CN112480576A - Preparation method of PVDF (polyvinylidene fluoride) film with high piezoelectric property - Google Patents
Preparation method of PVDF (polyvinylidene fluoride) film with high piezoelectric property Download PDFInfo
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- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention provides a preparation method of a PVDF film with high piezoelectric performance, belonging to the technical field of film material preparation. The principle is that PVDF is uniformly distributed in a lamellar structure of nano materials such as graphene and the like to form a certain lamellar network, so that the arrangement of the PVDF is more compact, and meanwhile, the film after proportioning, mixing, heating, tape casting and drying can be polarized under low voltage, so that internal molecules are directionally arranged by virtue of the lamellar network structure, a uniform beta-phase PVDF film is finally formed, and the piezoelectric performance of the PVDF film is also improved.
Description
Technical Field
The invention belongs to the technical field of thin film material preparation, and particularly relates to a preparation method of a functional thin film with high piezoelectric property.
Background
Polyvinylidene fluoride (PVDF for short) has excellent piezoelectric, ferroelectric and thermoelectric properties, and is widely used for the preparation of novel memories, capacitors, piezoelectric and thermoelectric converters. The PVDF film can be prepared by two methods of melt extrusion biaxial stretching and solution casting. The PVDF film prepared by melt extrusion biaxial stretching has good compactness and high electric strength, but has large investment and high loss. The PVDF film prepared by the solution casting method has simple process, small investment and easy operation.
Molecular chains with different configurations in the crystal unit cell can be configured into five crystal phases during the crystallization of PVDF: alpha, beta, gamma, delta, lambda phases. The PVDF film prepared by the conventional method mostly has an alpha phase and does not have piezoelectricity, the PVDF film with a polar beta phase has piezoelectricity, and the PVDF film converted from the alpha phase to the beta phase can be converted only by adopting high-temperature treatment or stretching or high-voltage polarization, so that the energy requirement is great, the process is complex, and the yield is not high.
Meanwhile, molecules in the prepared PVDF film are arranged in a disordered manner, so that the piezoelectric performance of the PVDF film is influenced, and therefore, how to improve the ordered arrangement of the molecules in the PVDF film so as to improve the piezoelectric performance of the PVDF film is very important.
Disclosure of Invention
The invention aims to solve the problems that the yield of a beta-phase PVDF film with piezoelectricity is not high, the power consumption is high and the piezoelectricity of a conventional alpha phase is poor in the conventional method, and provides a PVDF film which can replace the conventional method, uniformly distribute PVDF in a network of graphene and other sheet materials and activate the PVDF film into the beta phase under rapid temperature difference or low voltage so that the PVDF film is regularly arranged and has polarity as a whole.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing a functional film with high piezoelectric property comprises the following steps:
(1) mixing PVDF, a lamellar nano material and a solvent according to a certain proportion, and stirring for 5-24 hours at normal temperature (15-25 ℃);
(2) vacuumizing the mixture after stirring, heating the mixture to 40 ℃ and preserving heat for 1h, and heating the mixture to 100-150 ℃ and preserving heat for 1-24 h;
(3) casting to form a film, and drying;
(4) polarization at low voltage.
The invention also provides a preparation method of the functional film with high piezoelectric performance, which comprises the following steps:
(1) mixing PVDF, a lamellar nano material and a solvent according to a certain proportion, and stirring for 5-24 hours at normal temperature (15-25 ℃);
(2) vacuumizing the mixture after stirring, heating the mixture to 40 ℃, preserving the heat for 1 hour, heating the mixture to 100-150 ℃, and preserving the heat for 1-24 hours;
(3) filling inert gas, and rapidly cooling to normal temperature;
(4) casting to form film and drying.
Preferably, the lamellar nano material can be graphene, graphene oxide, redox graphene, C3N4And the like, preferably graphene oxide.
Preferably, the solvent may be one or a combination of several of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, butanone, tetrahydrofuran, and the like, and preferably N-methylpyrrolidone.
Preferably, the PVDF, the lamellar nano material and the solvent are mixed according to a certain proportion, and in the mixed solution, the weight percentage of the PVDF is 30-70 wt%, the weight percentage of the lamellar nano material is 5-10 wt%, and the weight percentage of the solvent is 20-65 wt%.
More preferably, the PVDF, the lamellar nano material and the solvent are proportioned according to a certain proportion, wherein the weight ratio of the PVDF: and (3) graphene oxide: n-methylpyrrolidone = 7: 1: 2.
preferably, the electric field intensity is kept between 10kV/cm and 100kV/cm during polarization.
Preferably, the thickness of the functional film is 1 to 100 μm.
