CN115926231B - Layered polyester-based high-energy-storage composite medium film and preparation method and application thereof - Google Patents
Layered polyester-based high-energy-storage composite medium film and preparation method and application thereof Download PDFInfo
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- CN115926231B CN115926231B CN202310060553.5A CN202310060553A CN115926231B CN 115926231 B CN115926231 B CN 115926231B CN 202310060553 A CN202310060553 A CN 202310060553A CN 115926231 B CN115926231 B CN 115926231B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000004146 energy storage Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002033 PVDF binder Substances 0.000 claims abstract description 70
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 70
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052582 BN Inorganic materials 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims description 37
- 239000003960 organic solvent Substances 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 21
- 239000002346 layers by function Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003990 capacitor Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000003989 dielectric material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229920006267 polyester film Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 99
- 229920002799 BoPET Polymers 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 230000005684 electric field Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000004697 Polyetherimide Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001601 polyetherimide Polymers 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 208000037998 chronic venous disease Diseases 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to the technical field of polymer-based energy storage dielectric materials, and provides a layered polyester-based high energy storage composite dielectric film, and a preparation method and application thereof. The invention modifies the polyester film by using the wide forbidden band material boron nitride nano-sheet and the ferroelectric polymer polyvinylidene fluoride, and the obtained layered polyester-based high energy storage composite dielectric film has good breakdown characteristic and energy storage characteristic, higher dielectric constant, excellent insulating property, high discharge energy density and good charge-discharge cycle characteristic. The example results show that the dielectric constant of the laminated polyester-based high energy storage composite dielectric film prepared by the invention is between 3.0 and 4.0, the room temperature breakdown strength is more than 660kV/mm, and the discharge energy density reaches 8.71J/cm 3 The charge-discharge efficiency is more than 97%, and the charge-discharge cycle life is more than 10000 times. The preparation method provided by the invention has the advantages of simple flow, easiness in operation and low price of used equipment, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of polymer-based energy storage dielectric materials, in particular to a layered polyester-based high energy storage composite dielectric film, a preparation method and application thereof.
Background
The film capacitor has the advantages of low loss, high field intensity resistance, high operation reliability and the like, and is widely applied to the fields of pulse electromagnetic systems, new energy automobiles, power industries and the like. The biaxially oriented polypropylene BOPP film capacitor has the advantages of low loss (about 0.0002), good broadband stability, high insulating strength (about 600 kV/mm), good self-healing property and the like, and occupies a large market share. But the lower dielectric constant (2.2 under 1kHz electric field) of BOPP directly determines the lower energy storage density, so that the BOPP film capacitor occupies a larger space on the premise of meeting the same capacitance, and the defect seriously affects the popularization and application of the BOPP film capacitor in fields with severe requirements on equipment size such as new energy automobile industry, pulse power supply system and the like.
The polymer film with single component is difficult to simultaneously take advantage of multiple indexes, so that the research on the composite dielectric material becomes an important direction for preparing the material with high energy storage density. Modification treatment of the surface of the existing film is one of the viable ideas for large-scale preparation of high energy storage density polymer dielectric materials. In recent years, wang Qing and the like of pennsylvania state university transfer hexagonal boron nitride (h-BN) prepared by a chemical deposition method (CVD) to both sides of a polyetherimide PEI film to obtain an h-BN modified PEI film, thereby improving charge and discharge efficiency and energy storage density of PEI in a high-temperature environment. The university of Qinghai Li Qi et al realizes SiO deposition by Plasma Enhanced Chemical Vapor Deposition (PECVD) 2 Deposition on a variety of films such as BOPP, PI, PEI resulted in a composite film with improved properties. However, the CVD treatment method has complex steps and low efficiency, and is not suitable for large-scale application. The PECVD method depends on a complex control device, has limited materials which can be used for deposition, and has certain difficulty in realizing the large-scale modification of the polymer film; meanwhile, the comprehensive performance of the composite film is still to be further improved.
Therefore, a proper polymer organic film is selected and modified for large-scale application to obtain the polymer composite dielectric material with high energy storage density, and the effects of increasing the energy storage density of the capacitor and reducing the volume of the capacitor can be realized, so that the application scene of the film capacitor is widened, and the film capacitor has important significance for saving cost or application in severe environments.
