CN111040212A - PVDF (polyvinylidene fluoride) -based composite film and preparation method thereof - Google Patents
PVDF (polyvinylidene fluoride) -based composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a PVDF (polyvinylidene fluoride) -based composite film and a preparation method thereof, relates to the field of dielectrics, and can improve the breakdown strength and the energy storage density of the composite film. The invention adopts a layer-by-layer self-assembly technology to form a multilayer ordered sandwich structure, each heterogeneous functional layer respectively takes high-dielectric P (VDF-TrFE-CTFE) as the top layer and the bottom layer of the sandwich structure, and then takes cross-linked unsaturated P (VDF-CTFE-DB) with low dielectric and high breakdown field strength as the middle layer of the sandwich structure. The top and bottom high dielectric P (VDF-TrFE-CTFE) can provide larger electric displacement for the composite film, the cross-linked structure of the middle layer can effectively inhibit the accumulation of charges of the film under a high electric field, redistribute the interface electric field of the heterogeneous layer, prevent the further development of the electric tree and improve the breakdown strength of the composite film. Meanwhile, the preparation process is simple, the use of inorganic nano materials with complex preparation process and high cost is avoided while high energy storage performance is realized, and the flexibility and durability of the film are maintained to the maximum extent.
Description
Technical Field
The invention relates to the field of dielectrics, in particular to a PVDF (polyvinylidene fluoride) -based composite film and a preparation method thereof.
Background
With the widespread use of electronic devices and products, energy storage devices play an important role in the power, electronics, and smart manufacturing industries. The film capacitor is used as an energy storage device, and has the advantages of rapid charge and discharge, high voltage tolerance, high power density, stable performance and cyclic use. The polymer-based thin film capacitor with high energy storage density can be used for electromagnetic weapons, portable mobile equipment, electromagnetic launching platforms and the like. For both civil and military use, power storage systems with higher integration and better safety and reliability are required.
However, the relatively low energy storage density still limits the application prospect of the dielectric capacitor. For example, biaxially oriented polypropylene (BOPP) film, which is the most widely used commercial dielectric energy storage capacitor at present, can only release about 2J/cm due to its relatively low dielectric constant, although its dielectric breakdown field strength can reach 6000kV/cm or more3The energy density of (1).
The energy storage density of a dielectric is related to its dielectric constant and breakdown field strength, therefore, most researchers often compound some high dielectric filler in the polymer matrix to increase the dielectric constant of the dielectric to improve its energy storage performance. However, if a dielectric with a higher dielectric constant is to be obtained, it is usually achieved by adding inorganic filler with a high dielectric constant of 20 vol.% to 50 vol.%, and such a high filling amount will inevitably cause some inevitable defects and agglomeration of inorganic particles in the polymer matrix, which leads to a significant decrease in the breakdown field strength of the dielectric, and thus leads to a lower energy storage density and energy storage efficiency of the present dielectric.
Disclosure of Invention
The invention provides a PVDF-based composite film and a preparation method thereof, wherein a polymer with a cross-linked structure is introduced into a PVDF-based copolymer with a high dielectric constant, and through the design of a microstructure and the redistribution of an electric field, the leakage current of the composite film can be obviously reduced, the breakdown field strength of the composite film can be improved, and the composite film with high energy storage density can be prepared.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a PVDF-based composite film comprises the following steps:
synthesizing P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE);
adding a cross-linking agent into a P (VDF-CTFE-DB) matrix containing unsaturated double bonds, and forming the P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE) added with the cross-linking agent into a composite film with a multilayer ordered structure by adopting a layer-by-layer self-assembly method according to a certain arrangement method;
and carrying out thermal crosslinking on the composite film at the temperature of 120-180 ℃, and curing for 5-10 h to obtain the PVDF-based composite film.
Further, the arrangement method comprises the following steps:
p (VDF-CTFE-DB) which is only added with the cross-linking agent is mutually assembled into a multilayer film, or P (VDF-TrFE-CTFE) which is only added with the cross-linking agent is mutually assembled into a multilayer film.
