CN113725351B - Polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and preparation method thereof - Google Patents
Polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 95
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 15
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- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
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- -1 ester compounds Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
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- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/092—Forming composite materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
Abstract
The invention discloses a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof, comprising the following steps: s1: firstly, preparing an organic solvent, and then dispersing organic fluorine modified flower-like graphene in the organic solvent to prepare a mixed solution I; s2: adding PVDF into the mixed solution I in the step S1, and uniformly mixing to prepare a PVDF/flower-like graphene mixed solution II; s3: and (3) coating and drying the mixed solution II in the step S2 to obtain the PVDF/flower-shaped graphene composite piezoelectric film, wherein flower-shaped graphene is used as a beta crystal form nucleating agent, so that the beta crystal form content of the PVDF is improved, and the piezoelectric performance of the PVDF is improved. According to the PVDF/flower-like graphene composite piezoelectric film, after the flower-like graphene is subjected to organic fluorine chemical modification, the dispersibility of the flower-like graphene in a PVDF matrix is improved, and the charge accumulation between the flower-like graphene and the interface of the PVDF matrix is increased, so that the piezoelectric performance of the PVDF is greatly improved.
Description
Technical Field
The invention relates to the field of piezoelectric films and preparation methods thereof, in particular to a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof.
Background
Polyvinylidene fluoride (PVDF) is a semi-crystalline, polycrystalline polymer that can form five crystalline forms under certain conditions: alpha, beta, gamma, delta and epsilon crystal forms. The polycrystalline structure of the PVDF endows PVDF with good physical and chemical properties, high mechanical properties, impact resistance, high insulativity and good piezoelectric ferroelectric properties. The alpha crystal form is the most common, and has good mechanical properties; the beta crystal form has excellent piezoelectric property because of the unique structure of the beta crystal form with polarity, and is widely applied to sensors, nano generators and the like; the gamma-crystalline form chain is similar to the beta-crystalline form in configuration and has a certain polarity, and is generally formed by high-temperature melting crystallization.
The beta crystal form content in PVDF material can be increased by adding specific nucleating agent or changing the material heat treatment process, thereby achieving the purpose of improving the piezoelectric performance. For example, the nucleating agent lithium chloride is added into PVDF, when the dosage reaches a certain value, the content of beta crystal form reaches a peak value, and the material shows extremely high piezoelectric response sensitivity. The research also finds that the nano montmorillonite, silver nanowire, carbon nanotube and other nano materials are used as nucleating agents, which is more beneficial to promoting the conversion from alpha crystal form to beta crystal form of PVDF. The dielectric constant and dielectric loss of PVDF increased with increasing nano montmorillonite content, and the piezoelectric coefficient reached a maximum value (5.8X10-12C/N) when the nano montmorillonite content reached 2.0 wt%. The influence of annealing temperature and annealing time on PVDF crystallization is examined by a melting method, and the cooling mode is found to be capable of regulating and controlling the contents of beta phase and gamma phase in PVDF, so that the cooling rate is high, more beta phases are generated, and the formation of gamma phase is facilitated if the cooling rate is low.
The flower-like graphene has a unique three-dimensional porous structure, has large specific surface area, high conductivity and good stability, and is an ideal nucleating agent for the beta crystal form of PVDF. After the flower-like graphene is chemically modified by organic fluorine, the dispersibility of the flower-like graphene in a PVDF matrix is improved, and the surface fluorine groups interact with PVDF high polymer chains, so that the straightening of the PVDF high polymer chains can be promoted, the content of beta crystal forms is improved, and meanwhile, the charge accumulation between the flower-like graphene and the interface of the PVDF matrix is increased, so that the piezoelectric performance of the PVDF is improved.
Disclosure of Invention
The invention aims to provide a polyvinylidene fluoride flower-like graphene composite piezoelectric film and a preparation method thereof, so as to solve the problems in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a polyvinylidene fluoride flower-like graphene composite piezoelectric film and a preparation method thereof comprise the following steps:
s1: firstly, preparing an organic solvent, and then dispersing organic fluorine modified flower-like graphene in the organic solvent to prepare a mixed solution I;
S2: adding PVDF into the mixed solution I in the step S1, and uniformly mixing to prepare a PVDF/flower-like graphene mixed solution II;
s3: and (3) coating and drying the mixed solution II in the step (S2) to obtain the PVDF/flower-shaped graphene composite piezoelectric film.
