CN114989464A - PVDF/PMMA composite film and preparation method thereof - Google Patents
PVDF/PMMA composite film and preparation method thereof Download PDFInfo
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- CN114989464A CN114989464A CN202210625387.4A CN202210625387A CN114989464A CN 114989464 A CN114989464 A CN 114989464A CN 202210625387 A CN202210625387 A CN 202210625387A CN 114989464 A CN114989464 A CN 114989464A
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 85
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 85
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 79
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000005266 casting Methods 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000004146 energy storage Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 19
- 238000004804 winding Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 abstract description 6
- 229920006254 polymer film Polymers 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 77
- 239000003990 capacitor Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—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
- 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
- C08J2327/12—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 containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The invention discloses a PVDF/PMMA composite film and a preparation method thereof, wherein the preparation method comprises the steps of mixing PVDF and PMMA materials according to a certain mass ratio to obtain a premix; then feeding the premix into a blending device at a preset speed, heating and stirring the premix through one or more temperature zones to form a molten state, and obtaining a molten blend; pushing the obtained molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film; and finally, cooling the film formed by the convection casting by a cooling roller, and rolling by a rolling roller at a preset rotating speed to finish the preparation of the PVDF/PMMA composite film. The PVDF/PMMA composite film prepared by the preparation method has the characteristics of antiferroelectric ferroelectric hysteresis loop, high energy storage density and high energy storage efficiency. The PVDF/PMMA composite film preparation method provided by the invention can be used for continuously preparing the polymer film at a high speed, and has good industrialization prospect.
Description
Technical Field
The invention relates to the field of polymer energy storage medium materials, in particular to a PVDF/PMMA composite film and a preparation method thereof.
Background
The capacitor belongs to one of three passive components (capacitor, inductor and resistor), wherein the thin film capacitor belongs to one of main capacitor types (thin film capacitor, electrolytic capacitor and ceramic capacitor), and the thin film capacitor has the advantages of high voltage resistance, no polarity, long service life, self-healing property, low ESR, high reliability and the like; due to the special advantages of the thin film capacitor, the thin film capacitor is widely applied to the fields of medium and high voltage power, photovoltaics, new energy automobiles and the like.
The biaxially oriented polypropylene (BOPP) film which is widely used at present has the limitation that the energy storage density is only 2J/cm due to the lower dielectric constant 3 Left and right. Meanwhile, capacitors such as ceramic capacitors and electrolytic capacitors cannot play a role in replacement in the field of thin film capacitors, so that main technical innovation is the exploration and development of new base film materials and new processes.
The ferroelectric polymer represented by polyvinylidene fluoride (PVDF) has higher dielectric constant and is expected to become a novel composite film with high energy storage property, but the dielectric loss of the composite film is higher under the action of an external electric field, so that the charge-discharge efficiency of the composite film is lower. In addition, the linear polymer Polymethacrylate (PMMA) has higher breakdown field strength and energy storage efficiency, but the lower dielectric constant makes it difficult to obtain high energy storage density.
Disclosure of Invention
In view of the above, the invention provides a PVDF/PMMA composite film and a preparation method thereof, the PVDF/PMMA composite film has an electric hysteresis loop similar to antiferroelectric, low remanent polarization, high energy storage density, and can be used for a film capacitor, and meanwhile, the preparation method can be used for continuously preparing a polymer film at high speed, and has good industrial prospects.
The technical scheme adopted by the invention for solving the technical problem is as follows: according to one aspect of the invention, a preparation method of a PVDF/PMMA composite film is provided, which comprises the following steps:
premixing the PVDF and PMMA materials according to a certain mass ratio to obtain a premix;
melt blending, namely feeding the premix into a blending device at a preset speed, heating and stirring the premix through at least one temperature zone to form a molten state, and obtaining a molten blend;
casting film forming, namely pushing the molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film;
and cooling and winding, namely cooling the film formed by the convection casting by a cooling roller, and winding by a winding roller at a preset rotating speed.
As a further improvement of the invention, the method also comprises the step of drying the PVDF and PMMA materials before mixing the PVDF and PMMA materials.
As a further improvement of the invention, the feeding speed of the premix into the blending device is 0.5-2 kg/h.
