CN111682796A - Flexible piezoelectric energy collector based on negative Poisson ratio macroscopic graphene film - Google Patents
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/18—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction producing electrical output from mechanical input, e.g. generators
- H02N2/186—Vibration harvesters
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N2/00—Electric machines in general using piezoelectric effect, electrostriction or magnetostriction
- H02N2/22—Methods relating to manufacturing, e.g. assembling, calibration
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a flexible piezoelectric energy collector based on a negative Poisson ratio macroscopic graphene film, which comprises a flexible substrate and a laminated structure piezoelectric power generation unit fixed on the surface of the flexible substrate, wherein a lead is arranged on the surface of the laminated structure piezoelectric power generation unit and used for leading out charges/voltages generated after the flexible piezoelectric energy collector is stretched and deformed, and the laminated structure piezoelectric power generation unit comprises the negative Poisson ratio macroscopic graphene film and the flexible piezoelectric film. According to the invention, the flexible and high-conductivity macroscopic graphene film with the negative Poisson ratio effect is utilized, the negative Poisson ratio effect is introduced into the flexible piezoelectric energy collector, and the tensile deformation of the piezoelectric film is changed from the original unidirectional tension to the tension in two in-plane vertical directions by virtue of the strain coupling between the piezoelectric film in the piezoelectric power generation unit with the laminated structure and the negative Poisson ratio macroscopic graphene film, so that the electrical output performance of the device is improved.
Description
Technical Field
The invention relates to the technical field of environmental energy collection, in particular to a flexible piezoelectric energy collector based on a negative poisson ratio macroscopic graphene film.
Background
In recent years, wearable electronics have shown a wide market prospect with the development of electronic information technology and the progress of human social life. Meanwhile, the energy crisis and environmental pollution caused by the excessive consumption of fossil fuels have prompted people to find new renewable energy sources to supply energy for these electronic devices. In the wearable device, mechanical energy related to human body motion, such as bending of joints of fingers, elbows and the like, treading of feet during walking, even beating of heart or pulse, expansion of chest during breathing and the like, is collected and utilized, so that energy can be conveniently supplied to the wearable intelligent electronic device. The piezoelectric energy collector can realize conversion from mechanical energy to electric energy based on the piezoelectric effect principle of materials. Compared with other forms of environmental mechanical energy collection technologies, such as electrostatic type, electromagnetic induction type, triboelectric type and the like, piezoelectric type energy collection has the advantages of simple and compact device structure, high energy conversion efficiency, good electric energy output stability, easiness in flexibility, easiness in integration with electronic devices and the like, and has good development and application potentials.
To meet the requirements of flexible piezoelectric energy harvesting applications, piezoelectric materials should not only have excellent piezoelectric properties, but also must be flexible. For this reason, various flexible piezoelectric materials have been developed, mainly including piezoelectric nanomaterials, inorganic piezoelectric films, piezoelectric polymers, piezoelectric composites, and the like. In fact, the development of various flexible piezoelectric materials and the performance optimization thereof are always the key points of the development of flexible piezoelectric energy collectors. Nevertheless, the electrical output performance of most flexible piezoelectric energy harvesting devices is still low, and the power consumption requirement of most electronic devices cannot be met. One reason for this is that the mechanical structure of the device is not yet optimal, and the performance of the piezoelectric material is not fully utilized. Besides the optimization of the performance of the piezoelectric material, the optimization of the mechanical structure of the device is also an effective way for improving the electrical output performance of the flexible piezoelectric energy collecting device. Therefore, in order to develop a high-performance piezoelectric energy harvesting device, optimization of the performance of the piezoelectric material should be combined with optimization of the mechanical structure of the device.
