CN113725351A - Polyvinylidene fluoride flower-like graphene composite piezoelectric film and preparation method thereof - Google Patents
Polyvinylidene fluoride flower-like graphene composite piezoelectric film and preparation method thereof Download PDFInfo
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- 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
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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
- H10N30/852—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, wherein the preparation method comprises the following steps: s1: 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 obtained in the step S1, and uniformly mixing to obtain a PVDF/flower-like graphene mixed solution II; s3: and (5) coating and drying the mixed solution II obtained in the step (S2) to obtain the PVDF/flower-shaped graphene composite piezoelectric film, wherein the flower-shaped graphene is used as a beta crystal form nucleating agent, so that the beta crystal form content of the PVDF is increased, and the piezoelectric performance of the PVDF is improved. According to the PVDF/flower-like graphene composite piezoelectric film, the flower-like graphene is chemically modified by organic fluorine, so that the dispersibility of the flower-like graphene in a PVDF matrix is improved, the charge accumulation between the interface of the flower-like graphene and the PVDF matrix is increased, and the piezoelectric property 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, polymorphic polymer that forms five crystalline forms under certain conditions: alpha, beta, gamma, delta and epsilon crystal forms. The polycrystalline structure of the composite material endows PVDF with good physical and chemical properties, high mechanical properties, impact resistance, high insulating properties 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 performance due to the polarity of the unique structure, and is widely applied to sensors, nano generators and the like; the gamma crystal chain is similar to the beta crystal chain in structure and has certain polarity, and is generally formed in high-temperature melting crystallization.
The content of beta crystal form in the PVDF material can be improved by adding a specific nucleating agent or changing the heat treatment process of the material, thereby achieving the purpose of improving the piezoelectric property of the PVDF material. For example, a 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 presents extremely high piezoelectric response sensitivity. Researches also find that nano materials such as nano montmorillonite, silver nanowires and carbon nanotubes are used as nucleating agents, so that the transformation from the alpha crystal form to the beta crystal form of PVDF is promoted. The dielectric constant and dielectric loss of PVDF increase with the content of nano montmorillonite, and when the content of nano montmorillonite reaches 2.0 wt%, the piezoelectric coefficient reaches the maximum value (5.8 x 10-12C/N). 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 the content of beta phase and gamma phase in PVDF, the cooling rate is high, more beta phases are generated, and the gamma phase is favorably formed if the cooling rate is low.
The flower-like graphene has a unique three-dimensional porous structure, is large in specific surface area, high in conductivity and good in stability, and is an ideal nucleating agent for a beta crystal form of PVDF. After the flower-shaped graphene is modified by the organic fluorine chemistry, the dispersibility of the flower-shaped graphene in a PVDF matrix is improved, the interaction between the surface fluorine groups and the PVDF polymer chain can be generated, the straightening of the PVDF polymer chain can be promoted, the content of beta crystal form is improved, and the charge accumulation between the interface of the flower-shaped graphene and the PVDF matrix is increased, so that the piezoelectric property of the PVDF is improved.
Disclosure of Invention
The invention aims to provide a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof, and aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof comprise the following steps:
s1: 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 obtained in the step S1, and uniformly mixing to obtain a PVDF/flower-like graphene mixed solution II;
s3: and (5) coating and drying the mixed solution II obtained in the step (S2) to obtain the PVDF/flower-like graphene composite piezoelectric film.
Preferably, in 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 mixture is 8-15h, so as to obtain a PVDF/flower-like graphene mixed solution.
Preferably, in the step S3, the mixed solution two is coated at a laboratory temperature of 5-25 ℃ and a relative air humidity of 20-35%, and dried at 90-135 ℃ under vacuum for 8-18h 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 mixture thereof, and the volume usage amount of the organic solvent is 5 to 20 ml/g based on the mass of PVDF.
Preferably, in step S1, the method for preparing the organofluorine-modified flower-like graphene includes the following steps: dispersing a certain amount of flower-shaped graphene in a solvent, adding a certain amount of diphenylmethane diisocyanate, reacting for 2-6h at 35-80 ℃, adding a certain amount of trifluoroacetic acid, continuing to react for 3-6h, and separating to obtain the organic fluorine modified flower-shaped graphene.
Preferably, the feeding mass ratio of the flower-like graphene to the diphenylmethane diisocyanate to 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, ketone compounds; preferably one of the following: xylene, toluene, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, cyclohexanone.
