基于无机填料复合薄膜的摩擦纳米发电机研究进展

doi:10.15541/jim20200742

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 919-928.DOI: 10.15541/jim20200742 CSTR: 32189.14.10.15541/jim20200742

基于无机填料复合薄膜的摩擦纳米发电机研究进展

郭隐犇¹(), 陈子曦¹, 王宏志², 张青红³()

1.上海工程技术大学材料工程学院, 上海 201620
2.东华大学材料科学与工程学院, 纤维材料改性国家重点实验室, 上海 201620
3.东华大学教育部先进玻璃制造技术工程中心, 上海 201620

收稿日期:2020-12-29 修回日期:2021-02-22 出版日期:2021-09-20 网络出版日期:2021-03-12
通讯作者: 张青红, 教授 E-mail: zhangqh@dhu.edu.cn
作者简介:郭隐犇(1990-), 女, 讲师. E-mail: guoyb@sues.edu.cn
基金资助:
国家自然科学基金(51903151);上海市“晨光计划”(19CG66)

Progress of Inorganic Filler Based Composite Films for Triboelectric Nanogenerators

GUO Yinben¹(), CHEN Zixi¹, WANG Hongzhi², ZHANG Qinghong³()

1. College of Materials Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
3. Engineering Research Center of Advanced Glasses Manufacturing Technology, Ministry of Education, Donghua University, Shanghai 201620, China

Received:2020-12-29 Revised:2021-02-22 Published:2021-09-20 Online:2021-03-12
Contact: ZHANG Qinghong, professor. E-mail: zhangqh@dhu.edu.cn
About author:GUO Yinben(1990-), female, lecturer. E-mail: guoyb@sues.edu.cn
Supported by:
National Natural Science Foundation of China(51903151);Shanghai “ChenGuang” Project(19CG66)

摘要/Abstract

摘要：

摩擦纳米发电机(Triboelectric Nanogenerator, TENG)是一种将微小机械能转化为电能并加以收集利用的绿色能源器件, 具有活性材料种类广泛、器件结构简单以及易于集成等特点。较低的输出功率密度是目前阻碍其实际应用的主要因素之一。如何通过材料组分设计与制备提高其输出功率密度及能量转化效率, 是目前该领域研究者关注的热点问题。在摩擦纳米发电机常用的活性材料-高分子聚合物中引入功能性填料是一种简便且高效的改性方法, 不仅能够对薄膜摩擦电性能进行优化、提高输出性能, 还能够赋予其新功能, 可谓一举多得。因此, 此类复合薄膜已广泛应用于TENG领域, 例如TiO₂、SiO₂、BaTiO₃、ZnSnO₃、MoS₂、石墨烯、二维黑磷等无机填料对复合材料的性能均有不同程度的优化, TENG的输出功率密度最高提升了数十倍。本文结合国内外研究现状, 按照填料对基体材料表面性能以及电学性能优化作用两个方面进行阐述, 综述了复合材料薄膜在摩擦纳米发电机中的研究进展, 并展望了未来复合材料用于提高TENG输出性能研究的发展方向。

关键词: 无机填料, 复合薄膜, 表面性能, 电学性能, 输出功率密度, 摩擦纳米发电机, 综述

Abstract:

The triboelectric nanogenerator (TENG) is a kind of green power source which can harvest and transform small mechanical energy into electricity. Triboelectric nanogenerators have various active materials, simple structures, and easy to integrate with other devices. However, its relatively low output power density hinders the further practical application of TENGs. How to improve the output performance of TENGs through the modification of the active triboelectric materials is one of the hottest spots. It is a facile and effective way to introduce functional fillers into polymer substrates to fabricate composite materials, which improve the triboelectricity of pristine material and bring new functions for the device. Thus, composite films are widely used in TENGs. For example, inorganic fillers like TiO₂, SiO₂, BaTiO₃, ZnSnO₃, MoS₂, r-GO sheets, and nanofibril-phosphorene have been introduced into polymers to improve the output power density of TENGs by dozens of times. Based on domestic and international research, this review introduces the applications of the composite film in TENGs. The improvements of TENGs induced by the fillers are discussed from two aspects: the surface property and electrical property. Finally, future challenges in developing composites based TENGs are prospected.

