CN112622383B - Asymmetric three-layer structure all-polymer dielectric composite material and preparation method thereof - Google Patents
Asymmetric three-layer structure all-polymer dielectric composite material and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002033 PVDF binder Substances 0.000 claims abstract description 63
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 63
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 61
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000007731 hot pressing Methods 0.000 claims abstract description 10
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses an asymmetric three-layer structure all-polymer dielectric composite material and a preparation method thereof, belonging to the technical field of preparation of dielectric composite materials. The dielectric composite material comprises a first layer body, a second layer body and a third layer body which are sequentially arranged from bottom to top, wherein the first layer body is a pure polyvinylidene fluoride film, the second layer body is a mixed polyetherimide/polyvinylidene fluoride film, and the third layer body is a pure polyetherimide film. The invention combines the linear dielectric polyetherimide with high charge-discharge efficiency, the ferroelectric material polyvinylidene fluoride with high energy storage density and the PEI/PVDF three-layer film blended by the linear dielectric polyetherimide and the ferroelectric polyvinylidene fluoride with high energy storage density, and prepares the three-layer full polymer dielectric composite material by using a tape casting method and a hot pressing method. The intermediate transition layer is utilized to enable the electric field distribution to be more uniform and the synergistic effect of the linear dielectric layer and the ferroelectric layer, so that the energy storage density and the efficiency are jointly improved.
Description
Technical Field
The invention belongs to the technical field of preparation of dielectric composite materials, and particularly relates to an asymmetric three-layer structure all-polymer dielectric composite material and a preparation method thereof.
Background
At present, a big problem limiting the application of thin film capacitors is that the energy storage density is too low. Therefore, in order to increase the energy storage density of polymer composites, researchers have proposed various composite design strategies.
Research shows that the energy storage density can be remarkably improved by designing the multilayer composite material with the laminated structure and utilizing the synergistic effect among all functional layers. For example, the wang macro group at the west ampere traffic university reports a barium titanate/polyvinylidene fluoride composite material having a three-layer structure with a composition gradient, an outer layer having a high barium titanate content providing a high dielectric constant, and an intermediate layer having a low barium titanate content providing a high breakdown strength, which is greatly improved by composition optimization while maintaining a high dielectric constant. The Shenyang topic group of Qinghua university adopts the electrostatic spinning and hot pressing method to prepare the polyvinylidene fluoride/barium titanate composite film with up to 16 layers, and the discharge energy density of the polyvinylidene fluoride/barium titanate composite film is up to 35.4J/cm3。
Although the energy storage density of the composite material can be remarkably improved by designing the laminated structure, most of the currently reported charge-discharge efficiency of the composite material is lower than 80%, and the practical application of the composite material is greatly limited. That is, how to effectively achieve the synergistic improvement of the charge-discharge efficiency and the energy storage density remains a difficult problem to be solved urgently in the field of dielectric energy storage materials.
In order to maximize the increase of energy storage density, the currently reported laminated dielectric energy storage material generally adopts a ferroelectric polymer (such as polyvinylidene fluoride and copolymers thereof) as a matrix, and a ferroelectric ceramic (such as barium titanate) as a filler to construct a multilayer (more than three layers) material. Although the design can realize the remarkable improvement of dipole polarization and interface polarization strength, thereby obtaining high energy storage density, the polarization loss and leakage conduction loss of the ferroelectric phase are higher, and stronger interface polarization loss also exists at the interface between layers, thereby resulting in lower efficiency of the composite material.
Therefore, the prior art is subject to further improvement.
Disclosure of Invention
One of the objectives of the present invention is to provide an asymmetric three-layer all-polymer dielectric composite material, which can achieve the common improvement of energy storage density and efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the asymmetric three-layer structure full polymer dielectric composite material comprises a first layer body, a second layer body and a third layer body from bottom to top, wherein the first layer body is a pure polyvinylidene fluoride film, the second layer body is a mixed polyetherimide/polyvinylidene fluoride film, and the third layer body is a pure polyetherimide film.
Furthermore, the first layer, the second layer and the third layer have the same size and thickness.