As a further improvement of the invention, the premix is heated in three temperature zones to be molten, and the temperature of each temperature zone is between 150 and 300 ℃.
As a further improvement of the invention, when the molten blend flows through the casting head, the temperature of the casting head is 150-300 ℃, and the thickness of the molten blend flow outlet of the casting head is 5-30 μm.
As a further improvement of the invention, the temperature of the cooling roller is 50-100 ℃, the rotating speed of the cooling roller is 5-20 r/min, and the rotating speed of the winding roller is 5-20 r/min.
According to another aspect of the present invention, there is provided a PVDF/PMMA composite film prepared according to the preparation method, wherein the prepared PVDF/PMMA composite film has an antiferroelectric-like hysteresis loop and a storage density of more than 9J/cm under an electric field of 350MV/m 3 。
As a further improvement of the present invention, the PVDF material comprises at least one of PVDF, P (VDF-TrFE) or P (VDF-HFP).
The invention has the beneficial effects that: the embodiment of the invention provides a PVDF/PMMA composite film and a preparation method thereof, wherein the preparation method comprises the steps of mixing PVDF and PMMA materials according to a certain mass ratio to obtain a premix; then feeding the premix into a blending device at a preset speed, heating and stirring the premix through at least one temperature zone to be molten, and obtaining a molten blend; pushing the obtained molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film; and finally, cooling the film formed by the convection casting by a cooling roller, and rolling by a rolling roller at a preset rotating speed to finish the preparation of the PVDF/PMMA composite film. The PVDF/PMMA composite film prepared by the preparation method has the characteristics of antiferroelectric ferroelectric hysteresis loop, high energy storage density and high energy storage efficiency. Meanwhile, the preparation method can be used for continuously preparing the polymer film at high speed, and has good industrialization prospect.
Drawings
FIG. 1 is a flow chart of a PVDF/PMMA composite film preparation method provided by an embodiment of the invention;
FIG. 2 is an XRD test chart of a PVDF/PMMA composite film prepared by the preparation method provided by the embodiment of the invention;
FIG. 3 shows that the mass ratio of PVDF to PMMA is 0.65: 0.35 the electric hysteresis loop of the prepared composite film;
FIG. 4 shows that the mass ratio of PVDF to PMMA is 0.8: 0.2 the electric hysteresis loop of the prepared composite film;
FIG. 5 is a hysteresis loop of a comparative example;
FIG. 6 shows that the mass ratio of PVDF to PMMA is 0.65: 0.35 schematic diagram of the change of the energy storage density of the prepared composite film along with the electric field;
fig. 7 is a schematic structural diagram of a preparation system used in the preparation method according to an embodiment of the present invention.
The following description is made with reference to the accompanying drawings:
300-preparation system; 301-premix apparatus;
302-blanking device; 303-blending means;
304-casting film forming device; 305-cooling the winder;
306-drying device.
Detailed Description
A preferred embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
According to the PVDF/PMMA composite film and the preparation method and the preparation system thereof provided by the embodiment of the invention, in the preparation method, PVDF and PMMA materials are mixed according to a certain mass ratio to obtain a premix; then feeding the premix into a blending device at a preset speed, heating and stirring the premix through at least one temperature zone to be molten, and obtaining a molten blend; pushing the obtained molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film; and finally, cooling the film formed by the convection casting by a cooling roller, and rolling by a rolling roller at a preset rotating speed to finish the preparation of the PVDF/PMMA composite film. The PVDF/PMMA composite film prepared by the preparation method has the characteristics of antiferroelectric ferroelectric hysteresis loop, high energy storage density and high energy storage efficiency. Meanwhile, the preparation method can be used for continuously preparing the polymer film at high speed, and has good industrialization prospect.