Disclosure of Invention
In view of the above, the invention provides a layered polyester-based high energy storage composite dielectric film, and a preparation method and application thereof. The layered polyester-based high energy storage composite dielectric film provided by the invention has good breakdown characteristic and energy storage characteristic, excellent comprehensive performance, and simple preparation method, and is suitable for industrial production.
In order to achieve the above object, the present invention provides the following technical solutions:
a layered polyester-based high energy storage composite dielectric film comprises a polyester base film and a modified functional layer arranged on the surface of the polyester base film, wherein the modified functional layer comprises boron nitride nano-sheets and polyvinylidene fluoride.
Preferably, the mass of the boron nitride nano-sheet in the modified functional layer is 1.67-13.33% of the mass of polyvinylidene fluoride.
Preferably, the thickness of the layered polyester-based high energy storage composite medium film is 12-14 mu m; the thickness of the polyester base film was 11.8. Mu.m.
The invention also provides a preparation method of the layered polyester-based high energy storage composite medium film, which comprises the following steps:
mixing the boron nitride nano-sheet, polyvinylidene fluoride and an organic solvent to obtain a mixed dispersion liquid;
and (3) casting the mixed dispersion liquid on the surface of the polyester base film to form a film, and then removing the organic solvent to obtain the layered polyester base high energy storage composite medium film.
Preferably, the method of mixing the boron nitride nano-sheet, polyvinylidene fluoride and organic solvent comprises: stirring and mixing polyvinylidene fluoride and a first part of organic solvent to obtain a polyvinylidene fluoride solution; mixing the boron nitride nano-sheets with a second part of organic solvent for ultrasonic dispersion to obtain boron nitride dispersion liquid; and mixing the polyvinylidene fluoride solution and the boron nitride dispersion liquid to obtain a mixed dispersion liquid.
Preferably, the mass ratio of the polyvinylidene fluoride to the first part of organic solvent is 1:20; the temperature of the stirring and mixing is 50-60 ℃ and the time is 12h; the mass ratio of the boron nitride nano-sheet to the second part of organic solvent is (0.01-0.08) 20; the power of ultrasonic dispersion is 100W, and the time is 3h.
Preferably, the mixing of the polyvinylidene fluoride solution and the boron nitride dispersion liquid is carried out under the condition of heating and stirring, the temperature of the heating and stirring is 50-60 ℃, and the time is 8 hours.
Preferably, the organic solvent is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide.
Preferably, the method for removing the organic solvent is heating evaporation; the heating and evaporating temperature is 70 ℃ and the time is 12h.
The invention also provides the application of the layered polyester-based high energy storage composite dielectric film prepared by the preparation method in the thin film capacitor.
The invention provides a layered polyester-based high energy storage composite dielectric film which comprises a polyester-based film and a modified functional layer arranged on the surface of the polyester-based film, wherein the components of the modified functional layer comprise boron nitride nano-sheets and polyvinylidene fluoride. According to the invention, the thermoplastic Polyester (PET) film is modified by the wide band gap material boron nitride nano-sheets (BNNS) and the ferroelectric polymer polyvinylidene fluoride (PVDF), and the obtained layered polyester-based high-energy-storage composite dielectric film has good breakdown characteristic and energy storage characteristic, has higher dielectric constant, excellent insulating property, high discharge energy density and good charge-discharge cycle characteristic, and can solve the problems of low energy storage density and low charge-discharge cycle times of the traditional polymer dielectric. The example results show that the dielectric constant of the laminated polyester-based high energy storage composite dielectric film prepared by the invention is between 3.0 and 4.0, the room temperature breakdown strength is more than 660kV/mm, and the discharge energy density reaches 8.71J/cm 3 The charge-discharge efficiency is more than 97%, and the charge-discharge cycle life is more than 10000 times.
The invention also provides a preparation method of the layered polyester-based high energy storage composite medium film, which adopts the mixed dispersion liquid of the boron nitride nano-sheets and the polyvinylidene fluoride to cast and form a film on the surface of the polyester-based film, and then the solvent is removed to form the boron nitride nano-sheet-polyvinylidene fluoride composite layer; the preparation method provided by the invention has the advantages of simple flow, easiness in operation and low price of used equipment, and is suitable for industrial production.
