CN111961241B - Preparation method of high-energy-storage low-loss double-layer composite film - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000004146 energy storage Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 82
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 82
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 238000005266 casting Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229920000131 polyvinylidene Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 27
- 239000003990 capacitor Substances 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 239000012528 membrane Substances 0.000 abstract description 11
- 230000010287 polarization Effects 0.000 abstract description 8
- 230000020169 heat generation Effects 0.000 abstract description 4
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 93
- 239000010410 layer Substances 0.000 description 48
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 239000002355 dual-layer Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
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- 238000007792 addition Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000010248 power generation Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
- 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
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08J2427/00—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
- C08J2427/02—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
- C08J2427/12—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
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The application discloses a preparation method of a double-layer composite film with high energy storage and low loss, which comprises the following steps: selecting a high dielectric constant material, and preparing into a solution: dissolving a high dielectric constant material in an organic solvent, and stirring until the material is completely dissolved; preparing a polyetherimide solution: uniformly casting the polyetherimide solution on a substrate, and drying to obtain a polyetherimide film; uniformly casting a layer of high dielectric constant material solution on the surface of the polyetherimide film, and drying to obtain the double-layer composite film; the invention has the beneficial effects that: the PVDF-based material of the double-layer composite membrane can improve the dielectric constant and breakdown field strength of a Polyetherimide (PEI) membrane, so that the double-layer composite membrane can obtain higher energy storage density; the PEI film can reduce dielectric loss by inhibiting polarization relaxation and leakage current of the PVDF-based material, solve the problem of overhigh heat generation during the operation of the film capacitor and enable the application of the film capacitor with high energy storage to be possible.
Description
Technical Field
The application belongs to the field of capacitors, and particularly relates to a preparation method of a double-layer composite film with high energy storage and low loss.
Background
The organic film capacitor can stably work under the application scenes of ultrahigh voltage, ultrahigh current and ultrahigh power, is widely applied to a plurality of fields of national defense and military, basic scientific research and civil electric power, and is a basic element of new-concept weapons, new energy automobiles and renewable energy power generation systems. However, at present, the most used polypropylene (abbreviated as PP) dielectric films are difficult to meet the requirement of higher and higher energy storage density due to low dielectric constant, and materials with strong polarization (such as polyvinylidene fluoride and the like) cannot be put into practical application due to the defect of high dielectric loss. In order to meet the urgent requirements of various fields on a novel high-energy-storage-density film capacitor, the invention provides an application scheme, which can ensure that the dielectric loss of the polymer dielectric film is lower than a certain threshold value while improving the dielectric constant of the polymer dielectric film, thereby achieving the purpose of practical application.
Disclosure of Invention
The invention aims to provide a preparation method of a high-energy-storage low-loss double-layer composite film with high dielectric constant and low dielectric loss.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a double-layer composite film with high energy storage and low loss, which comprises the following steps:
(1) selecting a high dielectric constant material, and preparing into a solution: dissolving a high dielectric constant material in an organic solvent, and stirring until the material is completely dissolved; preferably, the high dielectric constant material is a material with a dielectric constant > 12;
(2) preparing a polyetherimide solution: dissolving polyetherimide in an organic solvent, heating and stirring until the polyetherimide is completely dissolved;
(3) uniformly casting the polyetherimide solution on a substrate, and drying to obtain a polyetherimide film; and uniformly casting a layer of high dielectric constant material solution on the surface of the polyetherimide film, and drying to obtain the double-layer composite film.
As a preferred embodiment, in step (1), the high dielectric constant material is polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene, preferably, the organic solvent is DMF, and more preferably, the concentration of the prepared solution is 8% to 17%.
The concentration of the composite film is selected to be 8% -17%, and the inventor obtains the composite film through a large amount of experimental research, and the composite film has good film forming property in the concentration range, so that the high dielectric and low loss performance of the obtained double-layer composite film is ensured.