Preferably, in the step S1, the graphene is dispersed by ultrasonic waves, and the dispersion time of the graphene is 1h, so as to prepare the organic fluorine modified flower-like graphene dispersion liquid.
Preferably, in the step S2, the PVDF is mixed by magnetic stirring, and the mixing time of the PVDF is 8-15 hours, so as to obtain the PVDF/graphene flower-like mixed solution.
Preferably, in the step S3, the second mixed solution is coated under the conditions of a laboratory temperature of 5-25 ℃ and an air relative humidity of 20-35%, and is dried under a vacuum condition at 90-135 ℃ for 8-18 hours to prepare the PVDF/flower-like graphene composite piezoelectric film.
Preferably, in the step S1, the organic solvent is one or more of N, N-dimethylformamide, acetone, butanone and a mixed solution thereof, and the volume amount of the organic solvent is 5-20 ml/g based on the mass of PVDF.
Preferably, in the step S1, the preparation method of the organic fluorine modified flower-like graphene includes the following steps: dispersing a certain amount of flower-like graphene in a solvent, adding a certain amount of diphenylmethane diisocyanate, reacting for 2-6 hours at 35-80 ℃, adding a certain amount of trifluoroacetic acid, continuously reacting for 3-6 hours, and separating to obtain the organic fluorine modified flower-like graphene.
Preferably, the feeding mass ratio of the flower-like graphene, the diphenylmethane diisocyanate and the trifluoroacetic acid is 100:5-10:5-15, wherein the volume dosage of the solvent is 50-200 ml/g based on the mass of the flower-like graphene.
Preferably, the solvent is selected from one of the following: aromatic hydrocarbons, ester compounds, halogenated hydrocarbons and ketone compounds; preferably one of the following: xylene, toluene, ethyl acetate, butyl acetate, methylene chloride, chloroform, acetone, butanone, cyclohexanone.
Preferably, the piezoelectric composite film is prepared by using the preparation method of the piezoelectric composite film according to any one of claims 1 to 5, and the piezoelectric composite film comprises: the organic fluorine modified flower-like graphene comprises PVDF and organic fluorine modified flower-like graphene, wherein the mass ratio of PVDF to organic fluorine modified flower-like graphene is 100:0.1-5.
Preferably, the piezoelectric composite film is formed by arranging at least 2-13 piezoelectric layers in parallel.
The invention has the technical effects and advantages that:
(1) According to the PVDF/flower-like graphene composite piezoelectric film, flower-like graphene is used as a beta crystal form nucleating agent, so that the beta crystal form content of PVDF is improved, the piezoelectric performance of PVDF is improved, and after the flower-like graphene is subjected to organic fluorine chemical modification, the dispersibility of the flower-like graphene in a PVDF matrix is improved, and the charge accumulation between the flower-like graphene and a PVDF matrix interface is increased, so that the piezoelectric performance of PVDF is improved;
(2) The preparation method of the organic fluorine modified flower-like graphene adopts a one-pot reaction, so that the synthetic process route is simplified, the reaction cost is reduced, the energy consumption and the pollutant emission are reduced, the piezoelectric film is made to be more environment-friendly and energy-saving, and the nature is protected;
(3) The PVDF/flower-like graphene composite piezoelectric film has the advantages of simple preparation process, easy recovery of solvent, convenient industrialized popularization and higher profit.
Drawings
Fig. 1 is an infrared spectrogram of the organic fluorine modified flower-like graphene of the present invention.
Fig. 2 is one of the scanning electron microscope images of the organic fluorine modified flower-like graphene of the present invention.
FIG. 3 is one of the X-ray photoelectron spectra of the present invention.
FIG. 4 is a second X-ray photoelectron spectrum of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof.