Preferably, the piezoelectric composite film is prepared by the method for preparing a piezoelectric composite film according to any one of claims 1 to 5, and the piezoelectric composite film includes: the composite material comprises PVDF and organic fluorine modified flower-like graphene, wherein the mass ratio of the PVDF to the organic fluorine modified flower-like graphene is 100: 0.1-5.
Preferably, the piezoelectric composite films are arranged in parallel by at least 2-13 layers of piezoelectric layers.
The invention has the technical effects and advantages that:
(1) the PVDF/flower-like graphene composite piezoelectric film takes flower-like graphene as a beta crystal form nucleating agent, improves the beta crystal form content of PVDF, thereby improving the piezoelectric property of PVDF, and the flower-like graphene is chemically modified by organic fluorine, so that the dispersibility of the flower-like graphene in a PVDF matrix is improved, the charge accumulation between the interface of the flower-like graphene and the PVDF matrix is increased, and the piezoelectric property of PVDF is improved;
(2) the preparation method of the organic fluorine modified flower-like graphene adopts a one-pot reaction, so that the synthesis process route is simplified, the reaction cost is reduced, the energy consumption and the pollutant emission are reduced, the piezoelectric film is more environment-friendly and energy-saving to manufacture, and the nature is protected;
(3) the PVDF/flower-like graphene composite piezoelectric film disclosed by the invention is simple in preparation process, easy in solvent recovery, convenient for industrial popularization and high in profit.
Drawings
FIG. 1 is an infrared spectrum of the organic fluorine modified flower-like graphene.
FIG. 2 is a scanning electron microscope image of the organic fluorine modified flower-like graphene according to 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 technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film and a preparation method thereof.
Example 1
Adding 1 g of flower-shaped graphene into 100ml of trichloromethane, performing ultrasonic dispersion for 30min, transferring the flower-shaped graphene into a dry four-mouth bottle provided with a magnetic stirring device, a thermometer, a reflux condenser tube and a dropping funnel, adding 0.1 g of diphenylmethane diisocyanate, reacting for 4h at 60 ℃, adding 0.15 g of trifluoroacetic acid, continuing to react for 4h, filtering the obtained suspension, repeatedly washing with methanol, and drying in an oven at 80 ℃ for 24h to obtain the organic fluorine modified flower-shaped graphene, wherein the yield is 97.8%, and the infrared spectrum, the scanning electron microscope image and the X-ray photoelectron energy spectrum are shown in attached figures 1, 2, 3 and 4.
Example 2
The procedure for preparing the organofluorine-modified flower-like graphene was the same as in example 1. Feeding mass ratio of flower-like graphene to diphenylmethane diisocyanate to trifluoroacetic acid is 100: 5: 5, taking toluene as an organic solvent, wherein the volume consumption of the toluene is 50 ml/g based on the mass of the flower-shaped graphene, the reaction temperature is 80 ℃, the reaction time is 5 hours, the yield is 92.6%, and preparing the PVDF/flower-shaped graphene composite piezoelectric film.
Example 3
The procedure for preparing the organofluorine-modified flower-like graphene was the same as in example 1. Feeding mass ratio of flower-like graphene to diphenylmethane diisocyanate to trifluoroacetic acid is 100: 7: and 9, preparing the 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 12 hours, and the yield is 92.4%.
Example 4
The procedure for preparing the organofluorine-modified flower-like graphene was the same as in example 1. Adding 0.01 g of organic fluorine modified flower-like graphene into 50 ml of DMF, and ultrasonically dispersing for 1h to prepare organic fluorine modified flower-like graphene dispersion liquid. And then adding 10 g of PVDF into the organic fluorine modified flower-like graphene dispersion liquid, and stirring for 8 hours by using magnetic force to obtain a PVDF/flower-like graphene mixed liquid. The mixed solution is subjected to film coating under the conditions that the laboratory temperature is 25 ℃ and the air relative humidity is 35%, and then is subjected to vacuum drying treatment at 135 ℃ for 8 hours to prepare the PVDF/flower-like graphene composite piezoelectric film.
Example 5
The procedure for preparing the organofluorine-modified flower-like graphene was the same as in example 1. The preparation operation of the PVDF/flower-like graphene composite piezoelectric film was the same as in example 4. The feeding 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 dosage 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 film coating conditions are as follows: the temperature is 5 ℃, the relative humidity of air is 30%, and the drying conditions are as follows: and (3) drying at 120 ℃ for 12h in vacuum to prepare the PVDF/flower-like graphene composite piezoelectric film.