Polyvinylidene fluoride (PVDF) based materials mostly have ferroelectric properties, and have high dielectric constant due to strong polarization under an electric field, but due to relaxation properties of polarization, namely, polarization cannot respond to changes of the electric field in time, PVDF based materials have high dielectric loss properties, and in the practical application process of a film capacitor, due to poor heat dissipation of an organic film, heat generated by dielectric loss of a dielectric layer is difficult to dissipate, so that the capacitor is easily damaged.
The PVDF-based material and Polyetherimide (PEI) form a double-layer membrane structure, on one hand, the PVDF-based material can improve the dielectric constant and breakdown field intensity of the PEI membrane, and the double-layer composite membrane can obtain higher energy storage density according to an energy storage density formula; on the other hand, the dielectric loss can be reduced by inhibiting the polarization relaxation and the leakage current of the PVDF-based material, the problem of overhigh heat generation during the operation of the thin film capacitor is solved, and the application of the thin film capacitor with high energy storage is possible.
In the above method for preparing a double-layer composite membrane with high energy storage and low loss, as a preferred embodiment, in the step (2), the organic solvent is NMP, preferably, the heating temperature is 40 to 80 ℃, and more preferably, the concentration of the polyetherimide solution is 10 to 18%.
NMP refers to N-methylpyrrolidone, is a colorless transparent oily liquid, has little amine smell, and has low volatility, good thermal stability and chemical stability.
The concentration of the polyetherimide solution is 10% -18%, and through a great deal of experimental study, if the concentration of the polyetherimide solution is higher or lower than the value, a film is not easy to form.
As a preferred embodiment, in the step (3), the substrate is a quartz substrate, preferably, the temperature of the two times of drying is 40-80 ℃, and the time of the two times of drying is 10-18 h. The organic solvent is difficult to be completely removed when the drying temperature is too low, and pores are generated on the film when the volatilization speed of the organic solvent is too high when the drying temperature is too high.
As a preferred embodiment, in step (3), the ratio of the thickness of the polyetherimide film in the double-layer composite film to the thickness of the high-dielectric-constant material film is 1: 2-8.
As a preferred embodiment, in the step (3), the thickness of the obtained double-layer composite film is 5-20 um.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the high-energy-storage low-loss double-layer composite film comprises a material (PVDF-based material) with the dielectric constant larger than 12 and polyetherimide, wherein the PVDF-based material and the polyetherimide are complementary, and the PVDF-based material can improve the dielectric constant and breakdown field strength of a Polyetherimide (PEI) film, so that the double-layer composite film can obtain higher energy storage density; the PEI film can reduce dielectric loss by inhibiting polarization relaxation and leakage current of the PVDF-based material, solve the problem of overhigh heat generation during the operation of the film capacitor and enable the application of the film capacitor with high energy storage to be possible.
The preparation method of the high-energy-storage low-loss double-layer composite membrane is simple in structure and easy to realize in the processing and production process, and the used raw materials, namely the PVDF-based material and the PEI material, are easy to obtain and are suitable for engineering application.
Drawings
FIG. 1: a dielectric constant variation curve chart along with the frequency of the electric field;
FIG. 2: a graph of dielectric loss versus electric field frequency;
FIG. 3: weibull distribution plot of breakdown.
Detailed Description
In order to make the technical solutions in the embodiments of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to examples, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The PVDF-based material contained in the preparation method of the high-energy-storage low-loss double-layer composite film can improve the dielectric constant and breakdown field intensity of the PEI film, and the double-layer composite film can obtain higher energy storage density according to an energy storage density formula; the PEI film can reduce dielectric loss by inhibiting polarization relaxation and leakage current of the PVDF-based material, solve the problem of overhigh heat generation during the operation of the film capacitor and enable the application of the film capacitor with high energy storage to be possible.
The PVDF-based material selected by the invention has the dielectric constant of 33. Polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene used in the present invention was purchased from Sigma Aldrich chemical company and had a molecular weight of about 800000.
