CN112216787A - Flexible piezoelectric generator based on PVDF/DAST composite fiber material and preparation method thereof - Google Patents

Flexible piezoelectric generator based on PVDF/DAST composite fiber material and preparation method thereof Download PDF

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CN112216787A
CN112216787A CN202010999279.4A CN202010999279A CN112216787A CN 112216787 A CN112216787 A CN 112216787A CN 202010999279 A CN202010999279 A CN 202010999279A CN 112216787 A CN112216787 A CN 112216787A
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dast
pvdf
composite fiber
fiber material
piezoelectric generator
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许向东
胡君杰
熊可
张敏刚
冯元婷
蒋亚东
谷雨
成晓梦
刘晋荣
周玉龙
李尤
徐明辉
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a PVDF/DAST composite fiber material-based flexible piezoelectric generator and a preparation method thereof, belonging to the field of piezoelectric energy conversion and comprising a middle piezoelectric layer, wherein the middle piezoelectric layer is a PVDF/DAST composite fiber intermediate layer, and DAST in the PVDF/DAST composite fiber intermediate layer accounts for 1-80 wt% of the total mass of PVDF and DAST. The PVDF/DAST flexible composite material is compounded with the DAST through electrostatic spinning to prepare a one-dimensional PVDF/DAST flexible composite material with excellent flexibility, excellent polarization effect and piezoelectric performance; the PVDF/DAST composite fiber material based flexible piezoelectric generator is prepared by respectively preparing a conductive layer on the upper surface and the lower surface of the PVDF/DAST flexible fiber material, leading out wires and respectively wrapping a polymer protective layer on the upper surface and the lower surface, and has wide application in the fields of biology, photoelectricity, renewable energy, wearable equipment and the like.

Description

Flexible piezoelectric generator based on PVDF/DAST composite fiber material and preparation method thereof
Technical Field
The invention belongs to the field of piezoelectric energy conversion, and particularly relates to a PVDF/DAST composite fiber material-based flexible piezoelectric generator and a preparation method thereof.
Background
At present, the increasing global population and the rapid development of the industry have caused the excessive consumption of fossil fuels and the drastic deterioration of climate, so that the piezoelectric generator that can convert the minute mechanical energy in the environment into electric energy has received a great deal of attention. The performance of a piezoelectric generator is mainly determined by the piezoelectric material between the two electrodes. The traditional inorganic piezoelectric materials such as barium titanate, lead titanate, gallium nitride and the like are not beneficial to preparing a wearable flexible piezoelectric generator due to the problems of low mechanical quality factor, large electrical loss, poor flexibility, poor biocompatibility, harmful heavy metal content and the like.
As a flexible organic piezoelectric material with wide application, polyvinylidene fluoride (PVDF) changes the structural symmetry of polyethylene through strong-polarity F atoms, not only shows excellent piezoelectric characteristics, but also has the advantages of light weight, good flexibility and the like. However, the PVDF material has the defects of small piezoelectric coefficient, low output signal, and the like, which greatly limits its practical application. To improve the piezoelectric output performance of PVDF, many effective methods have been proposed. Shi et al prepared a composite fiber material of barium titanate and PVDF using an electrospinning method, so that the piezoelectric output was greatly improved (see K.M.Shi, B.Sun, X.Y.Huang and P.K.Jiang, Nano Energy,2018,52, 153-. However, since barium titanate is inorganic and PVDF is organic, the compatibility between the two is poor, reducing the mechanical flexibility of the composite. Furthermore, Karan et al induced an increase in the proportion of β phase in the PVDF matrix by doping with highly conductive iron ions and redox graphene, improving the piezoelectric output performance of PVDF to some extent (see S.K. Karan, D.Mandal and B.B.Khutua, Nanoscale,2015,7, 10655-. Nevertheless, the performance improvement effect of this method is limited, and the PVDF still has the problem of low piezoelectric output.
