Effects of suface hydroxylated strontium titanate nanofibers on dielectric and energy storage properties of polyvinylidene fluoride composites

Wang Jiao; Liu Shao-Hui; Zhou Meng; Hao Hao-Shan; Zhai Ji-Wei

doi:10.7498/aps.69.20200592

Abstract

With the rapid development of the electronics industry, the dielectric materials with high energy storage density, fast charge and discharge speed, easy-to-process and easy-to-mold, and stable performance are urgently needed to meet the requirements for lightweight and miniaturization of electronic component equipment. Dielectric ceramics has a high dielectric constant, but low breakdown field strength. Polyvinylidene fluoride (PVDF) has the advantages of good flexibility, high breakdown field strength, and light weight, but its dielectric constant is low. Achieving the ability to tailor the interface between dielectric ceramics filler and PVDF polymer matrix is a key issue for realizing the desirable dielectric properties and high energy density in the nanocomposites. As a result, much effort has been made to prepare the polymer composites through the surface modification of the nanoparticles with high dielectric constant fillers dispersed in a matrix, with the hope of preparing composites containing the high dielectric constant of the ceramic fillers and the high breakdown strength of polymers. In this work, in order to obtain the high dielectric-constant and high-energy-storage-density dielectric ceramics, the electrospinning method is used to prepare the SrTiO₃ one-dimensional nanofibers as the inorganic fillers and the casting method is adopted to prepare PVDF as the polymer matrix. To improve the interface between inorganic nanofiber fillers and PVDF matrix, the SrTiO₃ nanofibers are modified by surface hydroxylation. The effects of suface hydroxylated SrTiO₃ nanofibers on the dielectric properties and energy storage properties of PVDF composites are studied. The correlation between interface modification and energy storage performance of composites is investigated to reveal the mechanism of enhanced energy storage performance of SrTiO₃ nanofibers/PVDF composites. The results show that the dispersion of surface-hydroxylating SrTiO₃ nanofibers in PVDF polymer can be improved. The composites exhibit improved dielectric properties and enhanced breakdown strength. When the filling quantity of the surface-hydroxylating SrTiO₃ nanofiber fillers is 2.5 vol%, the energy storage density of the composite reaches 7.96 J/cm³. Suface-hydroxylating SrTiO₃ nanofibers exhibit excellent dispersion in the PVDF polymer matrix and strong interfacial adhesion with the matrix, leading the composites to possess excellent dielectric constant and energy storage performance. The surface hydroxylation of ceramic fillers can improve the energy storage performance of the composites.

Keywords:

Authors and contacts

1.
School of Science, Henan Institute of Engineering, Zhengzhou 451191, China
2.
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China

Corresponding author: Wang Jiao, wangjiao_1203@163.com

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51902088), the Programs for Tackling Key Problems in Science and Technology of Henan Province, China (Grant Nos. 202102210002, 202102210041), and the Henan Province College Students′ Innovation and Entrepreneurship Training Program, China (Grant No. S201911517008)

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References

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Cited By

图 1 (a)静电纺丝法制备的ST NF的SEM图; (b)表面羟基化改性前后ST NF的XRD图

Figure 1. (a) SEM image of ST NF; (b) XRD patterns of ST NF and ST NF—OH.

DownLoad: Full-Size Img PowerPoint

图 2 ST NF和ST NF—OH的FTIR图

Figure 2. FTIR of ST NF and ST NF—OH.

DownLoad: Full-Size Img PowerPoint

图 3 (a) ST NF的XPS全谱扫描图; (b) ST NF—OH的XPS全谱扫描图; 插图为O 1 s元素的精细扫描谱线

Figure 3. (a) XPS spectra of ST NF; (b) XPS spectra of ST NF—OH. High-resolution XPS spectra of O 1 s are shown in the inset.

DownLoad: Full-Size Img PowerPoint

图 4 (a) 羟基化处理前ST NF的SEM图; (b) 羟基化处理后ST NF的SEM图

Figure 4. (a) SEM image of ST NF before hydroxylation; (b) SEM image of ST NF—OH.