Drawings
FIG. 1 is a cross-sectional SEM image of a composite dielectric film prepared according to example 2;
FIG. 2 is a graph showing the relationship between dielectric constant, dielectric loss and electric field frequency at room temperature of the PET film used in comparative example 1 and the composite dielectric films prepared in examples 1 to 4;
FIG. 3 is a graph showing the relationship between dielectric constant, dielectric loss and temperature of the PET film used in comparative example 1 and the composite dielectric films prepared in examples 1 to 4 under an electric field of 1000 Hz;
FIG. 4 is a diagram showing the Weber distribution of the breakdown field strength at room temperature of the PET film used in comparative example 1 and the composite dielectric films prepared in examples 1 to 4;
FIG. 5 is a graph showing the relationship between the discharge energy density and the charge-discharge efficiency with the applied electric field at room temperature of the PET film used in comparative example 1 and the composite dielectric films prepared in examples 1 to 4;
FIG. 6 is a charge-discharge cycle chart of the composite dielectric film prepared in example 2 under an electric field of 200kV/mm and at room temperature.
Detailed Description
The invention provides a layered polyester-based high energy storage composite dielectric film which comprises a polyester-based film and a modified functional layer arranged on the surface of the polyester-based film, wherein the components of the modified functional layer comprise boron nitride nano-sheets and polyvinylidene fluoride.
In the present invention, the mass of the boron nitride nanosheets in the modified functional layer is preferably 1.67 to 13.33%, more preferably 2 to 13%, and even more preferably 5 to 10% of the mass of polyvinylidene fluoride.
In the invention, the thickness of the layered polyester-based high energy storage composite medium film is preferably 12-14 mu m; the thickness of the polyester base film is preferably 11.8 μm.
The invention also provides a preparation method of the layered polyester-based high energy storage composite medium film, which comprises the following steps:
mixing the boron nitride nano-sheet, polyvinylidene fluoride and an organic solvent to obtain a mixed dispersion liquid;
and (3) casting the mixed dispersion liquid on the surface of the polyester base film to form a film, and then removing the organic solvent to obtain the layered polyester base high energy storage composite medium film.
The invention mixes the boron nitride nano-sheet, polyvinylidene fluoride and organic solvent to obtain mixed dispersion liquid. In the present invention, the organic solvent is preferably N, N-dimethylformamide, tetrahydrofuran or dimethylsulfoxide; the method for mixing the boron nitride nano-sheet, polyvinylidene fluoride and organic solvent preferably comprises the following steps: stirring and mixing polyvinylidene fluoride and a first part of organic solvent to obtain a polyvinylidene fluoride solution; mixing the boron nitride nano-sheets with a second part of organic solvent for ultrasonic dispersion to obtain boron nitride dispersion liquid; mixing the polyvinylidene fluoride solution and the boron nitride dispersion liquid to obtain a mixed dispersion liquid; the mass ratio of the polyvinylidene fluoride to the first part of organic solvent is preferably 1:20; the temperature of the stirring and mixing is preferably 50-60 ℃ and the time is preferably 12 hours, and in the specific embodiment of the invention, the stirring is preferably carried out until the polyvinylidene fluoride is completely dissolved, and the obtained polyvinylidene fluoride solution is transparent; the mass ratio of the boron nitride nano-sheet to the second part of the organic solvent is preferably (0.01-0.08): 20, more preferably (0.03-0.05): 20; the power of the ultrasonic dispersion is preferably 100W (the maximum power of the ultrasonic device is preferably 300W) and the time is 3h; the mixing of the polyvinylidene fluoride solution and the boron nitride dispersion liquid is carried out under the condition of heating and stirring, the temperature of heating and stirring is preferably 50-60 ℃, and the time is preferably 8 hours; the dosage ratio of the polyvinylidene fluoride to the boron nitride is preferably calculated according to the mass fraction of the boron nitride nano-sheets in the boron nitride nano-sheet-polyvinylidene fluoride composite layer according to the scheme.
After the mixed dispersion liquid is obtained, the mixed dispersion liquid is cast on the surface of a polyester base film to form a film, and then the organic solvent is removed to obtain the layered polyester base high energy storage composite medium film. The invention preferably fixes the polyester base film on a glass plate, and then the mixed dispersion liquid is cast on the surface of the polyester base film to form a film; the method for removing the organic solvent is preferably heating evaporation; the temperature of the heating evaporation is preferably 70 ℃ and the time is preferably 12 hours; and after heating and evaporating, separating the obtained layered polyester-based high energy storage composite medium film from the glass plate.