In particular, 4- (4-dimethylaminostyryl) picoline p-toluenesulfonate (DAST) as a novel organic piezoelectric material (see eastern grant, valley rain, plum blossoming, dreaminess, jiang asia east, liangyixiang, wangfu, qian lian, zhoufoxin, "DAST organic single crystal piezoelectric material and a preparation method thereof", invented chinese patent, filed in 2017, 24 th and 1 month, and patent application No. 201710053780.X) not only has high piezoelectric response, but also has simple preparation process and low cost. Moreover, DAST is a green organic piezoelectric material. However, solutions prepared from pure DAST powder have low viscosity and are difficult to form into films independently. Therefore, the DAST-based flexible two-dimensional composite piezoelectric film is prepared by the methods of spin coating, spray coating and the like by the schdong et al, and the mechanical properties of the DAST are improved (see schdong, plum blosson, valley rain, dawn dream, liangyuan, jiang east, wangfu, zhoufanan, qian, "a DAST flexible composite piezoelectric material and a preparation method thereof", a chinese patent of invention, 3, 9, 2017, filed on 3/month, and No. 201710138736.9). However, the polarization effect of the composite film obtained by the method is not ideal, and the piezoelectric performance of the prepared two-dimensional composite film is influenced. In addition, it is difficult to directly prepare a composite material with a one-dimensional structure by using methods such as spin coating and spray coating.
In conclusion, the existing flexible piezoelectric generator has the problems of low flexibility, low efficiency of converting mechanical energy into electric energy, high difficulty in preparing a high-performance one-dimensional material with an excellent polarization effect and the like, and the application of the high-performance one-dimensional material in practice is limited. Therefore, the development of a flexible piezoelectric generator with simple preparation process, environmental protection, strong mechanical flexibility and excellent piezoelectric performance is urgently needed in the field.
Disclosure of Invention
The invention aims to: aiming at the problems of low flexibility, low efficiency of converting mechanical energy into electric energy and high difficulty in preparing a high-performance one-dimensional material with an excellent polarization effect of the conventional flexible piezoelectric generator, the invention provides a flexible piezoelectric generator based on a PVDF/DAST composite fiber material and a preparation method thereof; under the condition of keeping excellent piezoelectric performance, the defect that DAST is difficult to independently form a film is overcome, and the mechanical property of the material is effectively improved; the one-dimensional composite piezoelectric material with excellent polarization effect is prepared, and the problems of low flexibility, biocompatibility, piezoelectric output and other performances of the piezoelectric generator based on the conventional piezoelectric film are solved.
The technical scheme adopted by the invention is as follows:
the utility model provides a flexible piezoelectric generator based on PVDF/DAST composite fiber material, includes middle piezoelectric layer, middle piezoelectric layer is PVDF/DAST composite fiber intermediate layer, DAST accounts for 1 ~ 80 wt% of PVDF and DAST total mass in the PVDF/DAST composite fiber intermediate layer.
Preferably, the PVDF/DAST composite fiber intermediate layer is prepared by an electrospinning method.
Preferably, the flexible piezoelectric generator further comprises conductive layers arranged on the upper surface and the lower surface of the PVDF/DAST composite fiber intermediate layer, polymer encapsulation layers respectively covering the surfaces of the conductive layers, and wires respectively connected with the conductive layers.
Preferably, the conductive layer is a composite conductive material of any one or more of aluminum, gold, titanium nitride, titanium silicide, titanium tungsten alloy, tungsten silicide, tungsten nitride, nickel silicide, nickel nitride, tantalum nitride, iron, platinum, copper, silver and chromium; the polymer packaging layer is made of a composite flexible medium film of any one or more of a polyimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polystyrene film and a benzocyclobutene film.
A preparation method of a PVDF/DAST composite fiber material in a PVDF/DAST composite fiber material-based flexible piezoelectric generator comprises the following steps:
(1) weighing a certain amount of PVDF and DAST crystals, dissolving the PVDF and DAST crystals in an organic solvent, sealing, stirring for 1-100 h, and then carrying out ultrasonic treatment for 10-1000 min to obtain an electrostatic spinning solution which is uniformly mixed;
(2) and (2) preparing the one-dimensional PVDF/DAST composite fiber material from the uniformly mixed electrostatic spinning solution prepared in the step (1) through an electrostatic spinning device, and drying the one-dimensional PVDF/DAST composite fiber material in a drying box to obtain the one-dimensional PVDF/DAST composite fiber material.