The energy storage density formula is: d-1/2 epsilon0εrE2
In the formula: d represents the energy storage density of the capacitor; epsilon0Is a vacuum dielectric constant; epsilonrIs the relative permittivity of the medium; and E is the working field strength of the capacitor.
Example 1
A preparation method of a double-layer composite film with high energy storage and low loss comprises the following steps:
(1) selecting 0.8g of polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material, dissolving the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material in 9.2g of organic solvent DMF, and stirring until the material is completely dissolved to prepare a PVDF-based material solution with the concentration of 8%;
(2) preparing a polyetherimide solution: dissolving 1g of polyetherimide in 9g of NMP (organic solvent), and stirring at the heating temperature of 40 ℃ until the polyetherimide is completely dissolved to prepare a 10% polyetherimide solution;
(3) uniformly casting the polyetherimide solution on a quartz substrate, and drying for 10 hours at the temperature of 40 ℃ to obtain a polyetherimide film with the thickness of 4 um; uniformly casting a layer of PVDF-based material solution on the surface of the polyetherimide film, and drying for 18h at the temperature of 40 ℃ to obtain the double-layer composite film with the thickness of 12 um.
Example 2
A preparation method of a double-layer composite film with high energy storage and low loss comprises the following steps:
(1) selecting 1g of polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material, dissolving the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material in 9g of organic solvent DMF, and stirring until the material is completely dissolved to prepare a PVDF-based material solution with the concentration of 10%;
(2) preparing a polyetherimide solution: dissolving 1.2g of polyetherimide in 8.8g of NMP (N-methyl pyrrolidone) as an organic solvent, and stirring the solution at a heating temperature of 60 ℃ until the polyetherimide is completely dissolved to prepare a 12% polyetherimide solution;
(3) uniformly casting the polyetherimide solution on a quartz substrate, and drying for 16h at the temperature of 50 ℃ to obtain a polyetherimide film with the thickness of 3 um; uniformly casting a layer of PVDF-based material solution on the surface of the polyetherimide film, and drying for 12 hours at the temperature of 50 ℃ to obtain the double-layer composite film with the thickness of 12 um.
Example 3
A preparation method of a double-layer composite film with high energy storage and low loss comprises the following steps:
(1) selecting 1.5g of polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material, dissolving the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material in 8.5g of organic solvent DMF, and stirring until the material is completely dissolved to prepare a PVDF-based material solution with the concentration of 15%;
(2) preparing a polyetherimide solution: dissolving 1.5g of polyetherimide in 8.5g of NMP (N-methyl pyrrolidone) as an organic solvent, and stirring the solution at a heating temperature of 60 ℃ until the polyetherimide is completely dissolved to prepare a polyetherimide solution with the concentration of 15%;
(3) uniformly casting the polyetherimide solution on a quartz substrate, and drying for 15h at the temperature of 70 ℃ to obtain a polyetherimide film with the thickness of 2.5 um; uniformly casting a layer of PVDF-based material solution on the surface of the polyetherimide film, and drying for 12 hours at the temperature of 70 ℃ to obtain the double-layer composite film with the thickness of 17.5 um.
Example 4
A preparation method of a double-layer composite film with high energy storage and low loss comprises the following steps:
(1) selecting 1.7g of polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material, dissolving the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene material in 8.3g of organic solvent DMF, and stirring until the material is completely dissolved to prepare a PVDF-based material solution with the concentration of 17%;
(2) preparing a polyetherimide solution: dissolving 1.8g of polyetherimide in 8.2g of NMP (N-methyl pyrrolidone) as an organic solvent, and stirring the solution at a heating temperature of 65 ℃ until the polyetherimide is completely dissolved to prepare a polyetherimide solution with the concentration of 18 percent;
(3) uniformly casting the polyetherimide solution on a quartz substrate, and drying for 18h at the temperature of 80 ℃ to obtain a polyetherimide film with the thickness of 1.5 um; uniformly casting a layer of PVDF-based material solution on the surface of the polyetherimide film, and drying for 10 hours at the temperature of 80 ℃ to obtain the double-layer composite film with the thickness of 13.5 um.