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图 5 5% (体积分数)填充量ST NF—OH/PVDF复合材料的(a)表面形貌和(b)截面形貌

Figure 5. (a) Surface SEM and (b) cross-section SEM of 5% (volume fraction) ST NF—OH/PVDF composites

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图 6 羟基化改性后ST NF与PVDF形成氢键的示意图

Figure 6. Schematic diagrams of formation a bridge between the F atoms on the PVDF and the —OH groups of the hydroxylation of ST NF.

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图 7 室温条件下不同填充量(体积分数) ST NF—OH/PVDF复合材料的(a)介电常数和(b)介电损耗随频率的变化

Figure 7. Frequency dependence of the dielectric constant (a) and loss tangent (b) of ST NF—OH/PVDF composites with various concentrations (volume fraction) of filler.

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图 8 不同填充量ST NF—OH/PVDF复合材料的介电常数测量值和数值模拟

Figure 8. Dielectric constant measurement and numerical simulation of ST NF—OH/PVDF composites with different loading.

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图 9 (a) 不同填充量ST NF—OH/PVDF复合材料的Weibull分布曲线; (b)不同填料浓度下ST NF—OH/PVDF复合材料的室温耐击穿强度

Figure 9. (a) Weibull plots and (b) breakdown strength for ST NF—OH/PVDF composites with various concentrations of fillers.

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图 10 (a)室温条件下不同ST NF—OH填料复合材料的P-E曲线; (b)不同ST NF—OH填料的复合材料的储能密度、放电效率随电场的变化

Figure 10. (a) P-E curves and (b) the efficiency and energy storage density of ST NF—OH/PVDF composites with various concentration (volume fration) fillers.

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表 1 羟基化处理前后样品的晶体结构

Table 1. Crystal structure of the samples before and after hydroxylation.

样品	PDF卡片编号	晶相	空间群	晶格参数/nm
ST NF	35-0734	立方相	Pm-3m	a = b = c = 0.3911
ST NF—OH	35-0734	立方相	Pm-3m	a = b = c = 0.3915

DownLoad: CSV

表 2 前期文献报道的PVDF基复合材料的储能密度与本文实验结果比较

Table 2. Comparison of the energy storage density of PVDF-based composite materials reported in previous literatures and the experimental results in this paper.

材料类型	表面改性方式	储能密度/J·cm^–3	文献
BaTiO₃/P (VDF-HFP)薄膜	氨甲基膦酸	3.2	[27]
SrTiO₃/PVDF 薄膜	聚乙烯吡咯烷酮	3.54	[25]
BaTiO₃/ P(VDF-HFP) 复合薄膜	—	4.89	[28]
Ba_0.7Sr_0.3TiO₃/P (VDF-CTFE)材料	KH-550偶联剂	6.5	[29]
SrTiO₃/PVDF薄膜	表面羟基化	7.96	本文