Preferably, the organic solvent is a mixed solution of N, N dimethylformamide ((DMF)) and acetone in a volume ratio of 0.01:1 to 1:1
Preferably, the mass fraction of DAST and PVDF crystals in the electrostatic spinning solution is 1-80 wt%, and the mass fraction of DAST crystals in the electrostatic spinning solution is 1-80 wt% of the total mass of PVDF crystals and DAST crystals. In the electrostatic spinning solution, the mass fraction of the total mass of the DAST and PVDF crystals in the total mass of the solution is optimally 15 wt%, 18 wt%, 20 wt%, 22 wt% and 25 wt%; the mass fraction of DAST crystals in the total mass of the PVDF crystals and DAST crystals is preferably 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%.
Preferably, the electrospinning conditions are as follows: the spinning voltage is 1-50 kV, the spinning humidity is 20-90%, the size of the syringe needle is 0.001-10 mm, the injection rate of the spinning solution is 0.0001-1 mL/min, the fiber receiving distance is 1-50 cm, and the spinning time is 1-10 h.
Preferably, in the drying process of the PVDF/DAST composite fiber material, the temperature of a drying oven is 20-400 ℃, and the time is 10-1000 min.
Preparation method of flexible piezoelectric generator based on PVDF/DAST composite fiber material, wherein the selected area of preparation is 1-1000 cm2The PVDF/DAST composite fiber material is used as a middle piezoelectric layer, and a conducting layer and a lead are respectively stuck on the upper surface and the lower surface of the piezoelectric layer and packaged to prepare the flexible piezoelectric generator.
The invention adopts the one-dimensional PVDF/DAST organic composite fiber material as the piezoelectric layer, the preparation method is simple, the obtained device not only has good mechanical toughness and ultrahigh piezoelectric output performance, but also has the characteristics of environmental protection and the like, and has wide application prospect in the fields of flexible electronics and wearable sensors.
Compared with the prior art, the invention has the beneficial effects that:
(1) the PVDF/DAST flexible composite material is compounded with the DAST through electrostatic spinning to prepare a one-dimensional PVDF/DAST flexible composite material with excellent flexibility, excellent polarization effect and piezoelectric performance; the VDF/DAST composite fiber material-based flexible piezoelectric generator is prepared by respectively preparing a conductive layer on the upper surface and the lower surface of the PVDF/DAST flexible fiber material, leading out wires and respectively wrapping a polymer protective layer on the upper surface and the lower surface, and has wide application in the fields of biology, photoelectricity, renewable energy, wearable equipment and the like;
(2) the PVDF/DAST composite film is in a one-dimensional nanofiber structure, and the piezoelectric output performance of the PVDF/DAST flexible piezoelectric generator is obviously improved due to the large surface area of the nanofiber structure. Wherein, the open-circuit voltage and the short-circuit current of the flexible piezoelectric generator based on PVDF/10 wt% DAST composite fiber material are respectively as high as 5V and 110 nA; meanwhile, the high flexibility is also shown;
(3) the one-dimensional piezoelectric composite material is prepared by adopting the electrostatic spinning technology, and has the advantages of simple equipment, low cost, simple operation and the like; because the electrostatic spinning process needs high voltage, the prepared piezoelectric material is polarized in the spinning process, so that the piezoelectric material with excellent polarization effect can be prepared, and the preparation steps of the flexible piezoelectric generator are reduced.
Drawings
FIG. 1 is a structural cross-sectional view of a PVDF/DAST composite fiber material-based flexible piezoelectric generator;
FIG. 2 is a scanning electron microscope image of piezoelectric fibers of a PVDF/DAST composite fiber material based flexible piezoelectric generator;
FIG. 3 is an X-ray diffraction pattern of a one-dimensional PVDF/DAST composite piezoelectric fiber under different organic material mixture concentrations;
FIG. 4 is an open circuit voltage response test result of a fabricated flexible piezoelectric generator under the same test conditions and with a mass fraction of total mass of PVDF and DAST in total mass of the solution of 20 wt% unchanged, but with a mass fraction of DAST in total mass of PVDF and DAST being different;
FIG. 5 shows the results of short circuit current response tests on flexible piezoelectric generators prepared under the same test conditions with a mass fraction of total mass of PVDF and DAST in total mass of the solution of 20 wt%, but with a mass fraction of DAST in total mass of PVDF and DAST different.
Labeled as: 1-polymer packaging layer, 2-conductive layer, 3-PVDF/DAST composite fiber intermediate layer and 4-wire.