Key words: inorganic filler, composite film, surface property, electrical property, output power density, triboelectric nanogenerator, review

中图分类号:

TB332

郭隐犇, 陈子曦, 王宏志, 张青红. 基于无机填料复合薄膜的摩擦纳米发电机研究进展[J]. 无机材料学报, 2021, 36(9): 919-928.

GUO Yinben, CHEN Zixi, WANG Hongzhi, ZHANG Qinghong. Progress of Inorganic Filler Based Composite Films for Triboelectric Nanogenerators[J]. Journal of Inorganic Materials, 2021, 36(9): 919-928.

图/表 7

图1 用于TENG的不同复合材料薄膜以及所制备的器件示意图[20,21,22,23,24,25,26,27]

Fig. 1 Schematic diagram of various composite films and devices for TENGs[20,21,22,23,24,25,26,27]

图2 基于rGONRs/PVDF复合薄膜的TENG器件示意图、复合薄膜的3D-AFM图片以及器件工作500个循环的输出电压图谱(a)[20]; 海绵状TiO2/PDMS的TENG器件示意图, TiO2/PDMS薄膜光催化原理图(b)[21]; 静电纺丝制备分层结构SiO2/P(VDF-TrFE)复合薄膜的SEM照片以及纯P(VDF-TrFE)膜(蓝色)和SiO2/P(VDF-TrFE)复合薄膜(红色)的表面电势对比(c)[40]

Fig. 2 Schematic diagram of rGONRs /PVDF based TENG, 3D-AFM image of the rGONRs/PVDF thin film, and output voltage of the rGONRs/PVDF based TENG for 500 cycles (a)[20], schematic diagram of TiO2/PDMS sponge based TENG, schematic of organic containment degradation by photocatalyst NPs in TiO2/PDMS sponge (b)[21], and SEM images of hierarchical structures for SiO2/P(VDF-TrFE) composite fabricated by electrospinning process, and the surface potentials of pure P(VDF-TrFE) film (blue) and SiO2/P(VDF-TrFE) composite film (red) (c)[40] (Colorful figures are available on website)

图3 不同BaTiO3含量的纤维素纸复合薄膜介电常数曲线(C/BT-1、 C/BT-3和C/BT-5样品中BaTiO3质量含量分别为50%、75%和83.3%)以及器件用于无线通讯的示意图(a)[22]; 不同BaTiO3含量的PVDF复合薄膜介电常数以及所组成器件表面电荷密度对比图(b)[23]; ZnSnO3@PDMS 复合薄膜的表面扫描电镜照片及其不同含量时的输出电流与电压曲线(c)[24]

Fig. 3 Dielectric constants of the cellulose/ BaTiO3 aerogel paper with different BaTiO3 contents (the mass ratios of BaTiO3 in C/BT-1, C/BT-3 and C/BT-5 were 50%, 75% and 83.3%, respectively) and schematic image of wireless application of the TENG(a)[22], dielectric constants and charge densities of the BaTiO3/PVDF nanocomposite films with different BaTiO3 volume fractions (b)[23], and SEM image of ZnSnO3@PDMS composite film, and output currents and voltages of the corresponding TENGs with different ZnSnO3 contents (c)[24] (Colorful figures are available on website)

图4 P(VDF-TrFE)、PDMS、PDMS-30wt% BTO(30BTO)和PDMS-30wt% CCTO (30CCTO)薄膜的开尔文探针力显微镜(KPFM)图像(a)以及其输出功率密度(b)[46]; 基于PDMS以及PDMS@F-MOF薄膜器件的电场分布(有限元模拟)(c)及其实际输出功率密度(d)[49]

Fig. 4 KPFM images (a) and power densities (b) of P(VDF-TrFE), PDMS, 30BTO and 30CCTO films[46], electrical field distributions (finite-element simulation) (c) and power densities as a function of the external resistance (d) of the devices based on PDMS and PDMS@F-MOF[49]

图5 不同GP含量的复合薄膜的TENG内阻以及输出功率, 插图为器件结构示意图(a)[25]; PDMS@GO@SDS复合薄膜的示意图, 基于不同薄膜的TENG输出电压对比图(b)[50]; 纯Nylon-11和PVDF-TrFE(黑色), Nylon-11@MoS2和P(VDF-TrFE)@MoS2复合薄膜组成的器件的未极化状态(红色)和极化状态(蓝色)的TENG的电荷密度比较(c)[51]; 纯PVDF薄膜和PVDF/TOML复合膜的TENG表面电荷对比图, 以及PVDF/TOML复合膜照片(d)[26]; CNF/黑磷复合薄膜的照片(e), 及单纯CNF与CNF/黑磷复合薄膜所制备的TENG输出电压对比图(f)[27]

