立方体状SrTiO<sub>3</sub>粉体/聚偏氟乙烯电介质复合薄膜的储能性能

刘少辉; 王娇; 王菲菲; 王远

立方体状SrTiO₃粉体/聚偏氟乙烯电介质复合薄膜的储能性能

刘少辉^{1, 2, ,},
王娇^{1, 2},
王菲菲^{1, 2},
王远¹

1.
河南工程学院　材料工程学院, 河南省电子陶瓷材料与应用重点实验室, 郑州, 451191
2.
河南工程学院　材料工程学院, 河南省稀土复合材料国际联合实验室, 郑州, 451191

基金项目: 国家自然科学基金项目(51902088)，河南省高校科技创新人才项目(21HASTIT014)，河南省优秀青年基金项目 (212300410031)，河南省科技攻关计划项目(222102240004)

详细信息

通讯作者:
刘少辉，博士，副教授，研究方向为复合材料　E-mail: qqliushaohui@163.com

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2022-09-08
- 修回日期: 2022-10-18
- 录用日期: 2022-10-25
- 网络出版日期: 2022-11-12
- 刊出日期: 2023-08-15

Energy storage performance of cubic SrTiO₃ powder/ polyvinylidene fluoride dielectric composite films

LIU Shaohui^{1, 2
, ,},
WANG Jiao^{1, 2},
WANG Feifei^{1, 2},
WANG Yuan¹

1.
Henan Key Laboratory of Electronic Ceramic Materials and Application, College of Materials Engineering, Henan University of Engineering, Zhengzhou, 451191
2.
Henan International Joint Laboratory of Rare Earth Composite Materials, College of Materials Engineering, Henan University of Engineering, Zhengzhou, 451191

Funds: National Natural Science Foundation of China (51902088), Program for Science and Technology Innovation Talents in Universities of Henan Province(21 HASTIT014) and the Excellent Youth Fund of Henan Natural Science Foundation(212300410031) and the Programs for Tackling Key Problems in Science and Technology of Henan Province (222102240004).