Comparative example 1
The preparation method of the double-layer composite film with high energy storage and low loss in the comparative example 1 is different from the double-layer composite film in the example 3 in that: the thickness of the polyetherimide film contained in the double-layer composite film obtained in the comparative example 1 is 6um, and the thickness of the PVDF-based material solution film contained in the double-layer composite film is 4 um.
Comparative example 2
The preparation method of the double-layer composite film with high energy storage and low loss in the comparative example 2 is different from the double-layer composite film in the example 3 in that: the thickness of the polyetherimide film contained in the double-layer composite film obtained in comparative example 1 was 1.5um, and the thickness of the film of the PVDF-based material solution contained was 13.5 um.
1. The dielectric constant research of the preparation method of the high-energy-storage low-loss double-layer composite film
The research method comprises the following steps: plating aluminum electrodes on two surfaces of the film by using a vacuum coating machine, measuring the capacitance of the capacitor by using an impedance analyzer, calculating the relative dielectric constant of the dielectric layer according to a formula, and drawing a change curve by using Origin;
the above formula is: c ═ epsilon0εrS)/4kπd
Remarking: c is the capacitance of the capacitor, epsilon0Is a vacuum dielectric constant of ∈rIs the relative dielectric constant of the dielectric, S is the area of the capacitor, and d is the thickness of the capacitor.
In the figure: p (VDF-TrFE-CFE) represents a polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film;
PEI stands for polyetherimide film;
p (VDF-TrFE-CFE)/PEI stands for composite membrane
The results of the study are shown in FIG. 1, from which it can be seen that: the relative dielectric constant of PEI is about 4.1, while the relative dielectric constant of the double-layer composite film of the invention is about 12.7, which is about three times that of PEI, and thus polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene (P (VDF-TrFE-CFE)) has an obvious effect of improving the dielectric constant of the PEI film.
2. The dielectric loss research of the preparation method of the high-energy-storage low-loss double-layer composite film is carried out.
The research method comprises the following steps: and (3) plating aluminum electrodes on two surfaces of the film by using a vacuum coating machine, directly measuring the change of the dielectric loss along with the change of the frequency of the electric field by using an impedance analyzer, and drawing a change curve by using Origin.
The results of the study are shown in FIG. 2, from which it can be seen that: the dielectric loss of the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene can reach 6.18%, and the dielectric loss of the double-layer composite film is 1.86%, namely the PEI can inhibit the relaxation property of the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene, so that the dielectric loss of the PEI is reduced.
3. Breakdown field intensity research of preparation method of high-energy-storage low-loss double-layer composite film
The research method comprises the following steps: and measuring the breakdown voltage of each sampling point by using a breakdown tester, calculating the breakdown field intensity of each point according to a formula E (U/d), and drawing the Weibull distribution of the breakdown electric field by using Origin, thereby obtaining the breakdown field intensity of the film.
The results of the study are shown in FIG. 3: as can be seen in fig. 3: the breakdown field intensity of the PEI is about 439.4MV/m, the breakdown field intensity of the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene is about 583.6MV/m, and the breakdown field intensity of the double-layer composite membrane is about 589.7MV/m, namely the PEI and the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene are compounded, so that the breakdown field intensities can be mutually improved, and the breakdown field intensity of the double-layer composite membrane can be improved; the energy storage density of the thin film capacitor is generally determined by the relative dielectric constant of the dielectric layer and the breakdown field strength, and the increase of the breakdown field strength also means the increase of the energy storage density of the double-layer composite film.