The invention also aims to provide a preparation method of the asymmetric three-layer structure all-polymer dielectric composite material.
The preparation method of the asymmetric three-layer structure full polymer dielectric composite material comprises the following steps: the first layer body, the second layer body and the third layer body are prepared by a hot pressing method, and the hot pressing method adopts the following process conditions: the temperature is 170-190 ℃, the pressure is 7.5-8.5 MPa, and the time is 20-40 min.
Furthermore, the first layer, the second layer and the third layer are all prepared by a tape casting method.
Further, the preparation method of the first layer body comprises the following steps:
firstly, weighing a certain amount of polyvinylidene fluoride, adding the polyvinylidene fluoride into a container filled with N-methyl-2-pyrrolidone, stirring at a certain temperature, and continuing stirring after the polyvinylidene fluoride is completely dissolved to obtain a polyvinylidene fluoride solution;
secondly, placing the polyvinylidene fluoride solution on a clean glass plate for film scraping and forming, then placing the polyvinylidene fluoride solution in a blast type drying box for heat preservation, wherein the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
Further, in the first step, stirring is carried out at a temperature of 75 ℃; the height of a scraper used in the second step of film scraping and forming is 10 mu m; in the third step, the drying temperature of the oven is 70 ℃, and the temperature is kept for 6 h.
Further, the preparation method of the second layer body comprises the following steps:
firstly, weighing a certain amount of polyvinylidene fluoride and polyetherimide, adding the polyetherimide into a container filled with N-methyl-2-pyrrolidone, adding the polyvinylidene fluoride after the polyetherimide is dissolved, and stirring to obtain a mixed solution;
and secondly, placing the mixed solution on a clean glass plate for film scraping and molding, and then placing the mixed solution in a blast type drying box for heat preservation, wherein the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
Further, in the first step, stirring is carried out at a temperature of 75 ℃; the height of a scraper used in the second step of film scraping and forming is 10 mu m; in the third step, the drying temperature of the oven is 70 ℃, and the temperature is kept for 6 h.
Further, the preparation method of the third layer body comprises the following steps:
firstly, weighing a certain amount of polyetherimide, adding the polyetherimide into a container filled with N-methyl-2-pyrrolidone, stirring at a certain temperature, and continuing stirring after the polyetherimide is completely dissolved to obtain a polyetherimide solution;
secondly, the polyetherimide solution is placed on a clean glass plate for film scraping and molding, and then is placed in a blast type drying box for heat preservation, and the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
Further, the hot pressing method adopts the following process conditions: the temperature is 180 ℃, the pressure is 8MPa, and the time is 30 min.
Compared with the prior art, the invention has the following beneficial technical effects:
in order to obtain the polymer composite material with high efficiency and high energy storage density, the invention combines the linear dielectric Polyetherimide (PEI) with high charge-discharge efficiency, the ferroelectric polyvinylidene fluoride (PVDF) with high energy storage density and the PEI/PVDF three-layer film blended by the PEI and the PVDF three-layer film, and prepares the three-layer full polymer composite material by using a tape casting method and a hot pressing method. The intermediate transition layer is utilized to enable the electric field distribution to be more uniform and the synergistic effect of the linear dielectric layer and the ferroelectric layer to realize the common promotion of the energy storage density and the efficiency.
The three-layer asymmetric structure with the intermediate transition layer is prepared by tape casting and hot press molding of the linear dielectric material and the nonlinear dielectric material, so that high breakdown strength, low dielectric loss and high energy storage density are obtained, and the high efficiency of more than 91 percent is maintained.
At an external electric field strength of 600kV/mm, the two-layer composite still exhibits an ultra-high discharge efficiency η (> 91%), which is much higher than most reported results so far;
the dielectric composite material is remarkably improved in breakdown strength, and the breakdown strength is even higher than that of pure polymer PEI and PVDF and can reach 758kV/mm at most; all the double-layer composite materials have lower dielectric loss (less than or equal to 0.055).