The PVDF/PMMA composite film and the preparation method thereof disclosed by the invention are described in detail by combining with specific embodiments. First, according to an aspect of the present invention, there is provided a method for preparing a PVDF/PMMA composite film, and fig. 1 is a flowchart of a method for preparing a PVDF/PMMA composite film according to an embodiment of the present invention, and referring to fig. 1, the method includes the following steps:
s100, premixing PVDF and PMMA materials according to a certain mass ratio to obtain a premix;
specifically, in embodiments of the present invention, the PVDF material is a PVDF-based ferroelectric polymer, such as one or more of polyvinylidene fluoride (PVDF), polyvinylidene fluoride copolymer P (VDF-TrFE), or polyvinylidene fluoride-hexafluoropropylene (P (VDF-HFP), and polymethyl methacrylate (PMMA) is a linear dielectric polymer, in this step, the PVDF and PMMA materials are agitated and mixed at a certain mass ratio and a predetermined agitation speed, such as, in one exemplary embodiment, the mass ratio of the PVDF and PMMA materials is 0.65: 0.35, in another exemplary embodiment, the mass ratio of the PVDF and PMMA materials is 0.8: 0.2, although not limited thereto, and other mass ratios are also possible, the agitation speed may be, for example, 10r/min, such that the PVDF and PMMA materials are thoroughly mixed to obtain a premix, in some embodiments of the present invention, the method also comprises the step of drying the PVDF and PMMA materials before stirring and mixing the PVDF and PMMA materials.
S200, carrying out melt blending, namely feeding the premix into a blending device at a preset speed, heating the premix through at least one temperature zone, and stirring the premix into a molten state to obtain a melt blend;
in this step, the speed of feeding the pre-mixture into the blending device may affect the thickness and the film forming quality of the final composite film, and specifically, the speed of feeding the pre-mixture into the blending device is 0.5 to 2kg/h, for example, 1 kg/h. The premix is heated and stirred in a blending device through at least one temperature zone to be molten, and the temperature of each temperature zone is set to be 150-300 ℃. Specifically, for example, in one embodiment, the blending device is provided with three temperature zones, the temperature settings of the three temperature zones are 190 ℃, 200 ℃, 210 ℃, respectively, although not limited thereto.
In detail, in an embodiment of the present invention, a screw is disposed in the blending device, the screw rotates to advance the pre-mixture to sequentially enter different temperature zones to be heated to a molten state, and the screw rotates to advance the pre-mixture while stirring the pre-mixture, so as to achieve sufficient blending of the melts. It should be noted that, a suitable screw rotation speed is favorable for uniform mixing and crystal phase improvement, and the screw rotation speed is 5 to 20r/min, for example, 8 r/min.
S300, casting to form a film, namely pushing the molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film;
the molten state blend fully mixed in the blending device is continuously pushed by the rotation of a screw, and finally extruded to a casting film forming device, and flows out of a casting head of the casting film forming device to form a film. In detail, a heating device is configured at the casting head for heating the casting head, so that when the molten blend flows through the casting head, the temperature of the casting head is 150-300 ℃, for example, the heating device is arranged, the molten blend is conveniently cast into a film, the molten blend is prevented from being solidified, and in addition, in one embodiment, the thickness of the molten blend outlet of the casting head is 5-30 μm, for example, so that a composite film meeting the requirement can be formed.
And S400, cooling and winding, wherein the film formed by convection casting is cooled by a cooling roller and wound at a preset rotating speed by a winding roller.
Specifically, in the step, the PVDF/PMMA composite film formed by the casting film forming device is cooled by a cooling roller and then wound by a winding roller, so that the batch preparation of the PVDF/PMMA composite film is completed. Wherein the number of wind-up roll can be a plurality ofly to be the interval setting, so set up, be favorable to carrying out longitudinal stretching to the film forming. Specifically, the temperature of the cooling roller is 50-100 ℃, for example 70 ℃, and it can be understood that the rotating speeds of the cooling roller and the winding roller are not easy to set too fast or too slow, for example, the rotating speeds of the cooling roller and the winding roller are respectively set to 8 r/min.
The PVDF/PMMA composite film prepared by the method is prepared by melting and blending the raw materials, has no other solvents in the whole process, and is environment-friendly. Meanwhile, the preparation method can be used for continuously preparing the film at a relatively high speed, and has good industrial application prospect.
