BaTiO3纳米线的制备及其复合物介电和储能性能研究

doi:10.15541/jim20180041

摘要/Abstract

摘要：

采用两步水热法合成钛酸钡(BaTiO₃)纳米线, 并以此为填充物, 聚偏氟乙烯六氟丙烯(P(VDF-HFP))为聚合物基体制备介电复合物, 研究不同含量BaTiO₃纳米线对复合物的介电及储能性能的影响。采用X射线衍射仪、扫描电镜、透射电镜、阻抗分析仪和铁电工作站等表征BaTiO₃纳米线及其复合物的物相、微观结构、介电和储能性能。结果表明: BaTiO₃纳米线具有典型的四方相, 且在聚合物基体中具有良好的分散性与相容性。相同频率下, 复合物的介电常数随着BaTiO₃纳米线含量的增加而增加。含量为20vol%的复合物, 在1 kHz频率下其介电常数取得最大值30.69。含量为5vol%的复合物, 在场强为240 kV/mm时, 获得了最大的储能密度与放电能量密度, 分别为4.89和2.58 J/cm³。

关键词: 钛酸钡, 介电复合物, 介电常数, 能量密度

Abstract:

In this study, BaTiO₃ nanofibers were synthesized by a two-step hydrothermal method and subsequently incorporated into poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) matrix to prepare nanocomposites for energy storage application. The crystalline phase, morphology and microstructure of BaTiO₃ nanofibers were observed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy, respectively. The dielectric properties and energy storage performance of the nanocomposites were characterized by dielectric and ferroelectric analyzer. The BaTiO₃ nanofibers with tetragonal phase structure exhibited high aspect ratios, good dispersibility and compatibility in polymer matrix. The effects of volume fraction of BaTiO₃ nanofibers on the dielectric constant, breakdown strength and discharged energy density of the nanocomposites were investigated systematically. The dielectric constant of the BaTiO₃-P(VDF-HFP) nanocomposites remarkably improved with the increase of BaTiO₃ nanofiber contents at the same frequency. At 1 kHz, the maximum dielectric constant of the composite with 20vol% BaTiO₃ nanofibers is up to 30.69. The composite with 5vol% BaTiO₃ nanofibers achieves the maximum energy storage density (4.89 J/cm³) and discharged energy density (2.58 J/cm³) at 240 kV/mm.

Key words: BaTiO₃, dielectric nanocomposite, dielectric constant, energy density

中图分类号:

TB34

王璐, 孔文杰, 罗行, 周学凡, 周科朝, 张斗. BaTiO₃纳米线的制备及其复合物介电和储能性能研究[J]. 无机材料学报, 2018, 33(10): 1059-1064.

WANG Lu, KONG Wen-Jie, LUO Hang, ZHOU Xue-Fan, ZHOU Ke-Chao, ZHANG Dou. Dielectric and Energy Storage Property of Dielectric Nanocomposites with BaTiO₃ Nanofibers[J]. Journal of Inorganic Materials, 2018, 33(10): 1059-1064.

图/表 6

图1 (a) BaTiO3纳米线的SEM照片; (b) Na2Ti3O7纳米线、BaTiO3纳米线的XRD图谱; BaTiO3纳米线的(c) TEM照片, (d)高分辨TEM照片及快速傅里叶变换图

Fig. 1 (a) SEM image of BaTiO3 nanofibers; (b) XRD patterns of Na2Ti3O7 and BaTiO3 nanofibers; (c) TEM image, (d) HRTEM and FFT image of BaTiO3 nanofibers

图2 (a)纯P(VDF-HFP)膜, (b) 5vol%, (c) 10vol%和(d) 20vol%的BaTiO3纳米线复合物膜表面SEM照片

Fig. 2 Surface SEM images of (a) pure P(VDF-HFP) and composites filled with various BaTiO3 nanofibers: (b) 5vol%; (c) 10vol%; (d) 20vol%

图3 BaTiO3纳米线复合物的(a)介电常数和(b)介电损耗随频率变化规律

Fig. 3 (a) Dielectric constant of BaTiO3-P (VDF-HFP) and (b) dielectric loss of BaTiO3-P (VDF-HFP) composites as a function of frequency

图4 BaTiO3纳米线的P(VDF-HFP)复合物与纯P(VDF-HFP)的抗击穿电场

Fig. 4 Breakdown strength of BaTiO3-P(VDF-HFP) composite and pure P(VDF-HFP)

表1 不同BaTiO3纳米线填充量的复合物拟合获得抗击穿电场的Weibull统计分析参数

Table 1 Weibull distribution of the dielectric breakdown strength of composites filled with various BaTiO3 nanofibers

Contents of BaTiO₃ nanofibers	β	E₀/(kV∙mm^-1)
0	8.24	397
5vol%	6.16	244
10vol%	5.46	198
20vol%	2.51	72

图5 (a) 5vol%, (b) 10vol%和(c) 20vol% BaTiO3纳米线复合物膜的电位移-电场曲线及其(d)能量密度

Fig. 5 Displacement hysteresis loops of composites filled with various BaTiO3 nanofibers(a) 5vol%, (b) 10vol%, (c) 20vol% and (d) energy density of composites