摘要

摘要: 电介质电容器因具备超高的功率密度、超快的充放电速率等优点，成为高能脉冲功率领域的核心储能器件，广泛用于新能源汽车、智能电网等诸多领域。目前电介质电容器的储能密度较低，阻碍了储能器件与系统向小型化与高容量化发展。目前单一的电介质材料已经不能满足脉冲功率型先进电容器的要求。研究学者提出利用复合思想，制备出聚合物和无机陶瓷组成的陶瓷/聚合物复合材料，综合聚合物和陶瓷各自的优点(陶瓷填料的高介电常数和聚合物的高击穿强度)，可以获得高储能密度电介质材料。本文采用混合碱法制备出立方体状SrTiO₃粉体作为陶瓷填料，采用聚乙烯吡咯烷酮(PVP)表面包覆改性对立方体状SrTiO₃粉体进行表面处理，利用流延法制备出了均匀的聚偏氟乙烯(PVDF)电介质复合薄膜。系统研究了表面PVP包覆改性立方体状SrTiO₃粉体对PVDF电介质复合薄膜介电性能和储能密度的影响。结果表明：混合碱法制备出的SrTiO₃粉体的形貌为立方体状，尺寸为 200-400 nm，粒径分布比较均匀，PVP的官能团和立方体状SrTiO₃粉体的表面建立起共价的相互作用，在立方体状SrTiO₃粉体表面形成PVP包覆层，可以有效防止立方体状SrTiO₃粉体在PVDF电介质复合薄膜中的团聚，同时PVP包覆层可以改善立方体状SrTiO₃粉体在PVDF聚合物中分散和结合情况。PVDF电介质复合薄膜具有良好的介电性能和耐击穿性能，PVDF电介质复合薄膜的介电常数随着填充量的增加而增加，当立方体状SrTiO₃粉体填充量为40vol.%时，电介质复合薄膜的介电常数为34.9。PVDF电介质复合薄膜的储能密度随着填充量的增加而先增加后降低，当表面PVP包覆改性处理立方体状SrTiO₃粉体的填充量为5vol%时，电介质复合薄膜的储能密度达5.3 J/cm³。1SrTiO₃粉体填充量为5vol%时，未处理表面改性SrTiO₃粉体/PVDF电介质复合薄膜和PVP改性SrTiO₃粉体/PVDF电介质复合薄膜的储能密度和放电效率曲线关系图
- 钛酸锶 /
- 复合薄膜 /
- 储能性能 /
- 介电性能 /
- 表面改性 /
- 聚偏氟乙烯(PVDF)
Abstract: Dielectric energy storage materials with high working field strength and high energy storage efficiency have an important impact on improving the performance of power equipment and reducing the volume of power equipment. The cubic SrTiO₃ powder was prepared as ceramic filler by the mixed alkali method, and the surface of the cubic SrTiO₃ particles was treated by polyvinylpyrrolidone (PVP) surface modification. The uniform polyvinylidene fluoride (PVDF) flexibility composite was prepared by the casting method. The effect of surface PVP modified cubic SrTiO₃ filler on the dielectric properties and energy storage density of PVDF dielectric composites was systematically studied. The results show that the morphology of the SrTiO₃ powder is cubic and the size is 200-400 nm. The particle size distribution is relatively uniform. The PVP coating layer formed on the surface of the cubic SrTiO₃ filler can effectively prevent the agglomeration of the cubic SrTiO₃ filler in the PVDF composites. At the same time, the PVP coating layer can improve the dispersion and bonding of the cubic SrTiO₃ filler in the PVDF polymer. PVDF dielectric composite has excellent dielectric properties and breakdown strength. The dielectric constant of PVDF composites increases with the increase of the filling amount. When the filling amount of cubic SrTiO₃ filler is 40vol.%, the dielectric constant of the composite is 34.9. And the Maxwell-Garnett model is used to simulate the dielectric constant of the composite. The fitted value is relatively consistent with the measured value. The energy storage density of PVDF dielectric composite increases first and then decreases with the increase of the filling volume. When the filling volume of the cubic SrTiO₃ filler modified by the surface PVP is 5vol%, the energy storage density of the composite reaches 5.3 J/cm³.
- Strontium titanate /
- composite films /
- energy storage property /
- dielectric performance /
- surface modification /
- polyvinylidene fluoride (PVDF)

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图 1 立方体状SrTiO₃粉体和聚乙烯吡咯烷酮(PVP)表面包覆改性SrTiO₃粉体的XRD图谱，插图为混合碱法制备SrTiO₃粉体的SEM

Figure 1. XRD patterns of cubic SrTiO₃ powder and polyvinylpyrrolidone (PVP) surface modified SrTiO₃ powder and SEM image of SrTiO₃ powder prepared by mixed alkali method is shown in the inset.

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图 2 为PVP、立方体状SrTiO₃粉体和PVP表面包覆改性SrTiO₃粉体的FT-IR吸收光谱

Figure 2. FT-IR absorption spectra of PVP, cubic SrTiO₃ powder and PVP surface coated modified SrTiO₃ powder

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图 3 (a)立方体状SrTiO₃粉体和PVP表面包覆改性SrTiO₃粉体的XPS全谱扫描图谱；(b) PVP表面改性前后的SrTiO₃粉体的O1 s元素的精细扫描谱线Fig. 3(a) XPS of cubic SrTiO₃ powder and PVP surface coated modified SrTiO₃ powder; (b) Fine scanning spectra of O1 s elements of SrTiO₃ powder before and after PVP surface modification

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图 4 表面PVP包覆改性后SrTiO₃粉体的TEM: (a)低倍数的TEM照片; (b)高倍数的TEM照片

Figure 4. TEM images of SrTiO₃ powder after surface PVP modification at low magnifications (a) and at high magnifications (b)

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图 5 PVP 表面改性前后立方体状SrTiO₃粉体的热失重曲线图

Figure 5. TG curve of cubic SrTiO₃ powder and PVP surface coated modified SrTiO₃ powder