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of a preparation process of a PEI-PEI/PVDF-PVDF three-layer composite material;
in FIG. 2, (a) is a morphology chart of a PEI-PEI/PVDF-PVDF three-layer composite material; (b) a Fourier infrared image of the PEI-PEI/PVDF-PVDF three-layer composite material;
in FIG. 3, (a) is a dielectric constant dispersion curve of a PEI-PEI/PVDF-PVDF three-layer composite material; (b) the dielectric loss dispersion curve of the double-layer composite material is shown;
in FIG. 4, (a) is a graph of the breakdown strength of a PEI-PEI/PVDF-PVDF three-layer composite material; (b) is a three-layer composite material breakdown strength histogram;
in FIG. 5, (a) is a discharge energy density map of the PEI-PEI/PVDF-PVDF three-layer composite, and (b) is a charge-discharge efficiency map of the three-layer composite.
Detailed Description
The invention provides an asymmetric three-layer structure all-polymer dielectric composite material and a preparation method thereof, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is described in detail with reference to specific embodiments.
"PEI" as referred to herein means polyetherimides;
"PVDF" as referred to in the present invention means polyvinylidene fluoride;
as used herein, the term "PEI/PVDF" refers to a blend of polyetherimide/polyvinylidene fluoride.
The starting materials described in the present invention are commercially available.
As the main improvement point of the invention, in the selection of raw materials, a three-layer asymmetric structure composite material consisting of a pure polyetherimide film, a mixed polyetherimide/polyvinylidene fluoride film and a pure polyvinylidene fluoride film can simultaneously obtain ultrahigh efficiency and high energy density.
The composite material with a three-layer structure comprises a first layer body, a second layer body and a third layer body from bottom to top respectively, wherein the first layer body is a pure polyvinylidene fluoride film, the second layer body is a mixed polyetherimide/polyvinylidene fluoride film, and the third layer body is a pure polyetherimide film.
The shape, size and thickness of each layer body are the same, and in the process, a single-layer film is prepared by adopting a tape casting method, and a three-layer film is prepared by adopting a hot pressing method.
The present invention will be described in detail with reference to specific examples.
The invention relates to a preparation method of an asymmetric three-layer structure all-polymer dielectric composite material, which specifically comprises the following steps:
first step, preparation of Pure PEI Polymer films
(1) 2g of polyetherimide was weighed out for use.
10ml of N-methyl-2-pyrrolidone was measured and placed in a 5ml beaker. Setting the temperature of a magnetic stirrer to be 75 ℃, after the temperature is stabilized at 75 ℃, placing a beaker in the stirrer to slowly stir, adding weighed polyetherimide after 10min, continuously and slowly stirring, quickly stirring for 5h after PEI particles are completely dissolved, and then slowly stirring at room temperature overnight;
(2) and cleaning and drying the high-temperature resistant glass plate by using alcohol and deionized water for later use. Setting the height of a scraper to be 10 mu m, placing a proper amount of stirred solution on a glass plate for film scraping and molding, and then placing the glass plate in a blast type drying box for heat preservation;
(3) the heat preservation is divided into two stages:
firstly, heating from room temperature to 100 ℃ at a heating speed of 1 ℃/min, and keeping the temperature for 4 h;
then heating from 100 ℃ to 200 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 5 min.
And then, rapidly placing the glass plate carrying the sample in ice water for quenching for about 1min, removing the film, paving the film on aluminum foil paper, placing the aluminum foil paper in an oven for drying again, setting the temperature to be 70 ℃, and preserving the heat for 6 h.
Second step, preparation of Pure PVDF polymer film
(1) Weighing 2g of polyvinylidene fluoride for later use.
10ml of N-methyl-2-pyrrolidone was measured and placed in a 5ml beaker. Setting the temperature of a magnetic stirrer to be 75 ℃, after the temperature is stabilized at 75 ℃, placing the beaker in the stirrer to be slowly stirred, adding weighed polyetherimide after 10min, continuously and slowly stirring, quickly stirring for 5h after PEI particles are completely dissolved, and then slowly stirring at room temperature overnight.
(2) And cleaning and drying the high-temperature resistant glass plate by using alcohol and deionized water for later use. Setting the height of a scraper to be 10 mu m, placing a proper amount of stirred solution on a glass plate for film scraping and molding, and then placing the glass plate in a blast type drying box for heat preservation;
(3) the heat preservation is divided into two stages:
firstly, heating from room temperature to 100 ℃ at a heating speed of 1 ℃/min, and keeping the temperature for 4 h;
then heating from 100 ℃ to 200 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 5 min.