参考文献 22

[1]	DANG Z M, YUAN J K, YAO S H, et al. Flexible nanodielectric materials with high permittivity for power energy storage. Advanced Materials, 2013, 25(44): 6334-6365.
[2]	YAO L M, PAN Z B, LIU S H,et al. Significantly enhanced energy density in nanocomposite capacitors combining the TiO2 nanorod array with poly(vinylidene fluoride). ACS Applied Materials & Interfaces, 2016, 8(39): 26343-26351.
[3]	SHEN Y, SHEN D S, ZHANG X,et al. High energy density of polymer nanocomposites at a low electric field induced by modulation of their topological-structure. Journal of Materials Chemistry A, 2016, 4(21): 8359-8365.
[4]	WANG C Y, CHEN W T, XU C,et al. Fluorinated polyimide/ POSS hybrid polymers with high solubility and low dielectric constant. Chinese Journal of Polymer Science, 2016, 34(11): 1363-1372.
[5]	ZIA T H, KHAN A N, HUSSAIN M,et al. Enhancing dielectric and mechanical behaviors of hybrid polymer nanocomposites based on polystyrene, polyaniline and carbon nanotubes coated with polyaniline. Chinese Journal of Polymer Science, 2016, 34(12): 1500-1509.
[6]	ZHANG X, SHEN Y, ZHANG Q,et al. Ultrahigh energy density of polymer nanocomposites containing BaTiO3@TiO2 nanofibers by atomic-scale interface engineering. Advanced Materials, 2015, 27(5): 819-824.
[7]	XIE L, HUANG X, YANG K,et al. "Grafting to" route to PVDF-HFP-GMA/BaTiO3 nanocomposites with high dielectric constant and high thermal conductivity for energy storage and thermal management applications. Journal of Materials Chemistry A, 2014, 2(15): 5244-5251.
[8]	TANG H X, LIN Y R, SODANO H A.Nanocomposite capacitors: enhanced energy storage in nanocomposite capacitors through aligned PZT nanowires by uniaxial strain assembly.Advanced Energy Materials, 2012, 2(4): 469-476.
[9]	LUO H, ROSCOW J, ZHOU X F,et al. Ultra-high discharged energy density capacitor using high aspect ratio Na0.5Bi0.5TiO3 nanofibers. Journal of Materials Chemistry A, 2017, 5(15): 7091-7102.
[10]	XIE L, HUANG X, HUANG Y,et al. Core-shell structured hyperbranched aromatic polyamide/BaTiO3 hybrid filler for poly (vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) nanocomposites with the dielectric constant comparable to that of percolative composites. ACS Applied Materials & Interfaces, 2013, 5(5): 1747-1756.
[11]	HU P H, SONG Y, LIU H Y,et al. Largely enhanced energy density in flexible P(VDF-TrFE) nanocomposites by surface-modified electrospun BaSrTiO3 fibers. Journal of Materials Chemistry A, 2013, 1(5): 1688-1693.
[12]	BOWEN C P, NEWNHAM R E, RANDALL C A.Dielectric properties of dielectrophoretically assembled particulate-polymer composites.Journal of Materials Research, 1998, 13(1): 205-210.
[13]	LUO H, ZHANG D, JIANG C,et al. Improved dielectric properties and energy storage density of poly(vinylidene fluoride-co- hexafluoropropylene) nanocomposite with hydantoin epoxy resin coated BaTiO3. ACS Applied Materials & Interfaces, 2015, 7(15): 8061-8069.
[14]	YANG Y, SUN H L, ZHU B P,et al. Enhanced dielectric performance of three phase percolative composites based on thermoplastic- ceramic composites and surface modified carbon nanotube. Applied Physics Letters, 2015, 106(1): 012902.
[15]	ZHAN J Y, TIAN G F, WU Z P,et al. Preparation of polyimide/ BaTiO3/Ag nanocomposite films via in situ technique and study of their dielectric behavior. Chinese Journal of Polymer Science, 2014, 32(4): 424-431.
[16]	PRATEEK, THAKUR V K, GUPTA R K. Recent progress on ferroelectric polymer-based nanocomposites for high energy density capacitors: synthesis, dielectric properties, and future aspects.Chemical Reviews, 2016, 116(7): 4260-4317.
[17]	TANG H X, LIN Y R, SADANO H A.Synthesis of high aspect ratio BaTiO3 nanowires for high energy density nanocomposite capacitors.Advanced Energy Materials, 2013, 3(4): 451-456.
[18]	RAHIMABADY M, MIRSHEKARLOO M S, YAO K,et al. Dielectric behaviors and high energy storage density of nanocomposites with core-shell BaTiO3@TiO2 in poly(vinylidene fluoride- hexafluoropropylene). Physical Chemistry Chemical Physics, 2013, 15(38): 16242-16248.
[19]	TANG H X, LIN Y R, ANDREWS C,et al. Nanocomposites with increased energy density through high aspect ratio PZT nanowires. Nanotechnology, 2011, 22(1): 15702-15709.
[20]	PAN Z B, YAO L M, ZHAI J W,et al. High-energy-density polymer nanocomposites composed of newly structured one-dimensional BaTiO3@Al2O3 nanofibers. ACS Applied Materials & Interfaces, 2017, 9(4): 4024-4033.
[21]	TANG H X, SODANO H A.Ultra high energy density nanocomposite capacitors with fast discharge using Ba0.2Sr0.8TiO3 nanowires.Nano Letters, 2013, 13(4): 1373-1379.
[22]	WANG Y, CUI J, YUAN Q,et al. Significantly enhanced breakdown strength and energy density in sandwich-structured barium titanate/poly(vinylidene fluoride) nanocomposites. Advanced Materials, 2015, 27(42): 6658-6663.

BaTiO₃纳米线的制备及其复合物介电和储能性能研究

Dielectric and Energy Storage Property of Dielectric Nanocomposites with BaTiO₃ Nanofibers

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