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图 6 填充量为5 vol.%时，PVDF电介质复合薄膜的SEM图：(a) 未表面改性SrTiO₃粉体/PVDF电介质复合薄膜的SEM; (b) 为PVP表面包覆改性SrTiO₃粉体/PVDF电介质复合薄膜的SEM图;(c)PVDF电介质复合薄膜的SEM界面图

Figure 6. (a) SEM images of unmodified SrTiO₃ powder/PVDF composite films; (b) the SEM images of PVP surface modified SrTiO₃ powder /PVDFdielectric composite films at a concentration of 5 vol.%;(c)cross-section SEM of PVP surface modified SrTiO₃ powder /PVDFdielectric composite films

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图 7 (a)不同填充量PVP表面包覆改性SrTiO₃粉体/PVDF电介质复合薄膜与未表面改性SrTiO₃粉体；/PVDF电介质复合薄膜的介电常数对比图; (b)为两种PVDF电介质复合薄膜的介电损耗对比图

Figure 7. Comparison of dielectric constants of surface modified SrTiO₃ powder/PVDF composite films and unmodified SrTiO₃ powder/ PVDF composite films with different filling amounts of fillers, and the comparison of dielectric loss of the PVDF composites films is shown in the inset

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图 8 不同填充量PVP表面包覆改性SrTiO₃粉体/PVDF电介质复合薄膜与未表面改性SrTiO₃粉体/PVDF电介质复合薄膜的耐击穿场强对比图

Figure 8. The breakdown strength comparison of PVP surface modified SrTiO₃ powder /PVDF composite films and unmodified SrTiO₃ powder / PVDF composite films with different filling amount fillers

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图 9 PVP表面包覆改性SrTiO₃粉体/PVDF电介质复合薄膜与未表面改性SrTiO₃粉体/PVDF电介质复合薄膜的电场强度分布有限元模拟图。

Figure 9. Finite element simulation of electric field distribution of PVP surface modified SrTiO₃ powder /PVDF composite films and unmodified SrTiO₃ powder/PVDF composite films

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图 10 SrTiO₃粉体/PVDF电介质复合薄膜内部电荷的分布示意图

Figure 10. Schematic diagram of internal charge distribution of SrTiO₃ powder /PVDF composite films

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图 11 电场为1000 kV/cm时，PVDF和不同填充浓度的PVDF电介质复合薄膜的P-E曲线

Figure 11. P-E curves of PVDF and PVDF dielectric composites films with different filling concentrations under 1000 kV/cm

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图 12 (a) 不同组分PVDF电解质薄膜最大击穿电场下的P-E曲线图(b)PVDF和不同填充浓度表面包覆改性SrTiO₃粉体/PVDF电介质复合薄膜的储能密度变化曲线

Figure 12. (a) . P−E curves of PVDF and PVDF dielectric composites films with filling concentrations. (b)Energy storage density of PVDF and PVDF composites films with different filling concentrations

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图 13 SrTiO₃粉体填充量为5vol%时，未处理表面改性SrTiO₃粉体/PVDF电介质复合薄膜和PVP改性SrTiO₃粉体/PVDF电介质复合薄膜的储能密度和放电效率曲线关系图

Figure 13. Energy storage density and discharge efficiency of untreated SrTiO₃ powder/ PVDF composite films and PVP modified SrTiO₃ powder/PVDF composite films at a concentration of 5vol.%

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图 14 5vol% PVP改性SrTiO₃粉体/PVDF电介质复合薄膜在不同测试频率下的P-E曲线

Figure 14. P-E curves of PVP modified SrTiO₃ powder/PVDF composite films at a concentration of 5vol.%

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表 1 为前期文献报道钛酸锶钡陶瓷/PVDF复合材料的储能密度与本文实验结果对比

Table 1. Comparison of the energy storage density of PVDF-based composites and the experimental results in this paper

Materials	Surface modification method	Energy storage density /(J·cm^-3)	Reference
BaTiO₃/P(VDF-HFP) films	Aminomethyl phosphonic acid	3.2	[24]
SrTiO₃/PVDF films	-	3.54	[25]
BaTiO₃/P(VDF-HFP) composite films	-	4.89	[26]
SrTiO₃/PVDF films	Polyvinylpyrrolidone	5.3	This paper

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