PVDF/PPy柔性直流纳米发电机的制备与性能

李金徽; 刘晓东; 金欣; 史善静; 王闻宇

doi:10.13801/j.cnki.fhclxb.20231122.001

PVDF/PPy柔性直流纳米发电机的制备与性能

doi: 10.13801/j.cnki.fhclxb.20231122.001

1.
天津工业大学　材料科学与工程学院，天津 300387
2.
天津工业大学　纺织科学与工程学院，天津 300387

基金项目: 国家自然科学基金(51573136)

详细信息

通讯作者:
金欣，博士，教授，博士生导师，研究方向为功能纤维材料结构与性能　E-mail: jinxin@tiangong.edu.cn

中图分类号: TB303；TB332
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- 文章访问数: 222
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- 被引次数: 0
出版历程
- 收稿日期: 2023-08-23
- 修回日期: 2023-10-12
- 录用日期: 2023-11-15
- 网络出版日期: 2023-11-23
- 刊出日期: 2024-06-15

Preparation and performance of PVDF/PPy flexible DC nano-generator

1.
College of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
2.
College of Materials Textile and Engineering, Tiangong University, Tianjin 300387, China

Funds: National Natural Science Foundation of China (51573136)

摘要

摘要: 针对传统纳米发电机为交流输出，仍需采用外部整流器进行直流转化而导致的难以高度集成、柔性化和较低的功率密度问题，本文将聚偏氟乙烯(PVDF)静电纺膜作为基底，在其表面气相聚合聚吡咯(PPy)，制得PVDF/PPy复合纳米纤维膜，并依据肖特基整流原理，以该复合纳米纤维膜构建直流纳米发电机。研究了不同聚合时间下氧化剂浓度对PVDF/PPy复合纳米纤维膜形貌和直流纳米发电机机电性能的影响。结果表明：当氧化剂浓度为2.0 mol/L，聚合时间为90 min时，电输出性能最优，对应峰值电压输出为1.23 V，峰值电流输出为210.55 μA，理论功率密度达到28.77 μW/cm²。本项研究展示的PVDF/PPy直流纳米发电机，其能源转换机制源于压电高分子的压电效应和肖特基结的整流效应。该类直流纳米发电机具备柔韧、集成式和自整流的特征，可灵活用于各种场所，直接为电子设备提供电能。
- 纳米发电机 /
- 压电聚合物 /
- 肖特基结 /
- PVDF /
- PPy
Abstract: To address the difficulty of high integration, flexibility and low power density caused by the traditional nanogenerators with alternating current (AC) output and still need to use external rectifiers for direct current (DC) conversion, in this paper, poly(vinylidene fluoride) (PVDF) electrostatically spun film was used as a substrate and polypyrrole (PPy) was gas-phase polymerized on the surface of the film to produce a composite nanofibrous film of PVDF/PPy, and based on the Schottky collation principle, a DC nanogenerator was constructed by this composite nanofibrous film. The composite nanofiber membrane was used to construct a DC nano-generator based on Schottky finishing principle. The effects of oxidant concentration on the morphology of PVDF/PPy composite nanofiber membrane and the electromechanical performance of DC nano-generator were investigated under different polymerization time. The results show that when the oxidant concentration is 2 mol/L and the polymerization time is 90 min, the electrical output performance is optimal, corresponding to a peak voltage output of 1.23 V, a peak current output of 210.55 μA, and a theoretical power density of 28.77 μW/cm². In this study, this PVDF/PPy DC nano-generator was demonstrated, and the energy conversion mechanism originates from the piezoelectric effect of piezoelectric polymer and the rectification effect of Schottky junction. These DC nano-generators are flexible, integrated and self-rectifying, and can be flexibly used in various places to provide power directly to electronic devices.
- nano-generator /
- piezoelectric polymer /
- Schottky junction /
- PVDF /
- PPy

HTML全文

图 1 聚偏氟乙烯/聚吡咯(PVDF/PPy)直流纳米发电机的制备及测试示意图：(a) PVDF 纳米纤维膜的制备；(b) 气相合成 PPy；(c) PVDF/PPy 直流(DC)纳米发电机；(d) 机电测试仪

Py—Pyrrole

Figure 1. Schematic diagram of preparation and test of poly(vinylidene fluoride)/poly(pyrrole) (PVDF/PPy) DC nano-generator: (a) Preparing PVDF nanofiber membrane; (b) Gas phase polymerization of PPy; (c) PVDF/PPy direct current (DC) nano-generator; (d) Electromechanical performance testing equipment

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图 2 纺丝流量对 PVDF 纳米纤维膜形貌的影响(纺丝时间为 5 h)：(a) 0.6 mL/h；(b) 0.7 mL/h；(c) 0.8 mL/h；(d) 0.9 mL/h；(e) 1.0 mL/h；(f) 纺丝流量对纤维直径的影响

Figure 2. Effect of spinning flow rate on microstructure of PVDF nanofiber membrane (Spinning time is 5 h): (a) 0.6 mL/h; (b) 0.7 mL/h; (c) 0.8 mL/h; (d) 0.9 mL/h; (e) 1.0 mL/h; (f) Effect of spinning flow-rate on fiber diameter

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图 3 纺丝时间为 3 h，纺丝流速对电压输出(a)和电流输出(b)的影响；纺丝时间和流速对电压输出(c)和电流输出(d)的影响