Example 6
The procedure for preparing the organofluorine-modified flower-like graphene was the same as in example 1. The preparation operation of the PVDF/flower-like graphene composite piezoelectric film was the same as in example 4. The feeding 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 usage of the mixed solvent is 10 ml/g based on the mass of PVDF, the magnetic stirring is carried out for 15 hours, and the film coating conditions are as follows: the temperature is 15 ℃, the relative humidity of air is 20%, and the drying conditions are as follows: and (3) drying for 18h at 90 ℃ in vacuum to prepare the PVDF/flower-like graphene composite piezoelectric film.
Comparative example 1
For comparison, the organic fluorine modified flower-like graphene in the formulation of the PVDF composite piezoelectric film in example 4 is replaced by the 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 feeding mass ratio of PVDF to the carbon nano tubes is 100: 1, the organic solvent is DMF, the volume consumption of the DMF is 5ml/g based on the mass of the PVDF, and the preparation process is the same as that of the embodiment 4; PVDF/flower-like graphene composite piezoelectric film: the composition formula and the preparation process are the same as those in example 4.
As can be seen from the piezoelectric coefficient, the dielectric constant and the dielectric loss, compared with the carbon nano tube, the organic fluorine modified flower-shaped graphene can effectively improve the piezoelectric property of the PVDF composite piezoelectric film, and the mechanical property modification effect of the organic fluorine modified flower-shaped graphene on the PVDF composite piezoelectric film is better than that of the carbon nano tube. According to the PVDF/flower-like graphene composite piezoelectric film prepared by the invention, after the flower-like graphene is chemically modified by organic fluorine, the dispersibility of the flower-like graphene in a PVDF matrix is improved, the interaction between the surface fluorine group and the PVDF polymer chain is generated, the straightening of the PVDF molecular chain can be promoted, the content of a beta crystal form is improved, and the charge accumulation between the interface of the flower-like graphene and the PVDF matrix is increased, so that the piezoelectric property of the PVDF is improved.
Finally, it should be noted that: 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 or portions thereof without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a polyvinylidene fluoride flower-shaped graphene composite piezoelectric film is characterized by comprising the following steps:
s1: 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 obtained in the step S1, and uniformly mixing to obtain a PVDF/flower-like graphene mixed solution II;
s3: and (5) coating and drying the mixed solution II obtained in the step (S2) to obtain the PVDF/flower-like graphene composite piezoelectric film.
2. The method of claim 1, wherein in step S1, graphene is dispersed by ultrasonic waves, and the dispersion time of graphene is 1h, so as to prepare an organic fluorine modified flower-like graphene dispersion solution.
3. A method for preparing a 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 of claim 1, wherein in step S3, the mixed solution ii is coated at a laboratory temperature of 5-25 ℃ and a relative air humidity of 20-35%, and dried at 90-135 ℃ under vacuum for 8-18h to prepare the PVDF/graphene composite piezoelectric film.
5. A method for preparing a polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in step S1, the organic solvent is one or more of N, N-dimethylformamide, acetone, butanone and a mixture thereof, and the volume usage amount of the organic solvent is 5-20 ml/g based on the mass of PVDF.
6. The method for preparing a polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein in the step S1, the method for preparing the organic fluorine modified flower-like graphene comprises the following steps: dispersing a certain amount of flower-shaped graphene in a solvent, adding a certain amount of diphenylmethane diisocyanate, reacting for 2-6h at 35-80 ℃, adding a certain amount of trifluoroacetic acid, continuing to react for 3-6h, and separating to obtain the organic fluorine modified flower-shaped graphene.
7. The preparation method of polyvinylidene fluoride flower-shaped graphene composite piezoelectric film according to claim 6, wherein the feeding mass ratio of flower-shaped 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.
8. The method for preparing a polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 6, wherein the solvent is selected from one of the following solvents: aromatic hydrocarbons, ester compounds, halogenated hydrocarbons, ketone compounds; preferably one of the following: xylene, toluene, ethyl acetate, butyl acetate, dichloromethane, chloroform, acetone, butanone, cyclohexanone.
9. The polyvinylidene fluoride flower-like graphene composite piezoelectric film according to claim 1, wherein the piezoelectric composite film is prepared by the method for preparing a piezoelectric composite film according to any one of claims 1 to 5, and the piezoelectric composite film comprises: the composite material comprises PVDF and organic fluorine modified flower-like graphene, wherein the mass ratio of the PVDF to the organic fluorine modified flower-like graphene is 100: 0.1-5.
10. A polyvinylidene fluoride flower-like graphene composite piezoelectric film and method of making the same as claimed in claim 9, wherein the piezoelectric composite film is formed by at least 2-13 layers of piezoelectric layers in parallel.
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