静电纺P(VDF-TrFE)纳米纤维在柔性压电传感与能量收集领域的研究进展

屈展; 夏广波; 方剑

doi:10.13801/j.cnki.fhclxb.20230914.001

静电纺P(VDF-TrFE)纳米纤维在柔性压电传感与能量收集领域的研究进展

doi: 10.13801/j.cnki.fhclxb.20230914.001

屈展^{1, 2},
夏广波^{1, 2},
方剑^{1, 2, ,}

1.
苏州大学　纺织与服装工程学院，苏州 215021
2.
苏州大学　现代丝绸国家工程实验室，苏州215023

基金项目: 国家自然科学基金面上项目(52173059)；江苏省高校自然科学研究项目重大项目(21KJA540002)

详细信息

通讯作者:
方剑，博士，教授，博士生导师，研究方向为电活性纤维材料和柔性智能可穿戴纺织品　E-mail：jian.fang@suda.edu.cn

中图分类号: TN384；TB332
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出版历程
- 收稿日期: 2023-06-15
- 修回日期: 2023-08-05
- 录用日期: 2023-09-03
- 网络出版日期: 2023-09-18
- 刊出日期: 2024-03-01

Research progress of electrospun P(VDF-TrFE) nanofibers in the field of flexible piezoelectric sensing and energy harvesting

QU Zhan^{1, 2},
XIA Guangbo^{1, 2},
FANG Jian^{1, 2
, ,}

1.
College of Textile and Clothing Engineering, Soochow University, Suzhou 215021, China
2.
National Engineering Laboratory for Modern Silk, Soochow University, Suzhou 215023, China

Funds: National Natural Science Foundation of China (52173059); Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions (21KJA540002)

摘要

摘要: 压电聚合物聚偏氟乙烯-三氟乙烯(P(VDF-TrFE)) 作为聚偏氟乙烯(PVDF)典型的共聚物，具有优异的压电性能、机械性能及生物相容性。因此基于P(VDF-TrFE) 静电纺压电网膜的柔性压电传感器与能量收集器在可穿戴电子设备、智能纺织品及医疗健康系统等领域有着广阔的前景，能够将触觉/压力、应变、声波甚至生理微振动等信号转换为电学信号或低功率的电能。本文旨在深入分析P(VDF-TrFE) 压电性能的机制，总结各种提升静电纺P(VDF-TrFE) 纳米纤维压电性的策略，全面概述P(VDF-TrFE) 基柔性压电传感与能量收集方面的应用，特别是在压力与触觉传感、声传感、生物组织传感、生理微振动传感及能量收集等领域的研究进展。阐述了静电纺压电聚合物纳米纤维的新兴应用场景，并讨论了该领域目前的挑战和未来前景。
- P(VDF-TrFE) /
- 静电纺丝法 /
- 纳米纤维 /
- 传感 /
- 能量收集 /
- PVDF /
- 压电
Abstract: Poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE)) is a copolymer of polyvinylidene fluoride (PVDF) that exhibits outstanding piezoelectric properties, mechanical properties, and biocompatibility. Therefore, the flexible piezoelectric sensors and energy harvesters based on P(VDF-TrFE) have a promising future in the fields of intelligent textiles, wearable electronic devices and medical and health systems. These devices can convert signals such as tactile, pressure, strain, acoustic waves or even physiological micro-vibrations into electrical signals or low-power electrical energy. This paper aims to provide an in-depth analysis of the mechanism of P(VDF-TrFE) piezoelectric properties, summarize various strategies to enhance the piezoelectricity of electrostatically spun P(VDF-TrFE) nanofibers, and provide a comprehensive overview of the applications of P(VDF-TrFE)-based flexible piezoelectric sensing and energy harvesting. Specifically, research advances in the areas of pressure and tactile sensing, acoustic sensing, biological tissue sensing, physiological micro-vibration sensing, and energy harvesting are summarized. Finally, the emerging application scenarios of electrospun piezoelectric polymer nanofibers are illustrated, the current challenges and future prospects in this field are discussed.
- P(VDF-TrFE) /
- electrospinning /
- nanofiber /
- sensing /
- energy harvesting /
- PVDF /
- piezoelectricity

HTML全文

图 1 P(VDF-TrFE)在受到机械作用时的压电性机制

E—Electromotive force

Figure 1. Piezoelectric mechanism of P(VDF-TrFE) under mechanical action

下载: 全尺寸图片幻灯片

图 2 (a) P(VDF-TrFE)共聚物中VDF摩尔含量与剩余极化(P_r)的关系^[27]；(b) P(VDF-TrFE)共聚物的相图^[28]

PTrFE—Polytrifluoroethylene; VDF—Vinylidene fluoride; PVDF—Poly(vinylidene fluoride); T_m—Melting temperature; T_c—Curie temperature

Figure 2. (a) Relationship between VDF molar content and remanent polarization (P_r) of P(VDF-TrFE) copolymers^[27]; (b) Phase diagram for a P(VDF-TrFE) copolymer^[28]

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图 3 P(VDF-TrFE)与BaTiO₃ (a)、MXene (b)、BaTiO₃与MXene (c) 的作用机制^{[41, 43]}

Figure 3. Mechanism diagram of P(VDF-TrFE) and BaTiO₃ (a), MXene (b), BaTiO₃ and MXene (c) ^{[41, 43]}

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图 4 静电纺聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))纳米纤维在传感和能量收集领域的应用^[37-41]