The invention also provides the application of the layered polyester-based high energy storage composite dielectric film prepared by the preparation method in the thin film capacitor. The layered polyester-based high energy storage composite dielectric film provided by the invention has good breakdown characteristic and energy storage characteristic, higher dielectric constant, excellent insulating property, high discharge energy density and good charge-discharge cycle characteristic, and has wide application prospect in the field of film capacitors; the invention is not particularly limited to the particular method of application described, but may be applied using methods well known to those skilled in the art.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Comparative example 1
A PET film 11.8 μm thick of an appropriate size was taken and placed in an oven at 70℃for 12 hours. The PET film after the baking treatment was used as a comparative example.
Example 1
0.6g of PVDF powder was added to 12g of DMF solution and stirred at 50-60℃for 12h until PVDF was completely dissolved. 0.01g BNNS powder was added to 20g DMF solution and sonicated at 100W (300W 33.3%) for 3h until the mixture color was uniform. Mixing the two liquids and stirring for 8 hours at 50-60 ℃ to obtain uniform dispersion liquid. The dispersion is cast on a PET film fixed on a glass plate to form a film, and the film is put into an oven to be dried at 70 ℃ for 12 hours until DMF is evaporated completely, so as to obtain a layered polyester-based high energy storage composite medium film with the thickness of about 12 mu m, which is marked as (BNNS-PVDF)/PET layered composite medium film, wherein the mass of BNNS in the modified functional layer is 1.67% of the mass of PVDF.
Example 2
0.6g of PVDF powder was added to 12g of DMF solution and stirred at 50-60℃for 12h until PVDF was completely dissolved. 0.02g BNNS powder was added to 20g DMF solution and sonicated at 100W (300W 33.3%) for 3h until the mixture color was uniform. Mixing the two liquids and stirring for 8 hours at 50-60 ℃ to obtain uniform dispersion liquid. The dispersion is cast on a PET film fixed on a glass plate to form a film, and the film is put into an oven to be dried at 70 ℃ for 12 hours until DMF is evaporated completely, so as to obtain a layered polyester-based high energy storage composite medium film with the thickness of about 12 mu m, which is denoted as (BNNS-PVDF)/PET layered composite medium film, wherein the mass of BNNS in the modified functional layer is 3.33% of the mass of PVDF.
Example 3
0.6g of PVDF powder was added to 12g of DMF solution and stirred at 50-60℃for 12h until PVDF was completely dissolved. 0.04g BNNS powder was added to 20g DMF solution and sonicated at 100W (300W 33.3%) for 3h until the mixture color was uniform. Mixing the two liquids and stirring for 8 hours at 50-60 ℃ to obtain uniform dispersion liquid. The dispersion is cast on a PET film fixed on a glass plate to form a film, and the film is put into an oven to be dried at 70 ℃ for 12 hours until DMF is evaporated completely, so as to obtain a layered polyester-based high energy storage composite medium film with the thickness of about 12 mu m, which is marked as (BNNS-PVDF)/PET layered composite medium film, wherein the mass of BNNS in the modified functional layer is 6.67% of the mass of PVDF.
Example 4
0.6g of PVDF powder was added to 12g of DMF solution and stirred at 50-60℃for 12h until PVDF was completely dissolved. 0.08g BNNS powder was added to 20g DMF solution and sonicated at 100W (300W 33.3%) for 3h until the mixture color was uniform. Mixing the two liquids and stirring for 8 hours at 50-60 ℃ to obtain uniform dispersion liquid. The dispersion is cast on a PET film fixed on a glass plate to form a film, and the film is put into an oven to be dried at 70 ℃ for 12 hours until DMF is evaporated completely, so as to obtain a layered polyester-based high energy storage composite medium film with the thickness of about 12 mu m, which is marked as (BNNS-PVDF)/PET layered composite medium film, wherein the mass of BNNS in the modified functional layer is 13.33% of the mass of PVDF.
Performance testing
FIG. 1 is a cross-sectional SEM image of a (BNNS-PVDF)/PET layered composite dielectric film prepared in example 2: as can be seen from FIG. 1, the composite dielectric film has flat surface and uniform thickness, and the modified functional layer is in good contact with the matrix film.
