CN114559719A - High-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film and preparation method thereof - Google Patents
High-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film and preparation method thereof Download PDFInfo
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- 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
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- 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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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
A high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film and a preparation method thereof relate to the technical field of composite film preparation. The invention aims to solve the problem that the traditional composite material film cannot have both high dielectric constant and high breakdown strength. The method comprises the following steps: and (3) placing the P (VDF-HFP) film between two layers of FPE films, carrying out hot-pressing treatment, and finally cooling to obtain the FPE and P (VDF-HFP) multi-layer structure composite film with high breakdown and high energy storage. The invention can obtain the FPE and P (VDF-HFP) based multi-layer structure composite film with high breakdown and high energy storage and the preparation method thereof.
Description
Technical Field
The invention relates to the technical field of composite film preparation, in particular to a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer composite film and a preparation method thereof.
Background
In order to meet the increasing demands of modern electronic and power systems, the development of advanced energy storage materials is pressing. Polymer dielectrics are currently the material of choice for high energy density capacitors due to their high breakdown strength and excellent mechanical properties. However, the energy density of polymer dielectrics is limited by their inherently low dielectric constant, and in order to increase the energy density of polymers, a great deal of research has been conducted, such as the introduction of inorganic fillers having a high dielectric constant into a polymeric matrix to form polymer composites. However, the increase in dielectric constant brought about by the introduction of high-dielectric-constant fillers is generally at the expense of a reduction in the breakdown field strength thereof, and therefore the increase in energy density is very limited. In recent years, the preparation of a multilayer structure from a polymer dielectric becomes a new method for solving the contradiction between high dielectric constant and high breakdown field strength existing in a single-layer composite film, so that the energy storage performance of the capacitor is remarkably improved.
Disclosure of Invention
The invention aims to solve the problem that the traditional composite material film cannot have high dielectric constant and high breakdown strength, and provides an FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film with high breakdown and high energy storage and a preparation method thereof.
The composite film comprises a layer of P (VDF-HFP) film and two layers of FPE films, wherein the P (VDF-HFP) film is arranged between the two layers of the FPE films, and the P (VDF-HFP) film and the two layers of the FPE films are combined through a hot pressing process.
A preparation method of a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film comprises the following steps:
firstly, adding fluorene polyester into a methyl pyrrolidone solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain an FPE solution; uniformly coating the FPE solution on one surface of a pretreated substrate, then carrying out gradient heating and heat preservation on the substrate, cooling to room temperature, and stripping a film on the substrate to obtain an FPE film;
secondly, adding P (VDF-HFP) into a dimethylformamide solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain a P (VDF-HFP) solution; uniformly coating a P (VDF-HFP) solution on one surface of a pretreated substrate, heating the substrate to 75-80 ℃, preserving heat at 75-80 ℃ for 12-15 h, cooling to room temperature, and peeling off the film on the substrate to obtain a P (VDF-HFP) film;
and thirdly, placing the P (VDF-HFP) film between the two FPE films, carrying out hot-pressing treatment, and finally cooling to obtain the FPE and P (VDF-HFP) multi-layer structure composite film with high breakdown and high energy storage.
The application of the FPE and P (VDF-HFP) -based multilayer composite film with high breakdown and high energy storage in the super capacitor.
The invention has the beneficial effects that:
(1) the invention relates to a preparation method of a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer composite film, which is prepared by taking FPE as an insulating layer and P (VDF-HFP) as a polarizing layer through a hot-pressing method. According to the series capacitance equivalent model, the electric fields applied to the two sides of the multilayer structure composite film are redistributed in the multilayer structure composite film, so that the FPE with low dielectric constant and high breakdown field strength bears higher applied voltage, and P (VDF-HFP) which is easier to breakdown is protected. In addition, in the multilayer structure composite film, the macroscopic interface between layers hinders the growth of a breakdown path. The electric field redistribution in the composite material and the blocking effect of a macroscopic interface on a breakdown path enable the multilayer structure composite film to have the breakdown field intensity higher than that of pure FPE and P (VDF-HFP), and finally the multilayer structure composite film greatly improves the breakdown performance and has ultrahigh energy density due to excellent breakdown strength. In addition, the FPE has an extremely high charge and discharge efficiency due to its low leakage current, so that the charge and discharge efficiency of the multi-layered structure composite thin film is significantly improved compared to pure P (VDF-HFP).