Detailed Description
The present invention will be described in further detail in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Fig. 1 is a cross-sectional view of a PVDF/DAST composite fiber material based flexible piezoelectric generator structure of the present invention. As shown in fig. 1, the PVDF/DAST composite fiber material-based flexible piezoelectric generator includes a PVDF/DAST flexible composite fiber material intermediate layer 3, conductive layers 2 respectively covering the upper surface and the lower surface of the PVDF/DAST flexible composite fiber material intermediate layer 3, wires 4 respectively led out from the conductive layers 2, and polymer encapsulation layers 1 respectively covering the surfaces of the conductive layers 2.
The following is a specific preparation method of the PVDF/DAST composite fiber material-based flexible piezoelectric generator:
(1) preparing a spinning solution: under the condition of keeping the mass fraction of the total mass of PVDF and DAST to the total mass of the solution to be 20 wt% unchanged at room temperature, the mass fractions of DAST to the total mass of PVDF and DAST are respectively 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt% and 25 wt%. Respectively placing 6 groups of PVDF and DAST which are respectively weighed according to the mass fraction in 6 beakers with the capacity of 10ml, then adding 2ml of DMF and 3ml of acetone into each beaker by using a rubber head dropper in sequence (the total mass of 2ml of DMF and 3ml of acetone is measured to be 3.98g), and sealing by using a preservative film; then placing the beaker into a magneton stirring device, stirring for 3 hours at 50 ℃, standing and cooling to room temperature; putting each beaker into an ultrasonic instrument for ultrasonic treatment for 30min to obtain 6 uniformly mixed PVDF/DAST electrostatic spinning solutions with different proportioning concentrations;
(2) preparing a composite fiber material: and (2) respectively preparing 6 PVDF/DAST composite fiber materials by using 6 uniformly mixed PVDF/DAST electrostatic spinning solutions prepared in the step (1) by using an electrostatic spinning device. Wherein the preparation process parameters are as follows: electrostatic spinning voltage is 18kV, spinning humidity is 60%, the size of the syringe needle is 0.60mm, the injection rate of the spinning solution is 0.010ml/min, the fiber receiving distance is 15cm, and the spinning is carried outThe time is 3 h. After spinning, 6 composite fiber materials prepared under 6 different concentrations are respectively put into a 60 ℃ oven for drying for 40min, after the organic solvent is completely volatilized, the 6 composite fiber materials are respectively cut into the composite fiber materials with the area of 1.8 multiplied by 1.8cm2The composite fiber material is ready for use;
(3) manufacturing a flexible piezoelectric generator: the area prepared by the step (2) is 1.8 multiplied by 1.8cm2The 6 PVDF/DAST composite fiber materials are respectively used as a middle piezoelectric layer, copper adhesive tapes are respectively adhered to the upper surface and the lower surface of the middle piezoelectric layer to be used as conductive layers, leads are led out at the same time, and then transparent polytetrafluoroethylene waterproof dressings are respectively adhered to the surfaces of the two conductive layers for packaging, so that the flexible piezoelectric generator is packaged. The piezoelectric properties were tested separately.
Fig. 2 is a scanning electron microscope image of the piezoelectric fiber layer of the flexible piezoelectric generator prepared in this embodiment. It can be seen that: the PVDF/DAST composite fiber material is in a one-dimensional nano or micron structure, has uniform diameter and smooth surface, and is beneficial to preparing a flexible piezoelectric generator with excellent performance.
Fig. 3 is an X-ray diffraction pattern of the piezoelectric fiber layer of the flexible piezoelectric generator prepared in this example. Wherein the diffraction peak of the piezoelectric fiber at 20.6 ° corresponds to the (200) crystal plane of PVDF, and the diffraction peaks at 9.8 °, 12.8 ° and 19.9 ° correspond to the (002), (111) and (004) crystal planes of DAST, respectively. The X-ray diffraction pattern shows that the one-dimensional piezoelectric fiber material prepared in the example contains PVDF and DAST components at the same time, and shows that the one-dimensional piezoelectric fiber material is a PVDF/DAST composite fiber material.