4. The effect of different thickness ratios of the PEI film and the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film on the energy storage density of the dual-layer composite film is shown in table 1:
TABLE 1 influence of PEI film and polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film having different thickness ratios on energy storage density of a dual-layer composite film
As can be seen from table 1, the thickness ratio of the PEI film to the pvdf-trifluoroethylene-chlorofluoroethylene film affects the energy storage density of the dual-layer composite film. When the thickness ratio of the PEI film to the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film is 1: when the temperature is within the range of 2-8, the obtained double-layer composite film has higher energy storage density. When the thickness ratio of the PEI film to the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film is more than 1: when 2, the energy storage density is obviously reduced; when the thickness ratio of the PEI film to the polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene film is less than 1: and 8, the energy storage density of the obtained composite film is obviously reduced due to the obvious reduction of the charge-discharge efficiency.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (2)
1. A preparation method of a double-layer composite film with high energy storage and low loss is characterized by comprising the following steps:
(1) selecting a high dielectric constant material, and preparing into a solution: dissolving a high dielectric constant material in an organic solvent, and stirring until the material is completely dissolved; the high dielectric constant material is a material with a dielectric constant more than 12; the high dielectric constant material is polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene, the organic solvent is DMF, and the concentration of the prepared solution is 8-17%;
(2) preparing a polyetherimide solution: dissolving polyetherimide in an organic solvent, heating and stirring until the polyetherimide is completely dissolved; the organic solvent is NMP, the heating temperature is 40-80 ℃, and the concentration of the polyetherimide solution is 10-18%;
(3) uniformly casting the polyetherimide solution on a substrate, and drying to obtain a polyetherimide film; uniformly casting a layer of high dielectric constant material solution on the surface of the polyetherimide film, and drying to obtain the double-layer composite film; the thickness ratio of the polyetherimide film in the double-layer composite film to the high-dielectric-constant material film is 1: 2-8, and the thickness of the obtained double-layer composite film is 5-20 μm.
2. The method for preparing the double-layer composite film with high energy storage and low loss according to claim 1, wherein in the step (3), the substrate is a quartz substrate, the temperature of the two times of drying is 40-80 ℃, and the time of the two times of drying is 10-18 h.
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| CN113045784A (en) * | 2021-03-16 | 2021-06-29 | 佛山(华南)新材料研究院 | Preparation method of high-temperature-resistant dielectric film |
| CN115304810A (en) * | 2022-09-02 | 2022-11-08 | 乌镇实验室 | Preparation method of PEI/MOF/PEI composite membrane material with sandwich structure |
| CN117683350B (en) * | 2023-11-21 | 2024-05-31 | 哈尔滨理工大学 | Polyetherimide-based energy storage composite medium film and preparation method and application thereof |
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| KR20130021079A (en) * | 2011-08-22 | 2013-03-05 | 전자부품연구원 | Separator for electrochemical energy storage device and manufacturing method thereof |
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| CN111361157A (en) * | 2020-03-03 | 2020-07-03 | 中国海洋大学 | Double-layer polymer composite material, preparation method and application thereof |
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| CN110070991A (en) * | 2018-09-25 | 2019-07-30 | 南方科技大学 | All-polymer multilayer structure composite material and preparation method and application thereof |
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| KR20130021079A (en) * | 2011-08-22 | 2013-03-05 | 전자부품연구원 | Separator for electrochemical energy storage device and manufacturing method thereof |
| CN110862683A (en) * | 2019-12-23 | 2020-03-06 | 华中科技大学 | High-energy-storage-density dielectric composite multilayer film and preparation method thereof |
| CN111361157A (en) * | 2020-03-03 | 2020-07-03 | 中国海洋大学 | Double-layer polymer composite material, preparation method and application thereof |
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| "Ultrahigh discharge efficiency and improved energy density in rationally designed bilayer polyetherimide-BaTiO3/P(VDF-HFP) composites";Sun Liang等;《JOURNAL OF MATERIALS CHEMISTRY A》;20200302;第8卷(第11期);第 5750-5757页 * |
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