协会青年人才托举工程(批准号: 2018QNRC001)和中央高校基本科研业务费(批准号: 193201002, 183101005, 182401004)资助的课题

Authors and contacts

1.
Center of Smart Materials and Devices, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China

2.
International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China

Corresponding author: Zhang Xin, zhang-xin@whut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51802237, 52072280, 41180991), the Young Elite Scientists Sponsorship Program by CAST, China (Grant No. 2018QNRC001), and the Fundamental Research Fund for the Central Universities, China (Grant Nos. 193201002, 183101005, 182401004)

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参考文献

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施引文献

图 1 D-E曲线示意图

Fig. 1. Schematic illustration of electric displacement (D)-electric field (E) loop.

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图 2 (a) PVDF晶体链构象示意图^[10]; (b) 沿c轴观察的PVDF晶体四个不同相的单胞^[11]

Fig. 2. (a) Schematic chain conformations^[10]; (b) unit cells of PVDF crystals with four different phases viewed along c-axis^[11].

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图 3 D-E曲线示意图(阴影区域代表释放的能量密度)　(a) 铁电; (b) 弛豫铁电; (c) 反铁电

Fig. 3. Schematic D-E hysteresis loops for (a) normal ferroelectric; (b) relaxor ferroelectric; (c) antiferroelectric behaviors. The shaded areas represent the released energy density.

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图 4 (a) PVDF和P(VDF-CTFE)-g-PS接枝共聚物的极化机制示意图; (b) P(VDF-CTFE)和P(VDF-CTFE)-g-PS接枝共聚物的D-E曲线^[21]; (c) PVDF的压折工艺图解; (d) 压折和拉伸PVDF薄膜储能性能的比较^[30]

Fig. 4. (a) Schematic models of polarization mechanisms for PVDF and P(VDF-CTFE)-g-PS; (b) D-E loops for the hot-pressed and stretched films of P(VDF-CTFE) and P(VDF-CTFE)-g-PS graft copolymers^[21]; (c) schematic demonstration of pressed-and-folding technique for PVDF; (d) a comparison of electric energy storage properties of pressed-and-folded and stretched films^[30].

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图 5 (a) PEI中超细纳米颗粒的体积分数与介电常数的关系^[33]; (b) 不同取向的纳米纤维填料对介电常数的影响^[37]; (c) 不同维度的Al₂O₃与c-BCB复合后的击穿场强与温度稳定性^[40]; (d) PVDF/Ca₂Nb₃O₁₀复合材料的击穿场强和储能密度^[41]

Fig. 5. (a) Relationship between volume fraction of ultrafine nanoparticles and dielectric constant in PEI^[33]; (b) influence of nanofiber fillers with different orientations on dielectric constant^[37]; (c) breakdown field strength and temperature stability of Al₂O₃ with different dimensions and c-BCB composites^[40]; (d) breakdown field strength and energy storage density of PVDF/Ca₂Nb₃O₁₀ composites^[41].

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图 6 (a) P(VDF-HFP)/BaTiO₃复合材料中不同梯度分布的示意图^[42]; (b) BNNS和BZT填料互穿结构的示意图^[43]; (c) BN和BT共混填料的制备过程和电镜图^[44]

Fig. 6. (a) Schematic diagram of different gradient distributions in P(VDF-HFP)/BaTiO₃ composites^[42]; (b) schematic diagram of interpenetrating structure of BNNS and BZT fillers^[43]; (c) preparation process and electron micrograph of BN and BT blend filler^[44].

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图 7 (a) 三明治结构复合薄膜的示意图和断面电镜图^[46]; (b) 分别掺有BNNS和BST的叠层结构示意图和电镜图^[47]; (c) 多层复合材料的制备流程图和示意图^[48]

Fig. 7. (a) Schematic diagram and sectional electron microscope of sandwich composite film^[46]; (b) schematic diagram and electron micrograph of laminated structure doped with BNNS and BST respectively^[47]; (c) preparation flow chart and schematic diagram of multilayer composite materials^[48].

