Interface modification and energy storage properties of barium titanate-based/ polyvinylidene fluoride composite

Wang Jiao; Liu Shao-Hui; Chen Chang-Qing; Hao Hao-Shan; Zhai Ji-Wei

doi:10.7498/aps.69.20201031

Abstract

With the development of power electronic device equipment towards miniaturization and high performance, the dielectric materials with high energy storage density, high charge and discharge efficiency, easy processing and molding, and stable performance are urgently needed. At present, Barium titanate-based dielectric ceramics have a high dielectric constant, but low breakdown field strength and poor flexibility. Polymer-based dielectric materials have ultra-high functional density, ultra-fast charge and discharge response time, good flexibility, high breakdown field strength, light weight and other advantages, but low dielectric constant and low polarization strength. Their energy storage density is low, which limits the power capacitor component size and application scope. In order to obtain material with high energy storage performance, it was proposed to add high dielectric constant inorganic ceramic fillers to the polymer through a composite method to improve the energy storage performance of the material. The interface plays a vital role in the performance of the composite material. In this article, we review the latest research advance in the interface design and control of barium titanate/polyvinylidene fluoride composite dielectric materials. The effects of interface modification methods such as organic surface modification, inorganic functionalization and organic-inorganic synergistic modification on the polarization and energy storage performance of composite materials are summarized. The existing interface models and theoretical research methods are discussed, and the existing challenges and practical limitations, and the future research directions are prospected.

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 ; Zhai Ji-Wei, apzhai@tongji.edu.cn

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

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References

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Cited By

图 1 电介质薄膜电容器的主要应用

Figure 1. Application of dielectric film capacitor.

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图 2 有机-无机复合材料模型

Figure 2. Model of organic-inorganic composite material model.

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图 3 钛酸钡纤维串联模型与并联模型的储能密度对比图^[28]

Figure 3. Comparison of energy storage density of barium titanate nanofibers in series and parallel models (BTnws, BaTiO₃ nanowires)^[28].

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图 4 核壳结构填料合成的示意图及TEM图^[51]

Figure 4. Schematic diagram and TEM diagram of core-shell structure fillers^[51]

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图 5 不同厚度核壳结构的Na₂Ti₃O₇@PMPC纳米纤维^[57]

Figure 5. Core-shell structure Na₂Ti₃O₇@PMPC nanofibers with different thickness^[57].

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图 6 复合材料能量存储和释放的示意图　(a) 没有界面极化; (b)界面极化较强; (c) 界面极化较弱^[65]

Figure 6. Schematic diagram of energy storage and release of composites: (a) No interfacial polarization; (b) stronger interfacial polarization; (c) weaker interfacial polarization^[65].

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图 7 复合材料的储能性能与有限元模拟结果^[54]

Figure 7. Energy storage performance and finite element simulation results of composite materials^[54].

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图 8 钛酸钡@TiO₂/聚合物复合材料储能密度与电场强度的关系^[71]

Figure 8. Relationship between energy storage density and electric field of BaTiO₃@TiO₂/polymer composites^[71].

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表 1 不同聚合物介电性能、储能性能的比较

Table 1. Comparison of dielectric properties and energy storage properties of different polymers.

薄膜材料	1 kHz介电常数	最高使用温度/℃	击穿电压/kV·m^–1	损耗/%	储能密度/J·cm^–3
聚丙烯 (PP)	2.2	105	6400	< 0.02	1—1.2
聚酯 (PET)	3.3	125	5700	< 0.50	1—1.5
聚碳酸酯 (PC)	2.8	125	5280	< 0.15	0.5—1
聚乙烯 (PEN)	3.2	125	5500	< 0.15	1—1.5
聚苯硫醚 (PPS)	3.0	200	5500	< 0.03	1—1.5
聚偏氟乙烯 (PVDF)	12	125	5900	< 1.80	2.4

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表 2 提高复合材料介电常数的方法及理论

Table 2. Methods and theories of improving dielectric constant of composite materials.

理论名称	渗流理论	Lichtenecher模型	Bruggeman模型	Maxwell-Garnett模型
公式	$\begin{array}{l} {\sigma _{\rm{c}}} \propto {(f - {f_{\rm{c}}})^t} \\ {\sigma _{\rm{c}}} \propto {({f_{\rm{c}}} - f)^{ - q}} \\ \end{array} $	$\varepsilon _{_{{\rm{eff}}}}^{^n} = {f_1}\varepsilon _1^n + {f_2}\varepsilon _2^n$	$f\dfrac{ { {\varepsilon _1} \!-\! {\varepsilon _{ {\rm{eff} } } } } }{ {2{\varepsilon _{ {\rm{eff} } } } \!+\! 2{\varepsilon _1} } } \!+\! (1 \!-\! f)\dfrac{ { {\varepsilon _2} \!-\! {\varepsilon _{ {\rm{eff} } } } } }{ { {\varepsilon _{ {\rm{eff} } } } \!+\! 2{\varepsilon _2} } } \!=\! 0$	$\dfrac{ { {\varepsilon _{ {\rm{eff} } } } - {\varepsilon _1} } }{ { {\varepsilon _{ {\rm{eff} } } } + 2{\varepsilon _1} } } = f\dfrac{ { {\varepsilon _1} - {\varepsilon _2} } }{ { {\varepsilon _1} + 2{\varepsilon _2} } }$
字母的含义	${f_{\rm{c}}}$表示渗流阈值, ${\sigma _{\rm{c}}}$为电导率, t和q分别为临界参数	${\varepsilon _{{\rm{eff}}}}$为复合材料的介电常数, ${\varepsilon _1}$为基相的介电常数, ${\varepsilon _2}$为分散相的介电常数, ${f_2}$为填料的体积分数, n = 1, –1, 0	${\varepsilon _{{\rm{eff}}}}$为复合材料的介电常数, ${\varepsilon _1}$, ${\varepsilon _2}$分别为填料和基体的介电常数, $f$为填料的体积分数	${\varepsilon _{{\rm{eff}}}}$为复合材料的介电常数, ${\varepsilon _1}$, ${\varepsilon _2}$分别为填料和基体的介电常数, $f$为填料的体积分数
适用条件	将体系的微观结构与宏观性能联系起来	可以判断两材料复合并联或者串联模型	可以成功解释复合材料由绝缘体向导体的转变	可以模拟两种绝缘体构成的复合材料的介电常数
不足之处	影响渗流值的因素众多, 如填料的尺寸、形貌等	填料含量较高时, 利用此模型与测量值有明显的差距.	仅当填料浓度小于渗流阈值时公式才成立	没有考虑到填料相的电阻率, 预测的介电常数值比实际值大

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Vol. 69, Issue 21 - 2020-11-05

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