According to another aspect of the present invention, there is provided a PVDF/PMMA composite film prepared by the above preparation method, and fig. 2 is an XRD test chart of the PVDF/PMMA composite film prepared by the above preparation method, wherein the mass ratio of the PVDF to the PMMA is 0.65: 0.35, and marking the XRD test pattern formed by the prepared composite film as an 'example 1' curve; the mass ratio of PVDF to PMMA is 0.8: 0.2 XRD test pattern formed by the prepared composite film, marked as "example 2" curve; as a comparative example, an XRD test pattern formed with a film prepared with PVDF only and no PMMA material, labeled as the "comparative example" curve. As can be seen from fig. 2, a strong peak is observed from the curve of the comparative example, which indicates that the crystalline phase of the film of the comparative example is high, while a broad peak is observed from the curves of the example one and the example two, and it can be seen from the scherrer equation that the grain size of the composite films prepared in the example one and the example two is reduced, which is mainly due to the addition of the amorphous PMMA, which reduces the grain size. And when the grain size is reduced, the size of the dipole is limited, so that the coercive field is reduced, the dipole turnover probability is improved, the residual polarization is reduced, and the energy storage density is improved.
In order to verify the hysteresis loop characteristics of the obtained PVDF/PMMA composite film, the PVDF/PMMA composite film prepared by the above method is subjected to electrode preparation, and the hysteresis loop test is performed on the film, and the test results are shown in fig. 3, fig. 4 and fig. 5, where fig. 3 is a graph in which the mass ratio of the PVDF to the PMMA material is 0.65: 0.35, and fig. 4 is a graph showing that the mass ratio of PVDF to PMMA is 0.8: 0.2, fig. 5 is the hysteresis loop of the comparative example, which is likewise still a film prepared by the above-described process with the starting material comprising only PVDF and no PMMA material, as can be seen from fig. 3, 4 and 5, with a mass ratio of PVDF to PMMA material of 0.65: 0.35 and 0.8: 0.2 the prepared composite film exhibited a ferroelectric hysteresis loop similar to that of antiferroelectric, while the comparative example film exhibited a normal ferroelectric hysteresis loop.
FIG. 6 shows that the mass ratio of PVDF and PMMA materials is 0.65: the change of the energy storage density of the composite film prepared by 0.35 along with the electric field is shown in the figure, and the energy storage density is more than 9J/cm under the electric field of 350MV/m 3 This shows that the PVDF/PMMA composite film prepared by the preparation method has higher energy storage density.
In order to better understand the preparation method of the PVDF-PMMA composite film provided by the embodiment of the invention, a preparation system used in the method is described below, fig. 7 is a schematic structural diagram of the preparation system used in the preparation method provided by the embodiment of the invention, and referring to fig. 7, the preparation system 300 includes a premixing device 301, generally, the premixing device 301 has a cavity for carrying PVDF and PMMA materials, and a stirring device for stirring and mixing the PVDF and PMMA materials to obtain a premix; the preparation system 300 further comprises a blanking device 302, wherein the blanking device 302 is arranged between the premix device 301 and the blending device 303 and is used for feeding the premix into the blending device 303 at a preset speed; the preparation system 300 further comprises a blending device 303, generally, the blending device 303 comprises a screw for stirring the pre-mixture and pushing the molten blend into a casting film forming device, at least one temperature zone for heating the pre-mixture, and a heating device for heating each temperature zone; the production system 300 further includes a casting film-forming device 304, and generally, the casting film-forming device 304 includes a casting head and a casting head heating device for heating the casting head; the production system 300 further includes a cooling wind-up device 305, and generally, the cooling wind-up device 305 includes a cooling roller for cooling down the film formed by casting and a wind-up roller for winding up the thin film. Preferably, some preparation systems 300 further include a drying device 306 for drying the PVDF and PMMA materials before mixing the PVDF and PMMA materials. In some preparation systems, the drying device 306 may be, for example, integrated in the premixing device 301, or may be a separate drying device, and the PVDF and PMMA materials are dried first, and then the dried PVDF and PMMA materials enter the premixing device 301 to be mixed, or of course, the PVDF and PMMA materials may be directly dried and mixed in the cavity of the premixing device 301.