DownLoad: CSV

[1]	Wang Y, Wang L, Yuan Q, Niu Y, Chen J, Wang Q, Wang H 2017 J. Mater. Chem. A 5 10849 Google Scholar
[2]	Luo H, Roscow J, Zhou X, Chen S, Han X, Zhou K, Zhang D, Bowen C R 2017 J. Mater. Chem. A 5 7091 Google Scholar
[3]	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
[4]	Zhu Y, Zhu Y, Huang X, Chen J, Li Q, He J, Jiang P 2019 Adv. Energy Mater. 9 1901826 Google Scholar
[5]	Luo H, Ma C, Zhou X, Chen S, Zhang D 2017 Macromolecules 50 5132 Google Scholar
[6]	Shen Z H, Wang J J, Jiang J Y, Lin Y H, Nan C W, Chen L Q, Shen Y 2018 Adv. Energy Mater. 8 1800509 Google Scholar
[7]	Zhang D, Zhou X, Roscow J, Zhou K, Wang L, Luo H, Bowen C R 2017 Sci. Rep. 7 45179 Google Scholar
[8]	Dang Z M, Yuan J K, Zha J W, Zhou T, Li S T, Hu G H 2012 Prog. Mate.r Sci. 57 660 Google Scholar
[9]	Zhou Y, Li Q, Dang B, Yang Y, Shao T, Li H, Hu J, Zeng R, He J, Wang Q 2018 Adv. Mater. 30 1805672 Google Scholar
[10]	Yao Z, Song Z, Hao H, Yu Z, Cao M, Zhang S, Lanagan M T, Liu H 2017 Adv. Mater. 29 1601727 Google Scholar
[11]	赵学童, 廖瑞金, 李建英, 王飞鹏 2015 物理学报 64 127701 Google Scholar Zhao X T, Liao R J, Li J Y, Wang F P 2015 Acta Phys. Sin. 64 127701 Google Scholar
[12]	冯奇, 李梦凯, 唐海通, 王晓东, 高忠民, 孟繁玲 2016 物理学报 65 188101 Google Scholar Feng Q, Li M K, Tang H T, Wang X D, Gao Z M, Meng F L 2016 Acta Phys. Sin. 65 188101 Google Scholar
[13]	Song Y, Shen Y, Liu H Y, Lin Y H, Li M, Nan C W 2012 J. Mate.r Chem. 22 8063 Google Scholar
[14]	Song Y, Shen Y, Hu P H, Lin Y H, Li M, Nan C W 2012 Appl. Phys. Lett. 101 152904 Google Scholar
[15]	Xie L Y, Huang X Y, Wu C, Jiang P K 2011 J. Mater. Chem. 21 5897 Google Scholar
[16]	Xie L Y, Huang X Y, Yang K, Li S T, Jiang P K 2014 J. Mater. Chem. A 2 5244 Google Scholar
[17]	Thakur V K, Lin M F, Tan E J, Lee P S 2012 J. Mater. Chem. 22 5951 Google Scholar
[18]	Thakur V K, Tan E J, Lin M F, Lee P S 2011 Polym. Chem. 2 2000 Google Scholar
[19]	Thakur V K, Yan J, Lin M F, Zhi C Y, Golberg D, Bando Y, Sim R, Lee P S 2012 Polym. Chem. 3 962 Google Scholar
[20]	Wang X, Dai Y Y, Wang W M, Ren M M, Li B Y, Fan C, Liu X Y 2014 ACS Appl. Mater. Interfaces 6 16182 Google Scholar
[21]	Almadhoun M N, Bhansali U S, Alshareef H N 2012 J. Mater. Chem. 22 11196 Google Scholar
[22]	Yuan X P, Matsuyama Y, Chung T C M 2010 Macromolecules 43 4011 Google Scholar
[23]	Zhang Q P, Xia W M, Zhu Z G, Zhang Z C 2013 J. Appl. Polym. Sci. 127 3002 Google Scholar
[24]	Zhang Z C, Chung T C M 2007 Macromolecules 40 9391 Google Scholar
[25]	Yu K, Wang H, Zhou Y C, Bai Y Y, Niu Y J 2013 J. Appl. Phys. 113 034105 Google Scholar
[26]	Wang Z P, Nelson J K, Miao J J, Linhardt R J, Schadler L S, Hillborg H, Zhao S 2012 IEEE Trans. Dielect. El. In. 19 960 Google Scholar
[27]	Kim P, Doss N M, Tillotson J P, Hotchkiss P J, Pan M J, Marder S R, Li J Y, Calame J P, Perry J W 2009 ACS Nano 3 2581 Google Scholar
[28]	王璐, 孔文杰, 罗行, 周学凡, 周科朝, 张斗 2018 无机材料学报 33 1060 Wang L, Kong W J, Luo H, Zhou X F, Zhou K C, Zhang D 2018 Journal of Inorganic Materials 33 1060
[29]	Xia W M, Xu Z, Wen F, Zhang Z C 2012 Ceram. Int. 38 1071 Google Scholar

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