Poisson's ratio is one of the basic mechanical properties of a material. Materials with a negative poisson's ratio exhibit an "auxetic effect," i.e., the material expands laterally when uniaxially stretched. The negative Poisson ratio effect of the material is reasonably utilized to improve the performance of the piezoelectric device. Li et al [ AIP adv, 20177,015104 ] and Ferguson et al [ sens.activators A,2018,282,90-96] respectively based on finite element calculations and experiments, have confirmed that the use of a negative Poisson ratio structure stainless steel substrate can significantly improve the electrical output power of a rigid vibrating piezoelectric energy harvesting device. However, the rigid vibration piezoelectric energy collector has insufficient flexibility and is difficult to apply to wearable devices; the negative poisson's ratio effect is introduced by the structural design of the stainless steel substrate, and also limits the flexibility of the device. Therefore, an effective method is found, a negative poisson's ratio effect is introduced into the flexible piezoelectric energy collector, and the method has great significance for developing the high-performance flexible piezoelectric energy collector and promoting the application of the high-performance flexible piezoelectric energy collector in wearable electronics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the invention aims to provide a flexible piezoelectric energy collector based on a negative Poisson ratio macroscopic graphene film.
The technical scheme for solving the technical problems is as follows:
the flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film comprises a flexible substrate and a laminated structure piezoelectric power generation unit fixed on the surface of the flexible substrate, wherein a lead is arranged on the surface of the laminated structure piezoelectric power generation unit and used for leading out charges/voltages generated after the flexible piezoelectric energy collector is stretched and deformed, and the laminated structure piezoelectric power generation unit comprises the negative Poisson ratio macroscopic graphene film and the flexible piezoelectric film.
Furthermore, in the piezoelectric power generation unit with the laminated structure, the negative poisson ratio macroscopic graphene film is fixed on the upper side and the lower side of the flexible piezoelectric film.
Further, the preparation method of the negative poisson ratio macroscopic graphene membrane comprises the following steps:
and 3, placing the graphene oxide membrane obtained in the step 2 in a high-temperature graphitization furnace, and carrying out high-temperature treatment at 3000 ℃ under the protection of inert atmosphere to obtain the negative poisson ratio macroscopic graphene membrane.
Further, the thickness of the negative Poisson ratio macroscopic graphene film is 5-200 μm, the Poisson ratio is-0.5-0, the Young modulus is 0.01-20GPa, and the conductivity is not lower than 104S/m。
Further, the piezoelectric film is made of PVDF and at least one of copolymer thereof or piezoelectric composite material, and has a thickness of 10-100 μm.
Further, the flexible substrate is made of at least one of PET, polyimide, epoxy, aluminum, copper, and stainless steel, and has a thickness of 50 to 500 μm.
Further, the number of the stacked piezoelectric power generating units is one or more, the stacked piezoelectric power generating units are arranged on the substrate in a transverse, longitudinal or array mode, and the electrical connection mode among the stacked piezoelectric power generating units is in series or in parallel.
Further, when the flexible piezoelectric energy collector works, the piezoelectric film in the piezoelectric power generation unit with the laminated structure and the negative Poisson's ratio macroscopic graphene film are in strain coupling, so that the piezoelectric film is stretched in two perpendicular directions in the plane of the piezoelectric film.
The invention has the beneficial effects that: according to the invention, the flexible and high-conductivity macroscopic graphene film with the negative Poisson ratio effect is utilized, the negative Poisson ratio effect is introduced into the flexible piezoelectric energy collector, and the tensile deformation of the piezoelectric film is changed from the original unidirectional tension to the tension in two in-plane vertical directions by virtue of the strain coupling between the piezoelectric film in the piezoelectric power generation unit with the laminated structure and the negative Poisson ratio macroscopic graphene film, so that the electrical output performance of the device is improved.
Drawings
FIG. 1 is a schematic structural view before and after deformation of the piezoelectric power generating unit of the present invention using a single lamination structure;
FIG. 2 is a photograph of a piezoelectric power generating element of the present invention having a laminated structure;
FIG. 3 is a photograph of a flexible piezoelectric energy harvester of the present invention;
FIG. 4 is a typical waveform of the output open circuit voltage during repeated bending of the present invention;
FIG. 5 is a typical waveform of the output short circuit current during the repeated bending process of the present invention;
FIG. 6 is a comparison of open circuit voltage versus short circuit current peak to peak for the present invention and a flexible piezoelectric energy harvester based on metallic silver;
FIG. 7 is a measurement of the Poisson ratio of a negative Poisson ratio macroscopic graphene film in the present invention;
FIG. 8 is a cross-sectional microscopic morphology of a negative Poisson's ratio macroscopic graphene film in the present invention;
FIG. 9 is a photograph of a negative Poisson ratio macroscopic graphene film in accordance with the present invention;
fig. 10 is a schematic structural view before and after deformation of the present invention when two piezoelectric power generating elements having a laminated structure are used.