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图 8 (a) GMA功能化PVDF-HFP的流程图^[56]; (b) PTFEMA, PHFBMA和PDFHM原位聚合的示意图和电镜图^[57]; (c) BaTiO₃@TiO₂多级结构的电镜图^[58]; (d) BaTiO₃@TiO₂@Al₂O₃同轴纤维的电镜图和示意图^[59]

Fig. 8. (a) Flow chart of GMA functionalized PVDF-HFP^[56]; (b) schematic diagram and electron micrograph of in-situ polymerization of PTFEMA, PHFBMA and PDFHM^[57]; (c) electron micrograph of BaTiO₂@TiO₂ multilevel structure^[58]; (d) electron micrograph and schematic diagram of BaTiO₃@TiO₂@Al₂O₃ coaxial fiber^[59].

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图 9 (a) 颗粒填料取向分布与介电常数的关系^[62]; (b) 多物理场协同击穿的路径演化及能量分布^[65]; (c) 不同填料种类的体积分数与击穿场强的关系^[64]; (d) 空间电荷分布的示意图^[67]

Fig. 9. (a) Relationship between orientation distribution of particulate filler and dielectric constant^[62]; (b) path evolution and energy distribution of multi-physical field cooperative breakdown^[65]; (c) the relationship between the volume fraction of different fillers and the breakdown field strength^[64]; (d) schematic diagram of space charge distribution^[67].