(2) The FPE and P (VDF-HFP) based multilayer composite material film prepared by the process has excellent dielectric property, breakdown property, energy storage property, heat conduction and heat resistance, provides a new material for a high-performance super capacitor, and can be widely applied to advanced fields of electric, electronic, new energy automobiles and the like. The preparation equipment has simple process, easy implementation, low cost, environmental protection and no pollution, and provides a good strategy for developing advanced polymer capacitors.
The invention can obtain the FPE and P (VDF-HFP) based multi-layer structure composite film with high breakdown and high energy storage and the preparation method thereof.
Drawings
FIG. 1 is a scanning electron microscope cross-sectional view of a composite film of FPE and P (VDF-HFP) multi-layer structure of example 3 in which the volume fraction of P (VDF-HFP) is 55.6%, wherein A represents the FPE film and B represents the P (VDF-HFP) film.
Fig. 2 is an X-ray diffraction chart of the FPE and P (VDF-HFP) -based multi-layered structure composite film prepared in examples 1 to 3 and the FPE and P (VDF-HFP) thin films prepared in comparative example 1, a represents the P (VDF-HFP) thin film in comparative example 1, b represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 3, c represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 2, d represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 1, and e represents the FPE thin film in comparative example 1.
FIG. 3 is a direct current breakdown Weibull distribution diagram of the FPE and P (VDF-HFP) -based multi-layer structure composite film prepared in examples 1-3 with the FPE film and the P (VDF-HFP) film prepared in comparative example 1, ● denotes the FPE film in comparative example 1, ■ denotes the P (VDF-HFP) film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
a multilayer composite film of FPE and P (VDF-HFP) in example 3 is shown.
Fig. 4 is a graph showing the results of dielectric constant tests of the FPE and P (VDF-HFP) -based multi-layered structure composite films prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
Fig. 5 is a graph showing the dielectric loss test results of the FPE and P (VDF-HFP) -based multi-layered structure composite films prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the film of example 3 is a composite film of FPE and P (VDF-HFP) -based multilayer structure, and ■ is a film of comparative example 1, P (VDF-HFP).
Fig. 6 is a graph showing the test results of the FPE and P (VDF-HFP) -based multi-layered structure composite film prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
Fig. 7 is a result of a charge and discharge efficiency test of the FPE and P (VDF-HFP) -based multi-layered structure composite film prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a high-breakdown and high-energy-storage FPE (flat panel display) and P (VDF-HFP) -based multilayer composite film, which consists of a layer of P (VDF-HFP) film and two layers of FPE films, wherein the P (VDF-HFP) film is arranged between the two layers of FPE films, and the P (VDF-HFP) film and the two layers of FPE films are combined through a hot pressing process.
The second embodiment is as follows: the embodiment of the invention relates to a preparation method of a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer composite film, which comprises the following steps:
firstly, adding fluorene polyester into a methyl pyrrolidone solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain an FPE solution; uniformly coating the FPE solution on one surface of a pretreated substrate, then carrying out gradient heating and heat preservation on the substrate, cooling to room temperature, and stripping a film on the substrate to obtain an FPE film;
secondly, adding P (VDF-HFP) into a dimethylformamide solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain the P (VDF-HFP) solution; uniformly coating a P (VDF-HFP) solution on one surface of a pretreated substrate, heating the substrate to 75-80 ℃, preserving heat at 75-80 ℃ for 12-15 h, cooling to room temperature, and peeling off the film on the substrate to obtain a P (VDF-HFP) film;
and thirdly, placing the P (VDF-HFP) film between the two FPE films, carrying out hot-pressing treatment, and finally cooling to obtain the FPE and P (VDF-HFP) multi-layer structure composite film with high breakdown and high energy storage.