The list of parts represented by the various reference numbers in the drawings is as follows:
1. a flexible substrate; 2. a piezoelectric film; 3. a negative poisson's ratio macroscopic graphene membrane; 4. and (4) conducting wires.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
In the description of this patent, the terms "intermediate," "upper," "lower," "lateral," "longitudinal," and the like are used in an orientation or positional relationship that is indicated for convenience in describing the patent and to simplify the description, and should not be construed as limiting the patent.
In the description of this patent, it is noted that, unless otherwise specifically stated or limited, the terms "bonded," "attached," "coated," "laminated," "secured," and the like are used in a generic sense to denote an interconnection. The specific meaning of the above terms in this patent may be understood by those of ordinary skill in the art as appropriate.
As shown in fig. 1, the flexible piezoelectric energy collector based on the negative poisson's ratio macroscopic graphene film provided by the invention comprises a flexible substrate and a laminated structure piezoelectric power generation unit fixed on the flexible substrate, wherein the laminated structure piezoelectric power generation unit is a sandwich structure formed by bonding the negative poisson's ratio macroscopic graphene films on the upper and lower sides of the flexible piezoelectric film.
The working mode of the flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film is that the flexible substrate is bent to drive the piezoelectric power generation unit with the laminated structure fixed on the flexible substrate to generate tensile deformation, and the generated voltage/current is led out from the surface of the graphene through a lead.
The flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film can be prepared according to the following steps:
step 4, adhering conductive copper foil tapes to the surfaces of the upper and lower layers of the negative Poisson ratio macroscopic graphene film 3 of the piezoelectric power generation unit with the laminated structure obtained in the step 3 to serve as leads for outputting electric signals;
step 5, selecting a PET sheet with the thickness of 260 mu m, and cutting the PET sheet to 10.0 × 2.0.0 cm2Flexibility as a piezoelectric energy harvesterA substrate 1;
and 6, fixing the laminated structure piezoelectric power generation unit adhered with the conductive copper foil lead 4 obtained in the step 4 to the middle position of the PET flexible substrate in the step 5 in a manner that epoxy resin glue is adopted to fix two ends of the laminated structure piezoelectric power generation unit to the PET flexible substrate respectively, and obtaining the flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film shown in the figure 3.
The flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film obtained by the steps is good in flexibility and can be easily bent.
The substrate is repeatedly bent to drive the laminated piezoelectric power generation unit fixed on the substrate to generate tensile deformation so as to generate voltage/current signal output, an electrometer is adopted to detect the voltage/current signal output generated by the device in the repeated bending process, a typical open-circuit voltage signal waveform is shown in fig. 4, and a typical short-circuit current signal waveform is shown in fig. 5, so that the electrical output of the device is continuous and stable.
The same structural design is adopted, but the negative poisson ratio macroscopic graphene is replaced by the metal silver, the flexible piezoelectric energy collector based on the metal electrode is obtained and used as a comparison group, the open-circuit voltage and the short-circuit current of the two piezoelectric energy collectors under the same working condition are compared, and the statistical result of 4 samples in each group is shown in fig. 6.
The negative poisson ratio macroscopic graphene membrane can be prepared according to the following steps:
step 1: dispersing graphene oxide serving as a raw material by using ultrapure water, and magnetically stirring at 400rpm for 4 hours to form a dispersion liquid with the concentration of 3%;
step 2: introducing graphene oxide into a glass mold, enabling the graphene oxide to be self-leveling, standing at room temperature, and drying to form a film;
and step 3: and (3) placing the graphene oxide film obtained in the step (2) in a high-temperature graphitization furnace, performing high-temperature treatment under the protection of Ar atmosphere, keeping the temperature for 2 hours at the temperature rising rate of 10 ℃/min and the temperature and time of 1300 ℃, keeping the temperature for 1 hour at 3000 ℃, and cooling to room temperature to obtain the negative poisson ratio macroscopic graphene film.