PENG—Piezoelectric nanogenerator

Figure 4. Application of electrospinning poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE)) nanofibers in sensing and energy harvesting^[37-41]

下载: 全尺寸图片幻灯片

图 5 基于自供电智能步态传感个人步态监测系统^[14]

Figure 5. Scheme diagram of personal gait judgment system based on self-powered sensor^[14]

下载: 全尺寸图片幻灯片

图 6 生理微振动传感示意图^[53]

Figure 6. Scheme diagram of physiological micro-vibration sensing^[53]

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表 1 静电纺丝法制备的P(VDF-TrFE) 纳米纤维应用总结

Table 1. Summary of application of P(VDF-TrFE) nanofibers prepared by electrospinning

Application	Mole ratio	F(β)/%	X_c/%	Special processing	Performance	Year	Ref.
Pressure sensor	70/30	—	—	Spray on PEDOT-CNT/rGO electrode	Sensitivity: 67.4 kPa⁻¹; Response time: 12 ms	2019	[58]
	70/30	—	—	Oil modified stacked porous nanofibers	Voltage output: 3.8 V; Current output: 243.6 nA	2021	[14]
	75/25	—	70	Doped with MXene	Voltage output: 1.58 V; Power density: 3.64 mW/m²; Stability: 1000 cycles	2021	[42]
	70/30	—	—	Doped with ZnO NPs	Voltage output: 1.788 V	2021	[59]
	80/20	92	90	Doped with rGO-MCNTs	Sensitivity: 16.125 kPa⁻¹	2022	[23]
	80/20	—	—	Doped with carbon nano powders as electrode	Sensitivity: 0.14 mV/N; Stability: 10⁶ cycles	2022	[60]
	75/25	81.04	50	Doped with BaTiO₃ and MXene	Voltage output: 7.6 V; Response time: 56 ms; Stability:5000 cycles	2023	[43]
	70/30	—	—	Polydopamine-assisted ZnO nanowires attached to P(VDF-TrFE) nanofibers	Sensitivity: (25.0±3.5) V/N; Range of forces: 970 N	2023	[44]
Tactile Sensor	75/25	—	—	The sensor is composed of two sections, TENG and PENG	Response time:100 ms	2020	[45]
	70/30	92	—	Designed a patterned piezoelectric array	Sensitivity: 2.5 mV/kPa; Response time: 5 ms; Stability: 25000 cycles	2022	[46]
	70/30	—	—	All electrospun fabrics doped with BaTiO₃	Sensitivity: 2.72 nA/N	2022	[47]
	80/20	—	—	Doped with CB as electrode	Sensitivity: 4 mV/N; Stability: 10⁶ cycles	2023	[61]
Acoustic sensor	55/45	—	—	8-hole electrode and package structure	Voltage output:14.5 V; Current output: 28.5 μA	2017	[48]
Acoustic sensor	70/30	—	—	—	Sensitivity: 10 V/Pa	2020	[49]
Biotissue engineering sensors	75/25	95	—	The aligned electrospun fiber scaffolds	Cell growth cycle: 10 days	2020	[40]
	70/30	88.49	—	The aligned electrospun fiber scaffolds	Current output:1.75 nA	2020	[50]
	—	—	—	Doped with CuO, P3HT, CuPc or MB	Cell viability: 77%	2023	[51]
Physiological micro-vibration sensor	70/30	—	—	Oily modification and combined with TENG	Voltage output: 13.1 V; Current output: 46 nA	2022	[52]
Physiological micro-vibration sensor	—	86.43	—	Doped with nanoclay	Bandwidth: 0.3-40 Hz; Stability: 10⁵ cycles; Sensitivity: 24.35 mV/kPa	2022	[53]
Energy harvester	75/25	—	—	The electrospun BNT-ST/PVDF-TrFE nanofibers are twined around a conductive thread	Voltage output: 2.1 V; Current output: 0.42 μA	2019	[62]
	70/30	—	—	Electrospun PVDF-TrFE nanofibers are deposited on copper wires	Current density: 22 nA/cm²; Power density: 8.6 μW/cm³	2021	[54]
	75/25	94	—	Doped with PMMA@BaTiO₃	Voltage output: 12.6 V; Current output: 1.30 μA; Output power: 4.25 μW; Stability: 6000 cycles	2021	[55]
	70/30	—	46.37	Doped with PEO and LiCl	Voltage output: 69.4 V; Output power: 40.7 µW/cm²	2022	[56]
	—	—	76	A nonpiezoelectric polymer core is introduced	Voltage output: 126 V; Current output: 7.2 μA; Power density: 710 mW/m²	2023	[57]
	70/30	—	52.9	Doped with amine-functionalized graphene oxide (AGO)	Energy density: 4.75 J/cm⁻³; Piezoelectric coefficient: –47 pm/V	2023	[63]
Notes: F(β)—β phase content of P(VDF-TrFE); X_c—Crystallinity of P(VDF-TrFE); PEO—Polyethylene oxide; P3HT—Poly(3-hexylthiophene); CuPc—Copper phthalocyanine; MB—Methylene blue; BNT-ST—Bismuth sodium titanate-strontium titanate; PMMA—Polymethyl methacrylate; CB—Carbon black; PEDOT—Poly(3, 4-ethylenedioxythiophene); CNT—Carbon nanotubes; rGO—Reduced graphene oxide; NPs—Nano particles; MCNTs—Multi-walled carbon nanotubes; TENG—Triboelectric nanogenerator.

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