Compared with the prior art, the PVDF film with high piezoelectric performance is essentially formed by wrapping PVDF by the flaky nano material, uniformly distributing the PVDF among the layers of the flaky nano material, and simultaneously enabling the PVDF and the flaky nano material to be combined under the condition of rapid temperature change or lower voltage polarization, so that the PVDF presents regular arrangement by virtue of a network of the flaky nano material, thereby generating a crystal effect, improving the piezoelectric performance of the PVDF film and being applicable to an electrochemical sensor.
The preparation method is simple, has good feasibility, improves the safety, has higher yield and higher piezoelectric performance.
Drawings
FIG. 1 is a schematic diagram of the structural arrangement of an alpha phase PVDF.
FIG. 2 is a schematic diagram of the structural arrangement of a beta-phase PVDF.
Fig. 3 is a molecular formula diagram of PVDF for achieving high piezoelectric performance by means of graphene oxide lamellar structure.
Fig. 4 is a schematic plan view of PVDF for achieving high piezoelectric performance via graphene oxide lamellar structure.
Fig. 5 is a three-dimensional schematic representation of PVDF achieving high piezoelectric performance via graphene oxide lamellar structures.
Detailed Description
In order to illustrate the invention more clearly, the following examples are given without any limitation thereto.
Example 1:
with reference to fig. 1 to 5, the present invention provides a method for preparing a PVDF film with high piezoelectric performance. The method comprises the following steps:
1. weighing 70mg of dry PVDF powder and 10mg of graphene oxide, and dissolving the PVDF powder and the graphene oxide in 20mg of N-methylpyrrolidone;
2. stirring for 5 hours at normal temperature;
3. heating the mixture in a vacuum environment to remove gas in the mixed solution;
4. heating to 40 ℃, and keeping the temperature for 1 h;
5. heating to 120 ℃, preserving heat for 3 hours, and then cooling in vacuum;
6. placing the cleaned glass plate on a film coating machine, and adjusting the slit width and the casting speed of a scraper;
7. putting the prepared PVDF solution into the solution, and preparing a PVDF film by tape casting;
8. then, placing the glass plate coated with the PVDF solution in a drying oven at 60 ℃ for drying for 24 hours;
9. stripping the prepared PVDF film from the glass plate;
10. at normal temperature, the electric field strength is kept at 100kV/cm, and the polarization is carried out.
Example 2:
with reference to fig. 1 to 3, the present invention provides a method for preparing a PVDF film with high piezoelectric performance. The method comprises the following steps:
1. weighing 70mg of dry PVDF powder and 10mg of graphene oxide, and dissolving the PVDF powder and the graphene oxide in 20mg of N-methylpyrrolidone;
2. stirring for 5 hours at normal temperature;
3. heating the mixture in a vacuum environment to remove gas in the mixed solution;
4. heating to 40 ℃, and keeping the temperature for 1 h;
5. then heating to 120 ℃, and preserving heat for 3 hours;
6. then introducing argon to rapidly cool the mixture;
7. placing the cleaned glass plate on a film coating machine, and adjusting the slit width and the casting speed of a scraper;
8. putting the prepared PVDF solution, preparing a PVDF film by tape casting, and enabling polyvinylidene fluoride molecules to be regularly arranged in the graphene by rapid annealing;
9. then, placing the glass plate coated with the PVDF solution in a drying oven at 60 ℃ for drying for 24 hours;
10. and peeling the prepared PVDF film from the glass plate.
FIG. 1 is a conventional alpha-phase PVDF molecular configuration, and FIG. 2 is a beta-phase PVDF molecular configuration.
Fig. 3 is a molecular formula schematic diagram of PVDF realizing high piezoelectric performance by means of graphene oxide lamellar structure, and PVDF molecules are orderly arranged by means of carbon chain lamellar structure of graphene, and after stirring, regular arrangement can be completed by sharp temperature difference change or low voltage polarization.
Fig. 4 is a schematic plan view of PVDF realizing high piezoelectric performance by means of a graphene oxide lamellar structure, PVDF molecules are orderly arranged by means of a carbon chain lamellar structure of graphene, and after stirring, regular arrangement can be completed by rapid temperature difference change or low voltage polarization, and the essence of the arrangement is the same as that of fig. 3.
Fig. 5 is a three-dimensional schematic diagram of PVDF realizing high piezoelectric performance by means of graphene oxide lamellar structure, PVDF molecules are orderly arranged by means of carbon chain lamellar structure of graphene, and after stirring, regular arrangement can be completed by rapid temperature difference change or low voltage polarization, and the essence is the same as that in fig. 3 and 4.