The beneficial effects of the embodiment are as follows:
(1) in this embodiment, a method for preparing a high breakdown and high energy storage FPE and P (VDF-HFP) -based multilayer composite film is provided, in which FPE is used as an insulating layer, and P (VDF-HFP) is used as a polarizing layer, and the composite film is prepared by a hot pressing method. According to the series capacitance equivalent model, the electric fields applied to the two sides of the multilayer structure composite film are redistributed in the multilayer structure composite film, so that the FPE with low dielectric constant and high breakdown field strength bears higher applied voltage, and P (VDF-HFP) which is easier to breakdown is protected. In addition, in the multilayer structure composite film, the macroscopic interface between layers hinders the growth of a breakdown path. The electric field redistribution in the composite material and the blocking effect of a macroscopic interface on a breakdown path enable the multilayer structure composite film to have the breakdown field intensity higher than that of pure FPE and P (VDF-HFP), and finally the multilayer structure composite film greatly improves the breakdown performance and has ultrahigh energy density due to excellent breakdown strength. In addition, the FPE has an extremely high charge and discharge efficiency due to its low leakage current, so that the charge and discharge efficiency of the multi-layered structure composite thin film is significantly improved compared to pure P (VDF-HFP).
(2) The FPE and P (VDF-HFP) based multilayer composite material film prepared by the process has excellent dielectric property, breakdown property, energy storage property, heat conduction and heat resistance, provides a new material for a high-performance super capacitor, and can be widely applied to advanced fields of electric, electronic, new energy automobiles and the like. The preparation equipment of the embodiment has the advantages of simple process, easy implementation, low cost, environmental protection and no pollution, and provides a good strategy for developing advanced polymer capacitors.
The third concrete implementation mode: the second embodiment differs from the first embodiment in that: the ratio of the mass of the fluorene polyester to the volume of the methyl pyrrolidone solution in the first step is (0.4-0.5) g: (3.5-4) mL.
The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the second or third differences from the present embodiment are as follows: the pretreated substrate in the first step is processed according to the following steps: cleaning the substrate with clear water for 3-5 times, then washing with deionized water for 3-5 times, then cleaning with absolute ethyl alcohol for 3-5 times, and finally drying at 75-80 ℃ for 12-15 h to obtain a pretreated substrate, wherein the substrate is a glass plate.
The other steps are the same as those in the second or third embodiment.
The fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: the step of gradient heating and heat preservation in the step one: the substrate is heated to 80 ℃ and kept at 80 ℃ for 12h, then heated to 120 ℃ and kept at 120 ℃ for 12 h.
The other steps are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: the thickness of the FPE film in the first step is 4 μm, 6 μm, 8 μm or 18 μm, and the thickness of the P (VDF-HFP) film in the second step is 2 μm, 6 μm, 10 μm or 18 μm.
The other steps are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: in the second step, the ratio of the mass of P (VDF-HFP) to the volume of the dimethylformamide solution is (1-1.2) g: (7-8) mL.
The other steps are the same as those in the second to sixth embodiments.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: the step of hot pressing process treatment in the step three: the method comprises the steps of putting a P (VDF-HFP) film between two layers of FPE films, then putting between two layers of iron plates, putting the iron plates in a flat vulcanizing machine at 160-170 ℃ for heat preservation for 0.5-1 h, finally carrying out hot pressing for 1-2 h under the pressure of 10-15 MPa, and cooling after the hot pressing is finished to obtain the composite film with the high-breakdown and high-energy-storage FPE and P (VDF-HFP) multi-layer structure, wherein the volume fraction of the P (VDF-HFP) film in the composite film with the high-breakdown and high-energy-storage FPE and P (VDF-HFP) multi-layer structure is 11.1%, 33.3% or 55.6%.
The other steps are the same as those in the second to seventh embodiments.
The specific implementation method nine: the second to eighth differences from the first embodiment are as follows: and (3) mechanically stirring in the first step and the second step by adopting a magnetic stirrer, wherein the stirring speed is 150-300 r/min.
The other steps are the same as those in the second to eighth embodiments.
The detailed implementation mode is ten: the embodiment of the invention relates to application of a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer composite film, and the FPE-P (VDF-HFP) -based multilayer composite film is applied to a super capacitor.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a high-breakdown and high-energy-storage FPE (FPE) -P (VDF-HFP) -based multilayer structure composite film comprises the following steps:
firstly, adding fluorene polyester into a methyl pyrrolidone solution, and mechanically stirring for 6 hours at a stirring speed of 150-300 r/min at a temperature of 25 ℃ to obtain an FPE solution, wherein the ratio of the mass of the fluorene polyester to the volume of the methyl pyrrolidone solution is 0.4 g: 3.5 mL; uniformly coating the FPE solution on one surface of a pretreated substrate, heating the substrate to 80 ℃, preserving heat at 80 ℃ for 12h, heating to 120 ℃, preserving heat at 120 ℃ for 12h, cooling to room temperature, and peeling off the film on the substrate to obtain an FPE film;
the pretreated substrate was processed as follows: the method comprises the following steps of cleaning a substrate for 5 times by using clear water, then washing for 5 times by using deionized water, then cleaning for 5 times by using absolute ethyl alcohol, and finally drying for 12 hours at 80 ℃ to obtain a pretreated substrate, wherein the substrate is a glass plate.