Further, the arrangement method comprises the following steps:
p (VDF-TrFE-CTFE) as the top and bottom layers and P (VDF-CTFE-DB) with crosslinker added as the middle layer. The volume fraction of the middle layer is 10-50 vol.% of the total volume of the top and bottom layers.
Further, the arrangement method comprises the following steps:
p (VDF-CTFE-DB) with crosslinker added as top and bottom layers and P (VDF-TrFE-CTFE) as an intermediate layer. The volume fraction of the middle layer is 10-50 vol.% of the total volume of the top and bottom layers.
Further, the arrangement method comprises the following steps:
p (VDF-CTFE-DB) with crosslinker added as the top layer and P (VDF-TrFE-CTFE) as the bottom layer. The volume ratio of the top layer to the bottom layer was 1: 1.
Further, the synthesis method of P (VDF-CTFE-DB) comprises the following steps:
dissolving P (VDF-CTFE) powder in a dry oxygen-free solvent under the anhydrous and oxygen-free conditions, and adding a catalyst into the obtained solution;
reacting the solution at 30-100 ℃ for 12-24 h, and separating out a product in deionized water;
washing the product, removing by-products, catalyst, polymer which is not completely reacted and other impurities, and drying in vacuum to obtain P (VDF-CTFE-DB).
Further, the synthesis method of P (VDF-TrFE-CTFE) comprises the following steps:
dissolving P (VDF-CTFE) powder and metal halide by adopting a dry oxygen-free solvent under the anhydrous and oxygen-free conditions, and adding a catalyst into the obtained solution;
injecting a pre-dissolved ligand solution into the solution, uniformly stirring, reacting for 12-24 h at 70-120 ℃, and separating out a product in deionized water;
washing the product to remove metal halide, unreacted ligand and other impurities, and vacuum drying to obtain P (VDF-TrFE-CTFE).
A PVDF-based composite film is prepared by the preparation method of the PVDF-based composite film.
The invention has the beneficial effects that:
the invention starts from the design of a microstructure, introduces a cross-linking structure, and forms a composite film which is all organic, has multiple layers of order, high breakdown field strength and high energy storage density. The high dielectric layer P (VDF-TrFE-CTFE) provides a large electric potential shift for the composite film, and the cross-linked structure in the P (VDF-CTFE-DB) can effectively inhibit the accumulation of charges of the film under the action of a high electric field and can effectively inhibit the further development of electric dendrites. In addition, the multilayer ordered structure plays a role in redistributing the electric field at the interface of the dissimilar materials, so that the leakage current of the multilayer ordered structure can be obviously reduced, and the breakdown field intensity and the energy storage density of the multilayer ordered structure can be improved.
In addition, the raw materials P (VDF-TrFE-CTFE) and P (VDF-CTFE-DB) used in the invention are PVDF copolymer, so that the two materials have good interface compatibility when being orderly compounded, and the defects of delamination, weak interface bonding force and the like caused by mismatching of surface energy or interface tension can not occur. Meanwhile, the composite film is simple in preparation process, has good film-forming property, can be formed according to various shape requirements of the base material, and effectively shortens the preparation period. In addition, the all-organic composite film avoids the use of inorganic nano materials in the traditional 0-3 type composite film, reduces the production cost, more importantly, maintains the essential characteristic of excellent flexibility of the polymer to the maximum extent, and can obviously improve the durability of the energy storage device. Meanwhile, a good foundation is laid for commercialization of the flexible high-efficiency energy storage device.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a synthesis route diagram of P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE);
FIG. 2 shows nuclear magnetic resonance of P (VDF-TrFE-CTFE) and P having double bond (VDF-CTFE-DB)1H NMR characterization;
FIG. 3 is a SEM image of a cross section of a composite film according to one embodiment.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described in detail with reference to the following detailed description.
The embodiment of the invention provides a preparation method of a PVDF-based composite film, which takes P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE) as synthetic materials. The synthetic pathways of P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE) are shown in FIG. 1, and nuclear magnetism1The H NMR characterization is shown in figure 2.