The macroscopic graphene film obtained according to the above steps has a negative poisson ratio, as shown in fig. 7, which is a relationship between longitudinal strain and transverse strain under uniaxial stretching condition, and the poisson ratio of the obtained macroscopic graphene film is about-0.39.
The thickness of the negative poisson's ratio macroscopic graphene film obtained according to the steps is about 200 mu m, as shown in fig. 8, the sectional microscopic morphology picture is shown, and the obtained negative poisson's ratio macroscopic graphene film is formed by stacking sheets and has a loose porous structure.
The negative poisson ratio macroscopic graphene film obtained by the steps has good flexibility, and the macroscopic graphene film can be easily bent as shown in fig. 9.
The negative Poisson ratio macroscopic graphene film obtained by the steps has good conductivity, and the conductivity test of the four-probe method shows that the conductivity is about 105S/m。
The negative poisson ratio macroscopic graphene film obtained according to the steps can be used for assembling the flexible piezoelectric energy collector based on the negative poisson ratio macroscopic graphene film.
In the invention, the number of the laminated structure piezoelectric power generation units is one or more, the laminated structure piezoelectric power generation units are arranged on a substrate in a transverse, longitudinal or array form, and the plurality of laminated structure piezoelectric power generation units are electrically connected in series or in parallel, as shown in fig. 1, the laminated structure piezoelectric power generation units are arranged on the substrate in a flexible piezoelectric energy collector structural schematic diagram; as shown in fig. 10, the structure of the flexible piezoelectric energy collector is schematically shown, wherein two piezoelectric generating units with laminated structures are arranged on a substrate in a transverse manner in parallel.
Fig. 10 shows a flexible piezoelectric energy collector of negative poisson's ratio macroscopic graphene, in which two piezoelectric power generation units with laminated structures are transversely arranged on a substrate and electrically connected in series.
The negative poisson ratio macroscopic graphene flexible piezoelectric energy collector with two piezoelectric power generation units in the laminated structure in fig. 10 can give a higher open-circuit voltage, and the value of the open-circuit voltage is about 2 times that of the piezoelectric energy collector with one piezoelectric power generation unit in the laminated structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The flexible piezoelectric energy collector based on the negative Poisson ratio macroscopic graphene film is characterized by comprising a flexible substrate (1) and a laminated structure piezoelectric power generation unit fixed on the surface of the flexible substrate (1), wherein a lead (4) is arranged on the surface of the laminated structure piezoelectric power generation unit, the lead (4) is used for leading out charges/voltages generated after the flexible piezoelectric energy collector is stretched and deformed, and the laminated structure piezoelectric power generation unit comprises a negative Poisson ratio macroscopic graphene film (3) and a flexible piezoelectric film (2).
2. The flexible piezoelectric energy collector based on the negative poisson's ratio macroscopic graphene film as claimed in claim 1, wherein in the piezoelectric power generation unit with the laminated structure, the negative poisson's ratio macroscopic graphene film (3) is fixed on the upper side and the lower side of the flexible piezoelectric film (2).
3. The flexible piezoelectric energy harvester based on negative poisson's ratio macroscopic graphene membrane according to claim 1, characterized in that the preparation method of the negative poisson's ratio macroscopic graphene membrane (3) comprises the following steps:
step 1, preparing graphene oxide by adopting an improved oxidation method or an electrochemical stripping method;
step 2, dispersing graphene oxide by using ultrapure water to form graphene oxide dispersion liquid with the solid content of 2-4%, and preparing the graphene oxide dispersion liquid into a graphene oxide film by adopting a tape casting method;
and 3, placing the graphene oxide membrane obtained in the step 2 in a high-temperature graphitization furnace, and carrying out high-temperature treatment at 3000 ℃ under the protection of inert atmosphere to obtain the negative Poisson ratio macroscopic graphene membrane (3).
4. The flexible piezoelectric energy collector based on the negative poisson's ratio macroscopic graphene film according to claim 2, characterized in that the negative poisson's ratio macroscopic graphene film (3) has a thickness of 5-200 μm, a poisson's ratio of-0.5-0, a young's modulus of 0.01-20GPa, an electrical conductivity of not less than 104S/m。
5. The flexible piezoelectric energy harvester based on negative poisson's ratio macroscopic graphene film according to claim 2, characterized in that the piezoelectric film (2) is made of at least one of PVDF and its copolymer or piezoelectric composite material with a thickness of 10-100 μm.