FIG. 2 is a graph showing the relationship between the dielectric constant and the dielectric loss at room temperature and the electric field frequency of the PET film used in comparative example 1 and the layered composite dielectric films prepared in examples 1, 2, 3 and 4, wherein curve 0 represents comparative example 1, curve 1,2. 3 and 4 represent examples 1 to 4, respectively; the results in fig. 2 show that: the dielectric constant of the (BNNS-PVDF)/PET layered composite dielectric film slightly decreases with increasing frequency, and the dielectric loss increases with increasing frequency. The dielectric constants of PET, example 1, example 2, example 3 and example 4 were calculated to be 10 2 ～10 6 The dielectric constants of the (BNNS-PVDF)/PET lamellar composite dielectric films are respectively reduced by 8.8%, 7.5%, 7.4%, 6.3% and 6.4% in the Hz range, and the result shows that the dielectric constants of the (BNNS-PVDF)/PET lamellar composite dielectric films have wide-band stability, which has important significance for the stability of capacitance values of the film capacitors.
FIG. 3 is a graph showing the relationship between dielectric constant and dielectric loss and temperature of the PET film used in comparative example 1 and the layered composite dielectric films prepared in examples 1, 2, 3, and 4 under an electric field of 1000Hz, wherein curve 0 represents comparative example 1 and curves 1, 2, 3, and 4 represent examples 1 to 4, respectively. The results in fig. 3 show that: the dielectric constant of the (BNNS-PVDF)/PET lamellar composite dielectric film slightly changes within the range of 20-100 ℃, wherein the maximum change amount is 3.5% (taking 20 ℃ as a reference) and is increased within the range of 100-120 ℃. Correspondingly, the dielectric loss remains almost constant in the range of 20-100 ℃ and increases in the range of 100-120 ℃ but remains generally at a lower level. This shows that the (BNNS-PVDF)/PET layered composite dielectric film has good thermal stability in dielectric constant and dielectric loss within the range of 20-100 ℃.
FIG. 4 is a graph showing the Weber distribution of the breakdown strength at room temperature of the PET film used in comparative example 1 and the layered composite dielectric films prepared in examples 1, 2, 3, and 4, wherein curve 0 represents comparative example 1, and curves 1, 2, 3, and 4 represent examples 1 to 4, respectively. The results in fig. 4 show that: the breakdown strength of the PET film and examples 1, 2, 3, 4 were 660kV/mm, 681kV/mm, 737kV/mm, 721kV/mm, and 671kV/mm, respectively. Compared with the PET film, the breakdown strength of the composite dielectric films prepared in examples 1, 2, 3 and 4 is respectively improved by 3.2%, 11.7%, 9.2% and 1.7%, which shows that the breakdown performance of the (BNNS-PVDF)/PET layered composite dielectric film is improved.
FIG. 5 shows the PET film used in example 1 and the layered composite media films prepared in examples 1, 2, 3, and 4The relationship between the discharge energy density and the charge-discharge efficiency of the film at room temperature with the applied electric field is shown in the graph, wherein curve 0 represents comparative example 1, and curves 1, 2, 3 and 4 represent examples 1 to 4, respectively. The results in fig. 5 show that: the maximum discharge energy density of the PET film was 6.80J/cm 3 The maximum discharge energy densities of the layered composite dielectric films prepared in examples 1, 2, 3 and 4 were 7.42J/cm, respectively 3 、8.71J/cm 3 、8.13J/cm 3 And 7.67J/cm 3 9.1%, 28.1%, 19.6% and 12.8% respectively. In terms of charge and discharge efficiency, the PET film and the composite dielectric films prepared in examples 1, 2, 3 and 4 were maintained at a level of 97% or more in the range of about 200kV/mm to 700 kV/mm. The data above show that the (BNNS-PVDF)/PET layered composite dielectric film has excellent energy storage characteristics.