The synthesis method of P (VDF-CTFE-DB), namely the poly (vinylidene fluoride-chlorotrifluoroethylene) containing double bonds, comprises the following steps: adding a certain amount of P (VDF-CTFE), namely poly (vinylidene fluoride-chlorotrifluoroethylene) powder into an anhydrous and oxygen-free four-neck flask, injecting dry and oxygen-free N-methylpyrrolidone into the flask to dissolve the polymer, and injecting a certain amount of triethylamine after the polymer is dissolved, wherein the molar ratio of the triethylamine to Cl element in the P (VDF-CTFE) is 1.02: 1. After being stirred evenly, the mixture reacts for 12 to 24 hours at the temperature of between 30 and 100 ℃, the product is separated out in deionized water, the by-product and triethylamine are removed by repeated dissolution-separation washing, then polymer which is not completely reacted and other impurities in the product are removed by repeated washing, and finally P (VDF-CTFE-DB) is obtained by vacuum drying.
The synthesis method of P (VDF-TrFE-CTFE), namely poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) comprises the following steps: adding a certain amount of P (VDF-CTFE) powder and metal halide into an anhydrous and oxygen-free four-neck flask, injecting dry and oxygen-free N-methyl pyrrolidone into the flask to dissolve the polymer and the metal halide, injecting a certain amount of pre-dissolved ligand solution after the substances are dissolved, reacting at 70-120 ℃ for 12-24 h after uniformly stirring, separating out the product in deionized water, repeatedly washing the solution-separated out to remove the metal halide, then washing the product for multiple times by using methanol to remove the unreacted ligand and other impurities in the product, and finally drying in vacuum to obtain pure P (VDF-TrFE-CTFE).
Wherein the combination of metal halide and ligand is: CuCl/Bpy (Bipyridine Bipyridine), Cu and CuCl2Mixture of (1)/Bpy, CuCl/aqueous ammonia.
Example one
Respectively dissolving P (VDF-TrFE-CTFE) and P (VDF-CTFE-DB) by using N-dimethylformamide to form 10 wt% of polymer solution, then adding BPO (dibenzoyl peroxide) with the mass fraction of 5 wt% (based on the mass of P (VDF-CTFE-DB)) into the P (VDF-CTFE-DB) solution, and stirring until the mixture is completely dissolved for later use.
The method comprises coating a layer of film with thickness of about 3 μm on a clean glass plate with P (VDF-TrFE-CTFE) solution as a bottom layer, and oven drying the film in a vacuum drying oven at 80 deg.C. Then, a solution of P (VDF-CTFE-DB) containing BPO was coated on the surface of the above-mentioned P (VDF-TrFE-CTFE) thin film, the volume fraction of the coated P (VDF-CTFE-DB) was controlled to about 30 vol.% of the top and bottom P (VDF-TrFE-CTFE) thin films, and the two-material coated glass plates were placed in a vacuum drying oven at 80 ℃ to be dried, and the temperature was raised to 150 ℃ to cause a crosslinking reaction of the BPO-containing P (VDF-CTFE-DB) layer. Finally, coating a solution of P (VDF-TrFE-CTFE) on the two layers of films to form a top layer, wherein the thickness of the top layer is the same as that of the bottom layer P (VDF-TrFE-CTFE), and continuously placing the top layer in a vacuum drying oven at 80 ℃ for drying. And finally, placing the composite film with the sandwich structure on a heating table at 180 ℃ for melting for 5 minutes, then quickly placing the composite film into ice water for quenching, drying the composite film at 60 ℃, plating gold electrodes on the upper surface and the lower surface of the composite film, and carrying out subsequent performance test.