6. The flexible piezoelectric energy harvester based on negative poisson's ratio macroscopic graphene film according to claim 1, characterized in that the flexible substrate (1) is made of at least one of PET, polyimide, epoxy, aluminum, copper and stainless steel with a thickness of 50-500 μ ι η.
7. The flexible piezoelectric energy harvester based on negative poisson's ratio macroscopic graphene film according to claim 1, wherein the number of the laminated structure piezoelectric power generation units is one or more, the laminated structure piezoelectric power generation units are arranged on the substrate in a transverse, longitudinal or array mode, and the electrical connection mode among the laminated structure piezoelectric power generation units is series connection or parallel connection.
8. The flexible piezoelectric energy collector based on the negative poisson's ratio macroscopic graphene film according to claim 1, wherein when the flexible piezoelectric energy collector is in operation, strain coupling exists between the piezoelectric film (2) and the negative poisson's ratio macroscopic graphene film (3) in the piezoelectric power generation unit with the laminated structure, so that the piezoelectric film (2) is stretched in two perpendicular directions in the plane of the piezoelectric film.
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| CN112532106A (en) * | 2020-10-30 | 2021-03-19 | 武汉汉烯科技有限公司 | Flexible piezoelectric energy collector based on macroscopic graphene film negative Poisson ratio structure |
| CN112600461A (en) * | 2020-12-04 | 2021-04-02 | 武汉柏禾智科技有限公司 | Piezoelectric energy harvester |
| CN113630040A (en) * | 2021-08-11 | 2021-11-09 | 武汉理工大学 | Flexible piezoelectric energy collection system based on graphene assembly film |
| CN113904589A (en) * | 2021-09-13 | 2022-01-07 | 广东墨睿科技有限公司 | Preparation method and application of piezoelectric film substrate-enhanced graphene power generation device |
| US20220009199A1 (en) * | 2020-06-18 | 2022-01-13 | Swift Textile Metalizing LLC | Auxetic fabric reinforced elastomers |
| CN114221577A (en) * | 2021-12-14 | 2022-03-22 | 哈尔滨工业大学 | Nonlinear piezoelectric energy collector based on elastic cable and negative Poisson ratio structure |
| CN115259145A (en) * | 2022-07-29 | 2022-11-01 | 武汉汉烯科技有限公司 | Preparation method of high-conductivity macroscopic graphene assembly film close to lower limit of Poisson ratio |
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| 强亮生，赵久蓬，杨玉林: "《人工超材料复合结构中的光的传输与调控》", 哈尔滨：哈尔滨工业大学出版社, pages: 157 - 20 * |
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| US11905651B2 (en) * | 2020-06-18 | 2024-02-20 | Swift Textile Metalizing LLC | Auxetic fabric reinforced elastomers |
| CN112532106A (en) * | 2020-10-30 | 2021-03-19 | 武汉汉烯科技有限公司 | Flexible piezoelectric energy collector based on macroscopic graphene film negative Poisson ratio structure |
| CN112600461A (en) * | 2020-12-04 | 2021-04-02 | 武汉柏禾智科技有限公司 | Piezoelectric energy harvester |
| CN113630040A (en) * | 2021-08-11 | 2021-11-09 | 武汉理工大学 | Flexible piezoelectric energy collection system based on graphene assembly film |
| CN113904589A (en) * | 2021-09-13 | 2022-01-07 | 广东墨睿科技有限公司 | Preparation method and application of piezoelectric film substrate-enhanced graphene power generation device |
| CN114221577A (en) * | 2021-12-14 | 2022-03-22 | 哈尔滨工业大学 | Nonlinear piezoelectric energy collector based on elastic cable and negative Poisson ratio structure |
| CN115259145A (en) * | 2022-07-29 | 2022-11-01 | 武汉汉烯科技有限公司 | Preparation method of high-conductivity macroscopic graphene assembly film close to lower limit of Poisson ratio |
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