Claims (8)
1. A method for preparing a functional film with high piezoelectric performance is characterized by comprising the following steps:
(1) mixing PVDF, a lamellar nano material and a solvent according to a certain proportion, and stirring for 5-24 hours at normal temperature;
(2) vacuumizing the mixture after stirring, heating the mixture to 40 ℃ and preserving heat for 1h, and heating the mixture to 100-150 ℃ and preserving heat for 1-24 h;
(3) casting to form a film, and drying;
(4) polarization at low voltage.
2. A method for preparing a functional film with high piezoelectric performance is characterized by comprising the following steps:
(1) mixing PVDF, a lamellar nano material and a solvent according to a certain proportion, and stirring for 5-24 hours at normal temperature;
(2) vacuumizing the mixture after stirring, heating the mixture to 40 ℃, preserving the heat for 1 hour, heating the mixture to 100-150 ℃, and preserving the heat for 1-24 hours;
(3) filling inert gas, and rapidly cooling to normal temperature;
(4) casting to form film and drying.
3. The method according to claim 1 or 2,characterized in that the lamellar nano material is graphene, graphene oxide, redox graphene and C3N4Preferably graphene oxide.
4. The method according to claim 1 or 2, wherein the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, butanone and tetrahydrofuran, preferably N-methylpyrrolidone.
5. The method of claim 1 or 2, wherein the PVDF, the lamellar nanomaterial, and the solvent are mixed in a ratio such that the weight percentage of the PVDF, the lamellar nanomaterial, and the solvent in the mixed solution are 30 wt% to 70 wt%, 5 wt% to 10 wt%, and 20 wt% to 65 wt%, respectively.
6. The method according to claim 1 or 2, wherein the PVDF, the graphene oxide and the N-methylpyrrolidone are proportioned according to a certain proportion, wherein the weight ratio of the PVDF: and (3) graphene oxide: n-methylpyrrolidone = 7: 1: 2.
7. the method according to claim 1 or 2, wherein the electric field strength is maintained at 10kV/cm to 100kV/cm at the time of polarization.
8. The method according to claim 1 or 2, wherein the thickness of the functional film obtained is 1 to 100 μm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011313808.7A CN112480576A (en) | 2020-11-20 | 2020-11-20 | Preparation method of PVDF (polyvinylidene fluoride) film with high piezoelectric property |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953537A (en) * | 2022-07-27 | 2022-08-30 | 三三智能科技(日照)有限公司 | PVDF piezoelectric film tape casting process capable of controlling thickness |
| CN115101662A (en) * | 2022-08-24 | 2022-09-23 | 三三智能科技(日照)有限公司 | Piezoelectric film preparation process |
Citations (4)
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| CN103788550A (en) * | 2014-01-08 | 2014-05-14 | 重庆大学 | PVDF-HFP/CB (poly(vinylidene fluoride-hexafluoropropylene)/carbon black) piezoelectric composite film and preparation method thereof |
| WO2016171486A1 (en) * | 2015-04-23 | 2016-10-27 | 전북대학교산학협력단 | Graphene oxide/polymer composite material functionalized with sulfonated poly(ether-ether-ketone) and gas barrier film comprising same |
| CN107955196A (en) * | 2017-11-28 | 2018-04-24 | 电子科技大学 | A kind of PVDF-HFP/GO preparation method of composite film for being used to improve β crystal contents |
| CN108948390A (en) * | 2018-07-24 | 2018-12-07 | 电子科技大学 | A kind of step curtain coating preparation method of PVDF based polymer film |
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2020
- 2020-11-20 CN CN202011313808.7A patent/CN112480576A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103788550A (en) * | 2014-01-08 | 2014-05-14 | 重庆大学 | PVDF-HFP/CB (poly(vinylidene fluoride-hexafluoropropylene)/carbon black) piezoelectric composite film and preparation method thereof |
| WO2016171486A1 (en) * | 2015-04-23 | 2016-10-27 | 전북대학교산학협력단 | Graphene oxide/polymer composite material functionalized with sulfonated poly(ether-ether-ketone) and gas barrier film comprising same |
| CN107955196A (en) * | 2017-11-28 | 2018-04-24 | 电子科技大学 | A kind of PVDF-HFP/GO preparation method of composite film for being used to improve β crystal contents |
| CN108948390A (en) * | 2018-07-24 | 2018-12-07 | 电子科技大学 | A kind of step curtain coating preparation method of PVDF based polymer film |
Non-Patent Citations (2)
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| JUNWOO LEE等: "Polarization behavior of polyvinylidene fluoride films with the addition of reduced grapheme oxide", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114953537A (en) * | 2022-07-27 | 2022-08-30 | 三三智能科技(日照)有限公司 | PVDF piezoelectric film tape casting process capable of controlling thickness |
| CN115101662A (en) * | 2022-08-24 | 2022-09-23 | 三三智能科技(日照)有限公司 | Piezoelectric film preparation process |
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