The SEM cross-section of the composite film is shown in FIG. 3, in which the top and bottom layers are P (VDF-TrFE-CTFE) and the middle layer is cross-linked P (VDF-CTFE-DB), with a volume fraction of 30 vol.% of P (VDF-TrFE-CTFE)
Example two
P (VDF-TrFE-CTFE) and P (VDF-CTFE-DB) were dissolved in N-dimethylformamide to prepare a 10 wt% polymer solution, and BPO (based on the mass of P (VDF-CTFE-DB)) was added to the P (VDF-CTFE-DB) solution in a mass fraction of 5 wt% and dissolved with stirring for use.
Coating a layer of thin film with the thickness of about 3 microns on a clean glass plate by adopting a layer-by-layer self-assembly technology, drying the thin film in a vacuum drying oven at the temperature of 80 ℃, then coating the surface of the P (VDF-TrFE-CTFE) film with a P (VDF-TrFE-CTFE) solution, controlling the volume fraction of the coated P (VDF-TrFE-CTFE) to be about 30 vol% of the top and bottom layer P (VDF-CTFE-DB) film, placing the glass plate coated with the two materials in a vacuum drying oven at 80 ℃ for drying, then, a BPO-containing P (VDF-CTFE-DB) solution was coated on the above two films as a top layer, the thickness of the film is the same as that of the bottom layer P (VDF-CTFE-DB), and the film is continuously placed in a vacuum drying oven at 80 ℃ for drying. The temperature was raised to 120 ℃ to cause the BPO-containing P (VDF-CTFE-DB) layer to undergo a crosslinking reaction. And finally, placing the assembled composite film on a heating table at 180 ℃ for melting for 5 minutes, then quickly placing the composite film into ice water for quenching, drying the composite film at 60 ℃, plating gold electrodes on the upper surface and the lower surface of the composite film, and carrying out subsequent performance test.
EXAMPLE III
P (VDF-TrFE-CTFE) and P (VDF-CTFE-DB) were dissolved in N-dimethylformamide to prepare a 10 wt% polymer solution, and BPO (based on the mass of P (VDF-CTFE-DB)) was added to the P (VDF-CTFE-DB) solution in a mass fraction of 5 wt% and dissolved with stirring for use.
The method comprises the steps of coating a layer of thin film with the thickness of about 3 microns on a clean glass plate by using a layer-by-layer self-assembly technology, namely coating a layer of P (VDF-TrFE-CTFE) solution on the clean glass plate to serve as a bottom layer, drying the thin film in a vacuum drying box at the temperature of 80 ℃, coating a P (VDF-CTFE-DB) solution containing BPO on the surface of the P (VDF-TrFE-CTFE) thin film, enabling the coated P (VDF-CTFE-DB) and the bottom layer P (VDF-TrFE-CTFE) thin film to have the same volume fraction, placing the glass plate coated with the two materials in the vacuum drying box at the temperature of 80 ℃, drying the glass plate at the temperature of 180 ℃, and enabling the P (VDF-CTFE-DB) layer containing the BPO to have a crosslinking reaction. And finally, placing the dried three-layer film on a heating table at 180 ℃ for melting for 5 minutes, then quickly putting the composite film into ice water for quenching, drying at 60 ℃, plating gold electrodes on the upper surface and the lower surface of the composite film, and carrying out subsequent performance test.
Example four
P (VDF-TrFE-CTFE) was first dissolved in N-dimethylformamide to form a 10 wt% polymer solution for use. The P (VDF-TrFE-CTFE) solution was coated on a clean glass plate with a film of about 30 μm thickness and the film was dried in a vacuum oven at 80 ℃. And finally, placing the dried P (VDF-TrFE-CTFE) film on a heating table at 180 ℃ for melting for 5 minutes, then quickly placing the film in ice water for quenching, drying the film at 60 ℃, plating gold electrodes on the upper surface and the lower surface of the composite film, and carrying out subsequent performance test.