Example 1
Adding 1g flower-like graphene into 100ml chloroform, performing ultrasonic dispersion for 30min, transferring into a dry four-mouth bottle provided with a magnetic stirring device, a thermometer, a reflux condenser and a dropping funnel, adding 0.1 g diphenylmethane diisocyanate, reacting at 60 ℃ for 4h, adding 0.15 g trifluoroacetic acid for continuous reaction for 4h, filtering the suspension obtained by the reaction, repeatedly washing with methanol, and drying in an oven at 80 ℃ for 24h to obtain the organic fluorine-modified flower-like graphene with the yield of 97.8%, wherein the infrared spectrum, the scanning electron microscope and the X-ray photoelectron energy spectrum are shown as the accompanying figures 1,2,3 and 4.
Example 2
The preparation procedure of the organic fluorine modified flower-like graphene was the same as in example 1. The feeding mass ratio of the flower-like graphene, the diphenylmethane diisocyanate and the trifluoroacetic acid is 100:5: and 5, preparing the PVDF/flower-like graphene composite piezoelectric film by using toluene as an organic solvent, wherein the volume dosage of toluene is 50 ml/g based on the mass of flower-like graphene, the reaction temperature is 80 ℃, the reaction time is 5 hours, and the yield is 92.6%.
Example 3
The preparation procedure of the organic fluorine modified flower-like graphene was the same as in example 1. The feeding mass ratio of the flower-like graphene, the diphenylmethane diisocyanate and the trifluoroacetic acid is 100:7:9, preparing PVDF/flower-like graphene composite piezoelectric film, wherein the organic solvent is ethyl acetate, the volume consumption of the ethyl acetate is 200 ml/g based on the mass of the flower-like graphene, the reaction temperature is 35 ℃, the reaction time is 12h, and the yield is 92.4%.
Example 4
The preparation procedure of the organic fluorine modified flower-like graphene was the same as in example 1. Adding 0.01 g organic fluorine modified flower-like graphene into 50ml DMF, and performing ultrasonic dispersion for 1h to prepare an organic fluorine modified flower-like graphene dispersion liquid. And then adding 10g PVDF into the organic fluorine modified flower-like graphene dispersion liquid, and magnetically stirring for 8 hours to obtain the PVDF/flower-like graphene mixed liquid. The mixed solution is coated under the conditions that the laboratory temperature is 25 ℃ and the air relative humidity is 35%, and then is dried in vacuum at 135 ℃ for 8 hours, so that the PVDF/flower-shaped graphene composite piezoelectric film is prepared.
Example 5
The preparation procedure of the organic fluorine modified flower-like graphene was the same as in example 1. The preparation operation of the PVDF/flower-like graphene composite piezoelectric film is the same as that of example 4. The charging mass ratio of PVDF to organic fluorine modified flower-like graphene is 100:5, the organic solvent is a mixed solvent of DMF and butanone, and the volume ratio of DMF to butanone is 4:1, the volume consumption of the mixed solvent is 20 ml/g based on the mass of PVDF, the magnetic stirring is carried out for 12 hours, and the coating condition is as follows: the temperature is 5 ℃, the relative humidity of air is 30 percent, and the drying conditions are as follows: 120. and (3) performing vacuum drying treatment for 12 hours at the temperature to prepare the PVDF/flower-like graphene composite piezoelectric film.
Example 6
The preparation procedure of the organic fluorine modified flower-like graphene was the same as in example 1. The preparation operation of the PVDF/flower-like graphene composite piezoelectric film is the same as that of example 4. The charging mass ratio of PVDF to organic fluorine modified flower-like graphene is 100:1, the organic solvent is a mixed solvent of DMF and butanone, and the volume ratio of DMF to acetone is 3:1, the volume consumption of the mixed solvent is 10 ml/g based on the mass of PVDF, the magnetic stirring is carried out for 15h, and the coating condition is as follows: the temperature is 15 ℃, the relative humidity of air is 20 percent, and the drying conditions are as follows: 90. and (3) performing vacuum drying treatment at the temperature of 18 hours to prepare the PVDF/flower-like graphene composite piezoelectric film.
Comparative example 1
As a comparison, the organic fluorine modified flower-like graphene in the composition formula of the PVDF composite piezoelectric film of example 4 is replaced by carbon nanotubes with the same mass fraction, and the performance test results of the obtained PVDF/carbon nanotube composite piezoelectric film are compared as follows:
PVDF/carbon nanotube composite piezoelectric film: the charging mass ratio of PVDF to carbon nano tube is 100:1, using DMF as an organic solvent, wherein the volume dosage of DMF is 5ml/g based on the mass of PVDF, and the preparation process is the same as that of example 4; PVDF/flower-like graphene composite piezoelectric film: the formulation and preparation process were as in example 4.