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[3]	成桑, 李雨抒, 梁家杰, 李琦 2020 高分子学报 51 469 Google Scholar Chen S, Li Y S, Liang J J, Li Q 2020 Acta Polym. Sin. 51 469 Google Scholar
[4]	Barshaw E J, White J, Chait M J, Cornette J B, Rabuffi M 2007 IEEE Trans. Magn. 43 223 Google Scholar
[5]	Chen Q, Shen Y, Zhang S, Zhang Q M 2015 Annu. Rev. Mater. Res. 45 433 Google Scholar
[6]	Laihonen S J, Gafvert U, Schutte T, Gedde U 2007 IEEE Trans. Dielectr. Electr. Insul. 14 275 Google Scholar
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[9]	Lovinger A J 1983 Science 220 1115 Google Scholar
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[11]	Zhu L, Wang Q 2012 Macromolecules 45 2937 Google Scholar
[12]	Cheng Z Y, Zhang Q M, Bateman F B 2002 J. Appl. Phys. 92 6749 Google Scholar
[13]	Bharti V, Zhang Q M 2001 Phys. Rev. B 63 184103 Google Scholar
[14]	Li Z, Arbatti M D, Cheng Z Y 2004 Macromolecules 37 79 Google Scholar
[15]	Forsythe J S, Hill D 2000 Prog. Polym. Sci. 25 101 Google Scholar
[16]	Chu B, Zhou X, Neese B, Zhang Q M, Bauer F 2006 IEEE Trans. Dielectr. Electr. Insul. 13 1162 Google Scholar
[17]	Xu H, Cheng Z Y, Olson D, Mai T, Zhang Q M, Kavarnos G 2001 Appl. Phys. Lett. 78 2360 Google Scholar
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[29]	Zhang X, Shen Y, Shen Z H, Jiang J Y, Chen L Q, Nan C W 2016 ACS Appl. Mater. Interfaces 8 27236 Google Scholar
[30]	Meng N, Ren X, Santagiuliana G, Ventura L, Bilotti E 2019 Nat. Commun. 10 4535 Google Scholar
[31]	Yu K, Niu Y, Zhou Y, Bai Y, Wang H 2013 J. Am. Ceram. Soc. 96 2519 Google Scholar
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[33]	Thakur Y, Zhang T, Iacob C, Yang T, Bernholc J, Chen L Q, Runt J, Zhang Q M 2017 Nanoscale 9 10992 Google Scholar
[34]	Zhang T, Chen X, Thakur Y, Lu B, Zhang Q Y, Runt J, Zhang Q M 2020 Sci. Adv. 6 eaax6622 Google Scholar
[35]	Huang X, Sun B, Zhu Y, Li S, Jiang P 2019 Prog. Mater. Sci. 100 187 Google Scholar
[36]	Zhang H, Marwat M A, Xie B, Ashtar M, Ye Z G 2019 ACS Appl. Mater. Interfaces 12 1 Google Scholar
[37]	Tang H X, Lin Y R, Sodano H A 2012 Adv. Energy Mater. 2 469 Google Scholar
[38]	Wang G, Huang X, Jiang P 2015 ACS Appl. Mater. Interfaces 7 18017 Google Scholar
[39]	Zhang X, Jiang J Y, Shen Z H, Dan Z K, Shen Y 2018 Adv. Mater. 30 1707269 Google Scholar
[40]	Li H, Ai D, Ren L L, Yao B, Han Z B, Shen Z H, Wang J J, Chen L Q, Wang Q 2019 Adv. Mater. 31 1900875 Google Scholar
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[42]	Jiang Y D, Zhang X, Shen Z H, Li X H, Yan J J, Li B W, Nan C W 2020 Adv. Funct. Mater. 30 1906112 Google Scholar
[43]	Jiang J Y, Shen Z H, Cai X K, Qian Z K, Dan Z K, Lin Y H, Liu B L, Nan C W, C, Chen L Q, Shen Y 2019 Adv. Energy Mater. 9 1803411 Google Scholar
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[45]	Wang Y F, Chen J, Li Y, Niu Y J, Wang Q, Wang H 2019 J. Mater. Chem. 7 2965 Google Scholar
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[47]	Liu F H, Li Q, Cui J, Li Z Y, Yang G, Liu Y, Dong L J, Xiong C X, Wang H, Wang Q 2017 Adv. Funct. Mater. 27 1606292 Google Scholar
[48]	Jiang J Y, Shen Z H, Qian J F, Dan Z K, Guo M F, He Y, Lin Y H, Nan C W, Chen L Q, Shen Y 2019 Nano Energy 62 220 Google Scholar
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[52]	Borgani R, Pallon L K H, Hedenqvist M S, Gedde U W, Haviland D B 2016 Nano Lett. 16 5934 Google Scholar
[53]	Zhang X, Li B-W, Dong L J, Liu H X, Chen W, Shen Y, Nan C W 2018 Adv. Mater. Interfaces 5 1800096 Google Scholar
[54]	Pourrahimi A M, Olsson R T, Hedenqvist M S 2018 Adv. Mater. 30 1703624 Google Scholar
[55]	Huang X Y, Jiang P K 2015 Adv. Mater. 27 546 Google Scholar
[56]	Xie L, Huang X, Yang K, Li S T, Jiang P K 2014 J. Mater. Chem. 2 5244 Google Scholar
[57]	Zhang T, Guo M F, Jiang J Y, Zhang X Y, Lin Y H, Nan C W, Shen Y 2019 RSC Adv. 9 35990 Google Scholar
[58]	Zhang X, Shen Y, Xu B, Zhang Q H, Gu L, Jiang J Y, Ma J, Lin Y H, Nan C W 2016 Adv. Mater. 28 2055 Google Scholar
[59]	Pan Z B, Zhai J W, Shen B 2017 J. Mater. Chem. A 5 15217 Google Scholar
[60]	Chen L Q 2008 J. Am. Ceram. Soc. 91 1835 Google Scholar
[61]	Wang J J, Wang B, Chen L Q 2019 Annu. Rev. Mater. Res. 49 127 Google Scholar
[62]	Wang Y U, Tan D Q 2011 J. Appl. Phys. 109 104102 Google Scholar
[63]	Wang Y U, Tan D Q, Krahn J 2011 J. Appl. Phys. 110 034115
[64]	Shen Z H, Wang J J, Lin Y H, Nan C W, Chen L Q, Shen Y 2018 Adv. Mater. 30 1704380 Google Scholar
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