EXAMPLE five
P (VDF-CTFE-DB) is dissolved in N-dimethylformamide to form a 10 wt% polymer solution, and BPO (based on the mass of P (VDF-CTFE-DB)) with the mass fraction of 5 wt% is added to the P (VDF-CTFE-DB) solution and stirred and dissolved for later use. The BPO-containing P (VDF-CTFE-DB) solution was coated on a clean glass plate with a film about 30 μm thick, the film was dried in a vacuum oven at 80 ℃ and then heated to 150 ℃ to cause a crosslinking reaction. And finally, placing the cured P (VDF-CTFE-DB) film on a heating table at 180 ℃ for heat treatment for 5 minutes, then quickly placing the film in ice water for quenching, drying the film at 60 ℃, plating gold electrodes on the upper surface and the lower surface of the film, and carrying out subsequent performance test.
Comparison example one (section selected from Chinese patent, CN 108752612A)
Polymethyl methacrylate particles were dissolved in DMF (N, N-dimethyl formamide, N-Dimethylformamide) and stirred well until completely dissolved. The solid phase method is adopted to prepare the material PbZrO with the grain diameter R of 10nm3An antiferroelectric ceramic filler of a ceramic material. The ceramic filler is added into hydrogen peroxide with the concentration of 20 percent for surface activation. Adding the ceramic filler with the activated surface into absolute ethyl alcohol, adding dopamine with the mass of 10% of that of the ceramic filler, fully stirring, ultrasonically oscillating, circulating for 10 times, and drying at 80 ℃ for 10 hours to finish surface modification. Polyvinylidene fluoride was added to DMF and stirred well until completely dissolved. Then, the surface modified ceramic filler is added to the polymer solution and stirred and shaken well to form a stable suspension. Then coating a PMMA (polymethyl methacrylate) solution on the base film by adopting a tape casting method, wherein the coating thickness is 30 mu m, and then drying at 100 ℃ for 30min to form a PMMA layer; coating the prepared suspension on a PMMA layer with the coating thickness of 20 mu m, and continuously drying for 20min to form a ceramic filler layer; coating the PMMA solution on the ceramic filler layer, wherein the coating thickness is 30 mu m, and continuously drying for 30min to form a second PMMA layer; and finally, taking down the film with the three-layer structure from the base film. Melting the film at 200 ℃ for 300min, and then immediately putting the film into a low-temperature environment of-196 ℃ for quenching treatment for 3min to obtain the composite film material.
The breakdown field strength and energy storage density data for the different examples and comparative examples are shown in the following table:
as can be seen from the above table, the PVDF-based composite film prepared by the embodiment of the invention has higher breakdown field strength and energy storage density.
The invention has the beneficial effects that:
the invention starts from the design of a microstructure, introduces a cross-linking structure, and forms a composite film which is all organic, has multiple layers of order, high breakdown field strength and high energy storage density. The high dielectric layer P (VDF-TrFE-CTFE) provides a large electric potential shift for the composite film, and the cross-linked structure in the P (VDF-CTFE-DB) can effectively inhibit the accumulation of charges of the film under the action of a high electric field and can effectively inhibit the further development of electric dendrites. In addition, the multilayer ordered structure plays a role in redistributing the electric field at the interface of the dissimilar materials, so that the leakage current of the multilayer ordered structure can be obviously reduced, and the breakdown field intensity and the energy storage density of the multilayer ordered structure can be improved.
In addition, the raw materials P (VDF-TrFE-CTFE) and P (VDF-CTFE-DB) used in the invention are PVDF copolymer, so that the two materials have good interface compatibility when being orderly compounded, and the defects of delamination, weak interface bonding force and the like caused by mismatching of surface energy or interface tension can not occur. Meanwhile, the composite film is simple in preparation process, has good film-forming property, can be formed according to various shape requirements of the base material, and effectively shortens the preparation period. In addition, the all-organic composite film avoids the use of inorganic nano materials in the traditional 0-3 type composite film, reduces the production cost, more importantly, maintains the essential characteristic of excellent flexibility of the polymer to the maximum extent, and can obviously improve the durability of the energy storage device. Meanwhile, a good foundation is laid for commercialization of the flexible high-efficiency energy storage device.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a PVDF-based composite film is characterized by comprising the following steps:
synthesizing P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE);
adding a cross-linking agent into a P (VDF-CTFE-DB) matrix containing unsaturated double bonds, and forming the P (VDF-CTFE-DB) and P (VDF-TrFE-CTFE) added with the cross-linking agent into a composite film with a multilayer ordered structure by adopting a layer-by-layer self-assembly method according to a certain arrangement method;
and carrying out thermal crosslinking on the composite film at the temperature of 120-180 ℃, and curing for 5-10 h to obtain the PVDF-based composite film.
2. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the arranging method comprises:
and (3) assembling only by using the P (VDF-CTFE-DB) added with the cross-linking agent, or assembling only by using the P (VDF-TrFE-CTFE).
3. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the arranging method comprises:
the P (VDF-TrFE-CTFE) is used as a top layer and a bottom layer, and the P (VDF-CTFE-DB) added with the cross-linking agent is used as an intermediate layer;
the volume fraction of the middle layer is 10-50 vol.% of the total volume of the top and bottom layers.
4. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the arranging method comprises:
the crosslinker-added P (VDF-CTFE-DB) serves as a top and bottom layer, and the P (VDF-TrFE-CTFE) serves as an intermediate layer;
the volume fraction of the middle layer is 10-50 vol.% of the total volume of the top and bottom layers.
5. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the arranging method comprises:
the crosslinker-added P (VDF-CTFE-DB) serves as a top layer, and the P (VDF-TrFE-CTFE) serves as a bottom layer;
the volume ratio of the top layer to the bottom layer is 1: 1.
6. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the P (VDF-CTFE-DB) is synthesized by:
dissolving P (VDF-CTFE) powder by adopting dry oxygen-free N-methyl pyrrolidone under the anhydrous and oxygen-free conditions, and adding a catalyst into the obtained solution;
reacting the solution at 30-100 ℃ for 12-24 h, and separating out a product in deionized water;
washing the product, removing by-products, catalyst, polymer which is not completely reacted and other impurities, and drying in vacuum to obtain the P (VDF-CTFE-DB).
7. The method for preparing a PVDF-based composite film as defined in claim 1, wherein the P (VDF-TrFE-CTFE) is synthesized by:
dissolving P (VDF-CTFE) powder and metal halide by adopting dry oxygen-free N-methyl pyrrolidone under the anhydrous and oxygen-free conditions, and adding a catalyst into the obtained solution;
injecting a pre-dissolved ligand solution into the solution, uniformly stirring, reacting for 12-24 h at 70-120 ℃, and separating out a product in deionized water;
and washing the product to remove metal halide, unreacted ligand and other impurities, and drying in vacuum to obtain the P (VDF-TrFE-CTFE).
8. A PVDF-based composite film produced by the method for producing a PVDF-based composite film according to any one of claims 1 to 7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114522273A (en) * | 2022-01-06 | 2022-05-24 | 浙江大学 | Biomedical multilayer metal-based composite substrate with force-electricity and magnetism-electricity response characteristics and preparation method thereof |
| WO2024144095A1 (en) * | 2022-12-29 | 2024-07-04 | 국립부경대학교 산학협력단 | Modified polyvinylidene fluoride-based copolymer with improved hydrophilicity and method for preparing same |
| WO2024144097A1 (en) * | 2022-12-29 | 2024-07-04 | 국립부경대학교 산학협력단 | Method for controlling properties of polyvinylidene fluoride-based polymer having vinyl group by using multifunctional radical scavenger |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356603A (en) * | 2005-12-28 | 2009-01-28 | 宾夕法尼亚州研究基金会 | High electric energy density polymer capacitors with fast discharge speed and high efficiency based on unique poly(vinylidene fluoride) copolymers and terpolymers as dielectric materials |