Figure 3. Effect of spinning flow-rate with spinning time of 3 h on voltage output (a) and current output (b); Influence of spinning time and flow-rate on voltage output (c) and current output (d)

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图 4 氧化剂浓度0.5 mol/L (a)、1.0 mol/L (b)、1.5 mol/L (c)、2.0 mol/L (d)、2.5 mol/L (e)和聚合时间(f)对 PVDF/PPy 复合纳米纤维膜形貌及电阻的影响

Figure 4. Effect of oxidant concentration 0.5 mol/L (a), 1.0 mol/L (b), 1.5 mol/L (c), 2.0 mol/L (d), 2.5 mol/L (e) and polymerization time (f) on the microstructure and resistance of PVDF/PPy composite nanofiber membranes

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图 5 不同聚合时间下氧化剂浓度对 PVDF/PPy 纳米发电机电压输出的影响：(a) 30 min；(b) 60 min；(c) 90 min；(d) 120 min；(e) 150 min；(f) 聚合时间为 90 min 时不同氧化剂浓度下的电流-电压(I-V)曲线

Figure 5. Effect of oxidant concentration on voltage of the PVDF/PPy nano-generator under different polymerization time: (a) 30 min; (b) 60 min; (c) 90 min; (d) 120 min; (e) 150 min; (f) Current-voltage (I-V) curves under different oxidation concentrations at polymerization time of 90 min

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图 6 不同聚合时间下氧化剂浓度对PVDF/PPy纳米发电机电流输出的影响：(a) 30 min；(b) 60 min；(c) 90 min；(d) 120 min；(e) 150 min；(f) 聚合时间为90 min时不同氧化剂浓度下的电荷积累

Figure 6. Effect of oxidant concentration on current of the PVDF/PPy nano-generator at different polymerization time: (a) 30 min; (b) 60 min; (c) 90 min; (d) 120 min; (e) 150 min; (f) Charge accumulation under different oxidation concentrations at polymerization time of 90 min

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图 7 PVDF交流(AC)纳米发电机与PVDF/PPy DC纳米发电机的电压、电流输出及理论功率密度

Figure 7. Voltage, current output and theoretical power density of PVDF alternating current (AC) nano-generator and PVDF/PPy DC nano-generator

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图 8 PVDF/PPy 器件机制和性能：(a) 肖特基接触示意图及肖特基势垒和内建电场；(b) 不同电极的I-V曲线；(c) Al/PVDF/PPy/Cu器件示意图(氧化剂浓度 2 mol/L，聚合时间 90 min)、输出电压(d)和输出电流(e)；(f) 组合器件Al/PVDF/PPy/Cu/PVDF/Cu示意图及电压输出(g)和电流输出(h)；(i) 组合器件Cu/PVDF/Al/PVDF/PPy/Cu示意图及电压输出(j)和电流输出(k)

Figure 8. Mechanism and performance of PVDF/PPy devices: (a) Schottky contact schematic diagram, with an enlarged view showing Schottky barrier and built-in electric field; (b) I-V curves of different electrodes; Schematic diagram of PVDF/PPy device (Oxidant concentration 2 mol/L, polymerization time 90 min) (c), output voltage (d) and output current (e); Schematic diagram of the combined device Al/PVDF/PPy/Cu/PVDF/Cu (f) and output voltage (g) and output current (h); Schematic diagram of combined device Cu/PVDF/Al/PVDF/PPy/Cu (i) and output voltage (j) and output current (k)

ε—Built-in electric field; E_FM—Fermi energy levels of metals; E_FS—Fermi energy levels for semiconductors; E_C—Conduction zone bottom energy level; E_V—Valence band top energy level

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图 9 PVDF/PPy直流纳米发电机直接点亮商用LED灯(a)及对应电路图(b)

Figure 9. PVDF/PPy DC nano-generator can directly light commercial LED lamps (a) and its corresponding circuit diagram (b)

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表 1 直流纳米发电机的机电性能

Table 1. Electromechanical performance of DC nano-generator

Device configuration	Output voltage/V	Current density/(μA·cm⁻²)	Theoretical power/(μW·cm⁻²)	Ref.
Au/PPy/Al	0.7	218.6	153.02	[25]
Al/PEDOT:PSS	0.8	73(0.73 A/m²)	58.4	[26]
ZnO NWs/Pt	0.01	8.33(500 nA, 2 mm×3 mm)	0.08	[35]
Au/ZnO/Cu	0.3	3.11(7 μA, 2.25 cm²)	0.93	[36]
Au/ZnO-PAN/ZnO-Cu	1.6	7.2	11.52	[36]
Au/PANI/Al	0.6	(80.5 μA)	—	[37]
Cu/PANI/Ag	3.5	(800 μA)	—	[37]
Au/PPy-DMSO/Al	0.88	105.9	93.19	[38]
Au/PPy/Al	0.67	6.35(8.45 μA, 1.33 cm²)	4.25	[38]
PANI-coated fabric/PVDF	3.2	3.77	12.06	[39]
Al/PEDOT coating	0.45	2.5(2.5 μA, 1 cm²)	1.13	[40]
Cu/PVDF-PPy/Al	1.23	23.39(210.55 μA, 9 cm²)	28.77	This work
Notes: PEDOT:PSS—Poly(3, 4-ethylenedioxythiophene):polystyrene sulfonate; NWs—Nanowires; PAN—Polyacrylonitrile; PANI—Polyaniline; DMSO—Dimethyl sulfoxide.

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