In the previous description, numerous specific details were set forth in order to provide a thorough understanding of the present invention. The foregoing description is only a preferred embodiment of the invention, which can be embodied in many different forms than described herein, and therefore the invention is not limited to the specific embodiments disclosed above. And that those skilled in the art will be able to make many changes and modifications to the invention using the method and techniques disclosed above, or to modify and adapt equivalent embodiments to equivalent variations, without departing from the scope of the invention. Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a PVDF/PMMA composite film is characterized by comprising the following steps:
premixing the PVDF and PMMA materials according to a certain mass ratio to obtain a premix;
melt blending, namely feeding the premix into a blending device at a preset speed, heating and stirring the premix through at least one temperature zone to form a molten state, and obtaining a molten blend;
casting film forming, namely pushing the molten blend to a casting film forming device, and enabling the molten blend to flow out of the casting film forming device to form a film;
and cooling and winding, namely cooling the film formed by the convection casting by a cooling roller, and winding by a winding roller at a preset rotating speed.
2. The method for preparing PVDF/PMMA composite film according to claim 1, characterized in that: the method also comprises the step of drying the PVDF and PMMA materials before mixing the PVDF and PMMA materials.
3. The method for preparing PVDF/PMMA composite film according to claim 1, characterized in that: feeding the premix into a blending device at a feeding speed of 0.5-2 kg/h.
4. The method for preparing PVDF/PMMA composite film according to claim 1, characterized in that: heating the premix in three temperature zones to enable the premix to be in a molten state, wherein the temperature of each temperature zone is 150-300 ℃.
5. The method for preparing the PVDF/PMMA composite film according to claim 1, wherein: when the melt blend flows through the casting head, the temperature of the casting head is 150-300 ℃, and the thickness of a melt blend flow outlet of the casting head at the temperature of 5-30 mu m.
6. The method for preparing PVDF/PMMA composite film according to claim 1, characterized in that: the temperature of the cooling roller is 50-100 ℃, the rotating speed of the cooling roller at the temperature of 5-20 r/min, and the rotating speed of the winding roller is 5-20 r/min.
7. A PVDF/PMMA composite film produced by the production method according to any one of claims 1 to 6, wherein: the prepared PVDF/PMMA composite film has a ferroelectric hysteresis loop similar to antiferroelectric, and the energy storage density is more than 9J/cm under an electric field of 350MV/m 3 。
8. The PVDF/PMMA composite film according to claim 7, characterized in that the PVDF material comprises at least one of PVDF, P (VDF-TrFE) or P (VDF-HFP).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110002641A (en) * | 2009-07-02 | 2011-01-10 | 연세대학교 산학협력단 | Manufacturing method of ferroelectric pvdf/pmmf thin film with ultra low surface roughness and nonvolatile memory devices with the thin fim |
| CN104877278A (en) * | 2015-06-29 | 2015-09-02 | 北京化工大学 | Poly-n-butyl methacrylate/polyvinylidene fluoride vinyl compound dielectric film and preparation method thereof |
| CN105542363A (en) * | 2016-01-27 | 2016-05-04 | 燕山大学 | Method for preparing PVDF-based composite film through bidirectional synchronous drawing |
| CN107652588A (en) * | 2017-09-30 | 2018-02-02 | 清华大学 | A kind of ferroelectric polymers based dielectric film, and its production and use |
| CN110951195A (en) * | 2019-12-09 | 2020-04-03 | 哈尔滨理工大学 | PMMA/PVDF composite film and preparation method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110002641A (en) * | 2009-07-02 | 2011-01-10 | 연세대학교 산학협력단 | Manufacturing method of ferroelectric pvdf/pmmf thin film with ultra low surface roughness and nonvolatile memory devices with the thin fim |
| CN104877278A (en) * | 2015-06-29 | 2015-09-02 | 北京化工大学 | Poly-n-butyl methacrylate/polyvinylidene fluoride vinyl compound dielectric film and preparation method thereof |
| CN105542363A (en) * | 2016-01-27 | 2016-05-04 | 燕山大学 | Method for preparing PVDF-based composite film through bidirectional synchronous drawing |
| CN107652588A (en) * | 2017-09-30 | 2018-02-02 | 清华大学 | A kind of ferroelectric polymers based dielectric film, and its production and use |
| CN110951195A (en) * | 2019-12-09 | 2020-04-03 | 哈尔滨理工大学 | PMMA/PVDF composite film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 朱挺茂: "聚偏氟乙烯共混物结构调控与储能特性", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》, no. 01, pages 014 - 254 * |
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