And then, rapidly placing the glass plate carrying the sample in ice water for quenching for about 1min, removing the film, paving the film on aluminum foil paper, placing the aluminum foil paper in an oven for drying again, setting the temperature to be 70 ℃, and preserving the heat for 6 h.
Thirdly, preparing a PEI/PVDF polymer film
(1) 1.602g of polyvinylidene fluoride and 0.135g of polyetherimide were weighed out for further use. 9ml of N-methyl-2-pyrrolidone was measured and placed in a 5ml beaker. Setting the temperature of a magnetic stirrer to be 75 ℃, after the temperature is stabilized at 75 ℃, placing a beaker in the stirrer to slowly stir, adding weighed polyetherimide after 10min, continuing to slowly stir, adding PVDF particles after PEI particles are completely dissolved, quickly stirring for 5h, and then slowly stirring at room temperature overnight.
(2) And cleaning and drying the high-temperature resistant glass plate by using alcohol and deionized water for later use. Setting the height of a scraper to be 10 mu m, placing a proper amount of stirred solution on a glass plate for film scraping and molding, and then placing the glass plate in a blast type drying box for heat preservation;
(3) the heat preservation is divided into two stages:
firstly, heating from room temperature to 100 ℃ at a heating speed of 1 ℃/min, and keeping the temperature for 4 h;
then heating from 100 ℃ to 200 ℃ at the heating rate of 2 ℃/min, and preserving the heat for 5 min.
And then, rapidly placing the glass plate carrying the sample in ice water for quenching for about 1min, removing the film, paving the film on aluminum foil paper, placing the aluminum foil paper in an oven for drying again, setting the temperature to be 70 ℃, and preserving the heat for 6 h.
Fourthly, preparing a PEI-PEI/PVDF-PVDF three-layer polymer-based composite film
As shown in figure 1, Pure PEI, PEI/PVDF and Pure PVDF films with the same size are cut, and the three films are hot-pressed together under the conditions that the temperature is 180 ℃, the pressure is 8MPa and the heat preservation time is 30min, so that the dielectric composite material is obtained.
The results of examining the relative properties of the dielectric composite material prepared in the above examples are shown in fig. 2, fig. 3, fig. 4 and fig. 5, wherein, in fig. 2, (a) is a Scanning Electron Microscope (SEM) of a cross section of the three-layer film, and it can be clearly seen from the SEM that the three-layer film material is tightly hot-pressed together, and there are no obvious defects such as cracks and voids, and the PEI layer is the uppermost layer, and there is no obvious interface structure due to the very good flexibility of the PEI/PVDF layer and the PVDF layer. Fig. 2 (b) shows a fourier infrared spectrum of the three-layer film.
Fig. 3 (a) shows the dielectric constant dispersion curve of the three-layer composite, and it can be seen that the three-layer composite exhibits a moderate dielectric constant. Fig. 3 (b) is a dielectric loss dispersion curve of the two-layer composite material, and we can intuitively see that the three-layer composite material shows lower dielectric loss, and the lower loss has a great influence on the charge-discharge efficiency of the composite material.
The breakdown strength diagram of the three-layer composite material in fig. 4 visually shows the advantages of the two-layer material compared with the single-layer material and the two-layer material, in fig. 4, (a) the breakdown strength of the PEI-PEI/PVDF-PVDF three-layer composite material is shown, in fig. 4, (b) we can clearly see that the breakdown strength of the three-layer material is greatly improved, the breakdown strength of PEI-20 vol% PEI/PVDF is 758kV/mm, which is even higher than that of pure polymers PVDF (466kV/mm) and PEI (618 v/mm), and it can be seen that the breakdown strength of the three-layer composite material is comparable to that of the pure polymer, which has great benefits on the energy storage performance of the composite material.