Secondly, adding P (VDF-HFP) into the dimethylformamide solution, and mechanically stirring for 6 hours at the temperature of 25 ℃ and at the stirring speed of 150-300 r/min to obtain the P (VDF-HFP) solution, wherein the ratio of the mass of the P (VDF-HFP) to the volume of the dimethylformamide solution is 1 g: 7 mL; uniformly coating a P (VDF-HFP) solution on one surface of a pretreated substrate, heating the substrate to 80 ℃, preserving heat at 80 ℃ for 12 hours, cooling to room temperature, and peeling off the film on the substrate to obtain a P (VDF-HFP) film;
and thirdly, placing the P (VDF-HFP) film between two layers of FPE films, then placing the two layers of iron plates, placing the iron plates in a vulcanizing press at 170 ℃ for heat preservation for 0.5h, setting the pressure value of the vulcanizing press to 15MPa, carrying out hot pressing for 2h under the pressure of 15MPa, and cooling after the hot pressing is finished to obtain the composite film with the high-breakdown and high-energy-storage FPE and P (VDF-HFP) multi-layer structure. The thickness of the FPE film was 8 μm, the thickness of the P (VDF-HFP) film was 2 μm, the volume fraction of the P (VDF-HFP) film was 11.1%, and the volume fraction of the FPE film was 88.9%.
Example 2: in the present embodiment, the thickness of the FPE film is 6 μm, the thickness of the P (VDF-HFP) film is 6 μm, the volume fraction of the P (VDF-HFP) film is 33.3%, the volume fraction of the FPE film is 66.7%, and other experimental conditions are the same as those in example 1.
Example 3: in this example, the FPE and P (VDF-HFP) -based multilayer composite film with high breakdown and high energy storage has a thickness of 4 μm, a thickness of 10 μm, a volume fraction of 55.6% and a volume fraction of 44.4, and other experimental conditions are the same as those in example 1.
Comparative example 1: preparing a film of FPE and P (VDF-HFP);
the method comprises the following steps: according to a ratio of the mass of the FPE to the volume of the methylpyrrolidone solution of 0.4 g: 3.5mL of FPE and methyl pyrrolidone solution are respectively taken; adding FPE into a methyl pyrrolidone solution, mechanically stirring for 6h at the temperature of 25 ℃ to obtain an FPE solution, uniformly coating the FPE solution on one surface of a pretreated substrate, heating the substrate to 80 ℃, preserving heat at 80 ℃ for 12h, heating the substrate to 120 ℃, preserving heat for 12h, cooling to room temperature, and stripping a film on the substrate to obtain the FPE film.
Step two: according to the volume ratio of the mass of P (VDF-HFP) to the dimethylformamide solution of 1 g: 7mL of solutions of P (VDF-HFP) and dimethylformamide are respectively taken; adding P (VDF-HFP) into a dimethylformamide solution, mechanically stirring for 6 hours at 25 ℃ to obtain a P (VDF-HFP) solution, uniformly coating the P (VDF-HFP) solution on one surface of a pretreated substrate, heating the substrate to 80 ℃, keeping the temperature at 80 ℃ for 12 hours, cooling to room temperature, and then peeling off the film on the substrate to obtain the P (VDF-HFP) film.
Step three: and respectively carrying out hot-pressing treatment on the FPE film and the P (VDF-HFP) film to obtain the hot-pressed FPE film and the P (VDF-HFP) film.
FIG. 1 is a scanning electron microscope cross-sectional view of a composite film of FPE and P (VDF-HFP) multi-layer structure of example 3 in which the volume fraction of P (VDF-HFP) is 55.6%, wherein A represents the FPE film and B represents the P (VDF-HFP) film. As shown in fig. 1, the film structure of FPE and P (VDF-HFP) is complete and the layered structure is distinct.