Fig. 4 and 5 show the open-circuit voltage and short-circuit current test results of the PVDF/DAST composite fiber-based flexible piezoelectric generators with 6 different mixture concentrations, which were manufactured according to the examples, while keeping the test conditions unchanged. When the pressure is 1N and the force application frequency is 1Hz, the open-circuit voltage and the short-circuit current of the flexible piezoelectric generator based on the pure PVDF fiber film are only 1.3V and 30nA respectively. In contrast, the open circuit voltage and short circuit current of a flexible piezoelectric generator based on PVDF/10 wt% DAST composite fiber material were as high as 5V and 110nA, respectively, under the same test conditions. This demonstrates that the flexible piezoelectric generator based on PVDF/DAST composite fiber material prepared according to the examples has excellent piezoelectric performance. The excellent piezoelectric performance enables the flexible piezoelectric generator to have wide application prospects in the fields of biology, photoelectricity, renewable energy sources, wearable equipment and the like.
The above-mentioned embodiments only express the specific embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for those skilled in the art, without departing from the technical idea of the present application, several changes and modifications can be made, which are all within the protection scope of the present application.

Claims (10)

1. A flexible piezoelectric generator based on PVDF/DAST composite fiber material, comprising a middle piezoelectric layer, characterized in that: the middle piezoelectric layer is a PVDF/DAST composite fiber middle layer, and DAST in the PVDF/DAST composite fiber middle layer accounts for 1-80 wt% of the total mass of the PVDF and the DAST.
2. The PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 1, wherein: the PVDF/DAST composite fiber intermediate layer is prepared by an electrostatic spinning method.
3. The PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 1, wherein: the flexible piezoelectric generator further comprises conductive layers arranged on the upper surface and the lower surface of the PVDF/DAST composite fiber intermediate layer, polymer packaging layers respectively covering the surfaces of the conductive layers, and wires respectively connected with the conductive layers.
4. The PVDF/DAST composite fiber material-based flexible piezoelectric generator of claim 3, wherein: the conducting layer is a composite conducting material of any one or more of aluminum, gold, titanium nitride, titanium silicide, titanium-tungsten alloy, tungsten silicide, tungsten nitride, nickel silicide, nickel nitride, tantalum nitride, iron, platinum, copper, silver and chromium; the polymer packaging layer is made of a composite flexible medium film of any one or more of a polyimide film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polystyrene film and a benzocyclobutene film.
5. The method for preparing PVDF/DAST composite fiber material in the PVDF/DAST composite fiber material-based flexible piezoelectric generator according to any one of claims 1-4, is characterized by comprising the following steps:
(1) weighing a certain amount of PVDF and DAST crystals, dissolving the PVDF and DAST crystals in an organic solvent, sealing, stirring for 1-100 h, and then carrying out ultrasonic treatment for 10-1000 min to obtain an electrostatic spinning solution which is uniformly mixed;
(2) and (2) preparing the one-dimensional PVDF/DAST composite fiber material from the uniformly mixed electrostatic spinning solution prepared in the step (1) through an electrostatic spinning device, and drying the one-dimensional PVDF/DAST composite fiber material in a drying box to obtain the one-dimensional PVDF/DAST composite fiber material.
6. The method for preparing PVDF/DAST composite fiber material in the PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 5, wherein: the organic solvent is a mixed solution of N, N-dimethylformamide and acetone in a volume ratio of 0.01: 1-1: 1.
7. The method for preparing PVDF/DAST composite fiber material in the PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 5, wherein: in the electrostatic spinning solution, the mass fraction of DAST and PVDF crystals in the solution is 1-80 wt%, and the mass fraction of DAST crystals in the solution is 1-80 wt%.
8. The method for preparing PVDF/DAST composite fiber material in the PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 5, wherein: the electrostatic spinning conditions are as follows: the spinning voltage is 1-50 kV, the spinning humidity is 20-90%, the size of the syringe needle is 0.001-10 mm, the injection rate of the spinning solution is 0.0001-1 mL/min, the fiber receiving distance is 1-50 cm, and the spinning time is 1-10 h.
9. The method for preparing PVDF/DAST composite fiber material in the PVDF/DAST composite fiber material-based flexible piezoelectric generator according to claim 5, wherein: in the drying process of the PVDF/DAST composite fiber material, the temperature of a drying oven is 20-400 ℃, and the time is 10-1000 min.
10. The method for preparing a PVDF/DAST composite fiber material-based flexible piezoelectric generator according to any of claims 5 to 9, wherein: the selected area for preparation is 1-1000 cm2The PVDF/DAST composite fiber material is used as a middle piezoelectric layer, and a conducting layer and a lead are respectively stuck on the upper surface and the lower surface of the piezoelectric layer and packaged to prepare the flexible piezoelectric generator.
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