Fig. 5 (a) is a discharge energy density graph of a three-layer composite material, in which the energy storage density of the two-layer composite material is greatly increased compared to pure polymer PEI; compared with pure polymer PVDF, the double-layer composite material has excellent high-electric-field-intensity energy storage advantage, and the highest energy storage density can reach10.3J/cm3Left and right; FIG. 5 (b) is a graph of the charge-discharge efficiency of a three-layer composite material, and it can be seen that the three-layer composite material exhibits higher energy storage efficiency (compared to a single-layer pure polymer PVDF) (the three-layer composite material is intuitively)>91％)。
The parts which are not described in the invention can be realized by taking the prior art as reference.
It should be noted that: any equivalents or obvious modifications thereof which may occur to persons skilled in the art and which are given the benefit of this description are deemed to be within the scope of the invention.
Claims (9)
1. An asymmetric three-layer structure full polymer dielectric composite material is characterized in that: the multilayer composite film comprises a first layer body, a second layer body and a third layer body from bottom to top, wherein the first layer body is a pure polyvinylidene fluoride film, the second layer body is a mixed polyetherimide/polyvinylidene fluoride film, and the third layer body is a pure polyetherimide film; the first layer body, the second layer body and the third layer body are the same in size and thickness.
2. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 1, wherein: the first layer body, the second layer body and the third layer body are prepared by a hot pressing method, and the hot pressing method adopts the following process conditions: the temperature is 170-190 ℃, the pressure is 7.5-8.5 MPa, and the time is 20-40 min.
3. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 2, wherein: the first layer body, the second layer body and the third layer body are all prepared by a tape casting method.
4. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 2, wherein: the preparation method of the first layer body comprises the following steps:
firstly, weighing polyvinylidene fluoride, adding the polyvinylidene fluoride into a container filled with N-methyl-2-pyrrolidone, stirring at 75 ℃, and continuing stirring after the polyvinylidene fluoride is completely dissolved to obtain a polyvinylidene fluoride solution;
secondly, placing the polyvinylidene fluoride solution on a clean glass plate for film scraping and forming, then placing the polyvinylidene fluoride solution in a blast type drying box for heat preservation, wherein the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
5. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 4, wherein: the height of a scraper used in the second step of film scraping and forming is 10 mu m; in the third step, the drying temperature of the oven is 70 ℃, and the temperature is kept for 6 h.
6. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 2, wherein: the preparation method of the second layer body comprises the following steps:
weighing polyvinylidene fluoride and polyetherimide, adding the polyetherimide into a container filled with N-methyl-2-pyrrolidone, dissolving the polyetherimide, adding the polyvinylidene fluoride into the container, and stirring to obtain a mixed solution;
the second step, will the mixed solution place the plastic film of scraping in clean glass board and take shape, place the heat preservation in the blast type drying cabinet afterwards, the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
7. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 6, wherein: in the first step, stirring is carried out at a temperature of 75 ℃; the height of a scraper used in the second step of film scraping and forming is 10 mu m; in the third step, the drying temperature of the oven is 70 ℃, and the temperature is kept for 6 h.
8. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 2, wherein: the preparation method of the third layer body comprises the following steps:
firstly, weighing polyetherimide, adding the polyetherimide into a container filled with N-methyl-2-pyrrolidone, stirring at 75 ℃, and continuing stirring after the polyetherimide is completely dissolved to obtain a polyetherimide solution;
secondly, the polyetherimide solution is placed on a clean glass plate for film scraping and molding, and then is placed in a blast type drying box for heat preservation, and the heat preservation is divided into two stages:
the first stage is as follows: heating from room temperature to 100 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 4 h;
and a second stage: heating from 100 deg.C to 200 deg.C at a rate of 2 deg.C/min, and maintaining for 5 min;
and thirdly, quickly placing the glass plate loaded with the sample obtained in the second step into ice water for quenching, then removing the film, flatly paving the film on aluminum-foil paper, and placing the aluminum-foil paper into an oven for drying to obtain the glass plate.
9. The method for preparing an asymmetric three-layer structure all-polymer dielectric composite material as claimed in claim 2, wherein: the hot pressing method adopts the following process conditions: the temperature is 180 ℃, the pressure is 8MPa, and the time is 30 min.
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