Fig. 2 is an X-ray diffraction chart of the FPE and P (VDF-HFP) -based multi-layered structure composite film prepared in examples 1 to 3 and the FPE and P (VDF-HFP) thin films prepared in comparative example 1, a represents the P (VDF-HFP) thin film in comparative example 1, b represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 3, c represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 2, d represents the FPE and P (VDF-HFP) -based multi-layered structure composite film in example 1, and e represents the FPE thin film in comparative example 1.
As shown in fig. 2, the peaks corresponding to the α phase and β phase in the composite film become gradually apparent as the volume fraction of P (VDF-HFP) increases, demonstrating the difference in volume fraction of P (VDF-HFP) in the FPE and P (VDF-HFP) -based composite film.
FIG. 3 is a direct current breakdown Weibull distribution diagram of the FPE and P (VDF-HFP) -based multi-layer structure composite film prepared in examples 1-3 with the FPE film and the P (VDF-HFP) film prepared in comparative example 1, ● denotes the FPE film in comparative example 1, ■ denotes the P (VDF-HFP) film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
a multilayer composite film of FPE and P (VDF-HFP) in example 3 is shown.
As shown in fig. 3, the breakdown results of the composite film having the multi-layer structure are superior to those of the FPE film and the P (VDF-HFP) film having the single-layer structure. When an electric field is applied, based on a series capacitance model, the electric field in the multilayer structure composite film is redistributed, and the electric field obtained by the P (VDF-HFP) layer with higher dielectric constant is smaller, so that the protection is obtained; in addition, the interlayer interface effectively prevents the growth of the electric tree branches. The breakdown field strength of the FPE and P (VDF-HFP) based multilayer composite film with the volume fraction of P (VDF-HFP) being 11.1% can reach 545.0kV/mm, and is improved by 55.1% compared with a pure P (VDF-HFP) film.
Fig. 4 is a graph showing the results of dielectric constant tests of the FPE and P (VDF-HFP) -based multi-layered structure composite films prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
As shown in fig. 4, the dielectric constant of the FPE and P (VDF-HFP) -based multilayer composite film is between the dielectric constants of FPE and P (VDF-HFP), and the dielectric constant of the composite film gradually increases with the volume fraction of P (VDF-HFP).
FIG. 5 shows example 1-3 dielectric loss test results of the FPE and P (VDF-HFP) -based multi-layer structure composite film prepared in comparison with the FPE film and the P (VDF-HFP) film prepared in comparison example 1, ● represents the FPE film in comparison example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
As shown in fig. 5, compared with the pure P (VDF-HFP) film, the dielectric loss of the FPE and P (VDF-HFP) -based multilayer composite film is greatly reduced, and is lower than 0.04 at a frequency of 1 kHz.
Fig. 6 is a graph showing the test results of the FPE and P (VDF-HFP) -based multi-layered structure composite film prepared in examples 1 to 3 and the FPE film and P (VDF-HFP) film prepared in comparative example 1, ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
As shown in FIG. 6, the curve corresponding to the FPE and P (VDF-HFP) -based multi-layer composite film is between that of the pure FPE film and the pure P (VDF-HFP) film, wherein the FPE and P (VDF-HFP) -based multi-layer composite film with the volume fraction of P (VDF-HFP) of 33.3% shows the highest discharge energy density of 11.1J/cm3。
FIG. 7 shows FPE and P (VDF-HFP) -based multi-layer composite films prepared in examples 1-3 and comparative example 1The charge and discharge efficiency test results of the FPE film and the P (VDF-HFP) film prepared in (1), ● represents the FPE film in comparative example 1,
shows a FPE and P (VDF-HFP) -based multi-layer composite film in example 1, a t represents an FPE and P (VDF-HFP) -based multi-layer composite film in example 2,
the FPE and P (VDF-HFP) -based multilayer composite film in example 3 is shown, and ■ shows the P (VDF-HFP) film in comparative example 1.
As shown in fig. 7, the charging and discharging efficiency of the FPE and P (VDF-HFP) -based multilayer composite film is greatly improved compared to that of pure P (VDF-HFP), where the charging and discharging efficiency of the FPE and P (VDF-HFP) -based multilayer composite film with a P (VDF-HFP) volume fraction of 33.3% is always maintained above 86.7% in a wide field intensity range.