Fig. 5 Internal resistances and output powers of PDMS@GPs composite membranes with different GP contents with inset showing structural schematic of corresponding TENG device (a)[25], schematic image of PDMS@GO@SDS composite film and the output voltages of different TENGs (b)[50], comparison of charge densities for TENGs : pure Nylon-11 and PVDF-TrFE (black), Nylon-11@MoS2 and P(VDF-TrFE)@MoS2 composite films in non-poled state (red) and poled state (blue) (c)[51], comparison of charges for PVDF and PVDF/TOML nanocomposite films based TENGs with inset showing the picture of PVDF/TOML nanocomposite film (d)[26], optical image of the CNF/phosphorene hybrid paper (e), and the comparison of voltages between pure CNF based TENG and CNF/ phosphorene hybrid paper based TENG (f)[27]

图6 书形TENG的制备过程示意图(a), 具有不同mSiO2浓度的PVDF/mSiO2纳米纤维的表面电势衰减曲线(b)[55]; SiO2-FP在充电前、充电过程中电荷载流子的能量分布图, 以及高温下的表面电势衰减(c); 充电过程中在注入电荷位于水-FP界面(I), 注入电荷位于FP-氧化物界面(II)两种竞争情况下的电场分布(d)[57]

Fig. 6 Illustration of the fabrication process of a book-shaped TENG (a), normalized surface potential decay of PVDF/mSiO2 nanofibers with different concentrations of mSiO2 (b)[55]; energy landscapes for (injected) charge carriers for SiO2-FP before and during charging, and surface potential decays at elevated temperatures (c), electric field distributions during charging for two competing scenarios with injected charge residing at the aqueous-FP interface (I), and injected charge residing at the FP-oxide interface (II) (d)[57]

表1 用于TENG复合材料的填料种类

Table 1 Fillers used in composite materials for TENGs

Filler	Matrix	Optimal fillers ratio		Dielectric constant	Shape/Size	Increased percentage of output/%	Ref.
Filler	Matrix	wt%	vol%	Dielectric constant	Shape/Size	Increased percentage of output/%	Ref.
rGONRs	PVDF	97	—	—	Nanoribbon	200 (Voltage)	[20]
TiO₂	PDMS	0.05	—	—	Nanopaticle	—	[21]
SiO₂	P(VDF-TrFE)	30	—	—	Nanopaticle (D=10-20 nm)	300 (Voltage)	[40]
BaTiO₃	Cellulose paper	16.7	—	6.25	Nanopaticle (D=200 nm)	300 (Power)	[22]
BaTiO₃	PVDF	—	11.25	25	Nanopaticle (D=100 nm)	650 (Voltage)	[23]
ZnSnO₃	PDMS	6	—	—	Nanocube	620 (Current)	[24]
CaCu₃Ti₄O₁₂	PDMS	30	—	—	Nanopaticle	1000 (Power)	[46]
KUAST-8	PDMS	0.5	—	4.23	Nanopaticle	1100 (Power)	[49]
Graphite particle	PDMS	3	—	3	Nanopaticle (D=20-40 nm)	260 (Power)	[25]
GO	PDMS	—	16.7	—	Nanosheet	300 (Voltage)	[50]
MoS₂	Nylon-11/P(VDF-TrFE)	—	—	—	Nanosheet	800 (Power)	[51]
Monolayer titania	PVDF	1.5	—	11.51	Thickness=1.2 nm	5000 (Power)	[26]
Phosphorene	CNF	0.2	—	—	Nanosheet	4600 (Power)	[27]
Hydrophobic SiO₂	PVDF	0.8	—	—	Nanopaticle	530 (Power)	[55]
SiO₂	Thermoplastic nanofiber membranes	—	—	—	Nanopaticle	—	[57]

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基于无机填料复合薄膜的摩擦纳米发电机研究进展

Progress of Inorganic Filler Based Composite Films for Triboelectric Nanogenerators

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