| CN101691412A (en) * | 2009-09-30 | 2010-04-07 | 西安交通大学 | Method for preparing poly(VDF-CTFE-TrFE) or poly(VDF-TrFE) by using poly(VDF-CTFE) |
| KR101021509B1 (en) * | 2008-06-12 | 2011-03-16 | 성균관대학교산학협력단 | Organic pyroelectric sensors integrated in thin-film transistors and the method for producing the same |
| KR20170087318A (en) * | 2016-01-20 | 2017-07-28 | 울산대학교 산학협력단 | Artificial muscle fiber actuator |
| CN108047371A (en) * | 2017-11-22 | 2018-05-18 | 乳源东阳光氟树脂有限公司 | A kind of method for preparing P (VDF-TrFE) and P (VDF-TrFE-CTFE) |
| CN108752612A (en) * | 2018-06-01 | 2018-11-06 | 杭州电子科技大学 | High energy storage dielectric composite material preparation method based on PMMA sandwich structures |
| CN110256642A (en) * | 2019-03-13 | 2019-09-20 | 南京航空航天大学 | A kind of ferroelectric polymers and preparation method thereof with allochromy |
| CN110556247A (en) * | 2019-09-11 | 2019-12-10 | 邯郸学院 | preparation method of sandwich-structure high-energy-storage low-conductivity polymer-based composite film |
-
2019
- 2019-12-11 CN CN201911264493.9A patent/CN111040212A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356603A (en) * | 2005-12-28 | 2009-01-28 | 宾夕法尼亚州研究基金会 | High electric energy density polymer capacitors with fast discharge speed and high efficiency based on unique poly(vinylidene fluoride) copolymers and terpolymers as dielectric materials |
| KR101021509B1 (en) * | 2008-06-12 | 2011-03-16 | 성균관대학교산학협력단 | Organic pyroelectric sensors integrated in thin-film transistors and the method for producing the same |
| CN101691412A (en) * | 2009-09-30 | 2010-04-07 | 西安交通大学 | Method for preparing poly(VDF-CTFE-TrFE) or poly(VDF-TrFE) by using poly(VDF-CTFE) |
| KR20170087318A (en) * | 2016-01-20 | 2017-07-28 | 울산대학교 산학협력단 | Artificial muscle fiber actuator |
| CN108047371A (en) * | 2017-11-22 | 2018-05-18 | 乳源东阳光氟树脂有限公司 | A kind of method for preparing P (VDF-TrFE) and P (VDF-TrFE-CTFE) |
| CN108752612A (en) * | 2018-06-01 | 2018-11-06 | 杭州电子科技大学 | High energy storage dielectric composite material preparation method based on PMMA sandwich structures |
| CN110256642A (en) * | 2019-03-13 | 2019-09-20 | 南京航空航天大学 | A kind of ferroelectric polymers and preparation method thereof with allochromy |
| CN110556247A (en) * | 2019-09-11 | 2019-12-10 | 邯郸学院 | preparation method of sandwich-structure high-energy-storage low-conductivity polymer-based composite film |
Non-Patent Citations (3)
| Title |
|---|
| YANAN ZHANG ET AL.: ""Regulating Dielectric and Ferroelectric Properties of Poly(vinylidene fluoride-trifluoroethylene) with Inner CH=CH Bonds"", 《POLYMERS》 * |
| 李文静 等: ""聚偏氟乙烯基含氟聚合物介电和储能研究进展"", 《高分子通报》 * |
| 梁伯润 主编: "《高分子物理学（第二版）》", 31 January 2000, 中国纺织出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114522273A (en) * | 2022-01-06 | 2022-05-24 | 浙江大学 | Biomedical multilayer metal-based composite substrate with force-electricity and magnetism-electricity response characteristics and preparation method thereof |
| WO2024144095A1 (en) * | 2022-12-29 | 2024-07-04 | 국립부경대학교 산학협력단 | Modified polyvinylidene fluoride-based copolymer with improved hydrophilicity and method for preparing same |
| WO2024144097A1 (en) * | 2022-12-29 | 2024-07-04 | 국립부경대학교 산학협력단 | Method for controlling properties of polyvinylidene fluoride-based polymer having vinyl group by using multifunctional radical scavenger |
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