Claims (10)
1. The composite film with the FPE and P (VDF-HFP) based multi-layer structure is characterized by consisting of a layer of P (VDF-HFP) film and two layers of FPE films, wherein the P (VDF-HFP) film is arranged between the two layers of the FPE films.
2. The method for preparing a high breakdown and high energy storage FPE and P (VDF-HFP) -based multi-layer composite film according to claim 1, wherein the method comprises the following steps:
firstly, adding fluorene polyester into a methyl pyrrolidone solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain an FPE solution; uniformly coating the FPE solution on one surface of a pretreated substrate, then carrying out gradient heating and heat preservation on the substrate, cooling to room temperature, and stripping a film on the substrate to obtain an FPE film;
secondly, adding P (VDF-HFP) into a dimethylformamide solution, and mechanically stirring for 4-6 hours at the temperature of 15-25 ℃ to obtain a P (VDF-HFP) solution; uniformly coating a P (VDF-HFP) solution on one surface of a pretreated substrate, heating the substrate to 75-80 ℃, preserving heat for 12-15 hours at 75-80 ℃, cooling to room temperature, and peeling off the film on the substrate to obtain a P (VDF-HFP) film;
and thirdly, placing the P (VDF-HFP) film between the two FPE films, carrying out hot-pressing treatment, and finally cooling to obtain the FPE and P (VDF-HFP) multi-layer structure composite film with high breakdown and high energy storage.
3. The preparation method of the FPE and P (VDF-HFP) based multi-layer composite film with high breakdown and high energy storage according to claim 2, wherein the ratio of the mass of the fluorene polyester to the volume of the methyl pyrrolidone solution in the step one is (0.4-0.5) g: (3.5-4) mL.
4. The method according to claim 2, wherein the pre-treated substrate is treated by the following steps: cleaning the substrate with clear water for 3-5 times, then washing with deionized water for 3-5 times, then cleaning with absolute ethyl alcohol for 3-5 times, and finally drying at 75-80 ℃ for 12-15 h to obtain a pretreated substrate, wherein the substrate is a glass plate.
5. The method for preparing a high breakdown and high energy storage FPE and P (VDF-HFP) -based multi-layer composite film according to claim 2, wherein the step of gradient heating and temperature preservation in the step one comprises: the substrate is heated to 80 ℃ and kept at 80 ℃ for 12h, then heated to 120 ℃ and kept at 120 ℃ for 12 h.
6. The method as claimed in claim 2, wherein the FPE film in the first step has a thickness of 4 μm, 6 μm, 8 μm or 18 μm, and the P (VDF-HFP) film in the second step has a thickness of 2 μm, 6 μm, 10 μm or 18 μm.
7. The method for preparing a high-breakdown and high-energy-storage FPE and P (VDF-HFP) -based multilayer composite film according to claim 2, wherein the ratio of the mass of P (VDF-HFP) to the volume of the dimethylformamide solution in the second step is (1-1.2) g: (7-8) mL.
8. The method for preparing a high breakdown and high energy storage FPE and P (VDF-HFP) -based multi-layer composite film according to claim 2, wherein the step of hot pressing process in step three is as follows: the method comprises the steps of putting a P (VDF-HFP) film between two layers of FPE films, then putting between two layers of iron plates, putting the iron plates in a flat vulcanizing machine at 160-170 ℃ for heat preservation for 0.5-1 h, finally carrying out hot pressing for 1-2 h under the pressure of 10-15 MPa, and cooling after the hot pressing is finished to obtain the composite film with the high-breakdown and high-energy-storage FPE and P (VDF-HFP) multi-layer structure, wherein the volume fraction of the P (VDF-HFP) film in the composite film with the high-breakdown and high-energy-storage FPE and P (VDF-HFP) multi-layer structure is 11.1%, 33.3% or 55.6%.
9. The method for preparing a high breakdown and high energy storage FPE and P (VDF-HFP) -based multilayer composite film according to claim 2, wherein the mechanical stirring in the first step and the second step is performed by a magnetic stirrer, and the stirring speed is 150 to 300 r/min.
10. The use of the high breakdown and high energy storage FPE and P (VDF-HFP) -based multi-layer composite film according to claim 1, wherein said FPE and P (VDF-HFP) -based multi-layer composite film is used in a super capacitor.
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