Compared with carbon nanotubes, the organic fluorine modified flower-like graphene used by the invention can effectively improve the piezoelectric performance of the PVDF composite piezoelectric film, and the mechanical property modification effect of the organic fluorine modified flower-like graphene on the PVDF composite piezoelectric film is better than that of the carbon nanotubes. After the PVDF/flower-like graphene composite piezoelectric film is chemically modified by organic fluorine, the dispersibility of the flower-like graphene in a PVDF matrix is improved, and the surface fluorine groups interact with PVDF high polymer chains, so that the straightening of the PVDF molecular chains can be promoted, the beta crystal form content is improved, and meanwhile, the charge accumulation between the flower-like graphene and the interface of the PVDF matrix is increased, so that the piezoelectric performance of the PVDF is improved.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (9)
1. The preparation method of the polyvinylidene fluoride flower-shaped graphene composite piezoelectric film is characterized by comprising the following steps of:
s1: firstly, preparing an organic solvent, and then dispersing organic fluorine modified flower-like graphene in the organic solvent to prepare a mixed solution I;
in the step S1, the preparation method of the organic fluorine modified flower-like graphene includes the following steps: dispersing a certain amount of flower-like graphene in a solvent, adding a certain amount of diphenylmethane diisocyanate, reacting for 2-6 hours at 35-80 ℃, adding a certain amount of trifluoroacetic acid, continuously reacting for 3-6 hours, and separating to obtain organic fluorine-modified flower-like graphene;
S2: adding PVDF into the mixed solution I in the step S1, and uniformly mixing to prepare a PVDF/flower-like graphene mixed solution II;
s3: and (3) coating and drying the mixed solution II in the step (S2) to obtain the PVDF/flower-shaped graphene composite piezoelectric film.
2. The method for preparing the polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in the step S1, graphene is dispersed by ultrasonic waves, and the dispersion time of the graphene is 1h, so as to prepare an organic fluorine-modified flower-like graphene dispersion liquid.
3. The method for preparing the polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in the step S2, PVDF is mixed by magnetic stirring, and the mixing time of PVDF is 8-15h, so as to obtain a PVDF/flower-like graphene mixed solution.
4. The method for preparing a polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in the step S3, the second mixed solution is coated under the conditions of a laboratory temperature of 5-25 ℃ and an air relative humidity of 20-35%, and is dried under a vacuum condition at 90-135 ℃ for 8-18 hours to prepare the PVDF/flower-like graphene composite piezoelectric film.
5. The method for preparing a polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in the step S1, the organic solvent is one or more of N, N-dimethylformamide, acetone, butanone and a mixed solution thereof, and the volume amount of the organic solvent is 5-20 ml/g based on the mass of PVDF.
6. The preparation method of the polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1 is characterized in that the feeding mass ratio of flower-like graphene, diphenylmethane diisocyanate and trifluoroacetic acid is 100:5-10:5-15, wherein the volume dosage of the solvent is 50-200 ml/g based on the mass of the flower-like graphene.
7. The preparation method of the polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 6, wherein the solvent for dispersing flower-like graphene in preparing organic fluorine-modified flower-like graphene is selected from one of the following: xylene, toluene, ethyl acetate, butyl acetate, methylene chloride, chloroform, acetone, butanone, cyclohexanone.
8. A polyvinylidene fluoride flower-like graphene composite piezoelectric film, characterized in that the piezoelectric composite film is prepared by the preparation method of the piezoelectric composite film according to any one of claims 1 to 7, and the piezoelectric composite film comprises: the organic fluorine modified flower-like graphene comprises PVDF and organic fluorine modified flower-like graphene, wherein the mass ratio of PVDF to organic fluorine modified flower-like graphene is 100:0.1-5.
9. The polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 8, wherein the piezoelectric composite film is formed by arranging at least 2-13 piezoelectric layers in parallel.
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