FIG. 6 is a charge-discharge cycle chart of the layered composite dielectric film prepared in example 2 under an electric field of 200kV/mm and at room temperature. Example 2 was chosen as a representative example and tested at 200kV/mm electric field and room temperature. The results in FIG. 6 show that example 2 maintains stable discharge energy density (about 0.63J/cm) after 10000 charge-discharge cycles at room temperature and 200kV/mm electric field conditions 3 ) The (BNNS-PVDF)/PET layered composite medium film has excellent charge-discharge cycle stability and operation reliability, and has potential application value in the field of film capacitors.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The laminated polyester-based high energy storage composite medium film is characterized by comprising a polyester base film and a modified functional layer arranged on the surface of the polyester base film, wherein the modified functional layer comprises boron nitride nano-sheets and polyvinylidene fluoride; the thickness of the layered polyester-based high energy storage composite medium film is 12-14 mu m; the thickness of the polyester base film is 11.8 mu m; the preparation method of the layered polyester-based high energy storage composite medium film comprises the following steps: mixing the boron nitride nano-sheet, polyvinylidene fluoride and an organic solvent to obtain a mixed dispersion liquid; casting the mixed dispersion liquid on the surface of a polyester base film to form a film, and then removing the organic solvent to obtain a layered polyester base high energy storage composite medium film; the method for mixing the boron nitride nano-sheet, polyvinylidene fluoride and organic solvent comprises the following steps: stirring and mixing polyvinylidene fluoride and a first part of organic solvent to obtain a polyvinylidene fluoride solution; mixing the boron nitride nano-sheets with a second part of organic solvent for ultrasonic dispersion to obtain boron nitride dispersion liquid; mixing the polyvinylidene fluoride solution and the boron nitride dispersion liquid to obtain a mixed dispersion liquid; the mass ratio of the polyvinylidene fluoride to the first part of organic solvent is 1:20; the temperature of the stirring and mixing is 50-60 ℃ and the time is 12h; the mass ratio of the boron nitride nano-sheet to the second part of organic solvent is (0.01-0.08) 20; the power of the ultrasonic dispersion is 100W, and the time is 3h; the mixing of the polyvinylidene fluoride solution and the boron nitride dispersion liquid is carried out under the condition of heating and stirring, the temperature of heating and stirring is 50-60 ℃, and the time is 8 hours.
2. The layered polyester-based high energy storage composite dielectric film according to claim 1, wherein the mass of the boron nitride nano-sheets in the modified functional layer is 1.67-13.33% of the mass of polyvinylidene fluoride.
3. The method for preparing the layered polyester-based high energy storage composite dielectric film according to any one of claims 1 to 2, which is characterized by comprising the following steps:
mixing the boron nitride nano-sheet, polyvinylidene fluoride and an organic solvent to obtain a mixed dispersion liquid;
casting the mixed dispersion liquid on the surface of a polyester base film to form a film, and then removing the organic solvent to obtain a layered polyester base high energy storage composite medium film;
the method for mixing the boron nitride nano-sheet, polyvinylidene fluoride and organic solvent comprises the following steps: stirring and mixing polyvinylidene fluoride and a first part of organic solvent to obtain a polyvinylidene fluoride solution; mixing the boron nitride nano-sheets with a second part of organic solvent for ultrasonic dispersion to obtain boron nitride dispersion liquid; mixing the polyvinylidene fluoride solution and the boron nitride dispersion liquid to obtain a mixed dispersion liquid; the mass ratio of the polyvinylidene fluoride to the first part of organic solvent is 1:20; the temperature of the stirring and mixing is 50-60 ℃ and the time is 12h; the mass ratio of the boron nitride nano-sheet to the second part of organic solvent is (0.01-0.08) 20; the power of the ultrasonic dispersion is 100W, and the time is 3h; the mixing of the polyvinylidene fluoride solution and the boron nitride dispersion liquid is carried out under the condition of heating and stirring, the temperature of heating and stirring is 50-60 ℃, and the time is 8 hours.
4. A method of preparation according to claim 3, wherein the organic solvent is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide.
5. A method of preparing according to claim 3, wherein the method of removing the organic solvent is evaporation by heating; the heating and evaporating temperature is 70 ℃ and the time is 12h.
6. The use of the layered polyester-based high energy storage composite dielectric film according to any one of claims 1 to 2 or the layered polyester-based high energy storage composite dielectric film prepared by the preparation method according to any one of claims 3, 4 and 5 in a film capacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310060553.5A CN115926231B (en) | 2023-01-16 | 2023-01-16 | Layered polyester-based high-energy-storage composite medium film and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310060553.5A CN115926231B (en) | 2023-01-16 | 2023-01-16 | Layered polyester-based high-energy-storage composite medium film and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN108456324A (en) * | 2018-04-09 | 2018-08-28 | 南通洪明电工科技有限公司 | A kind of surface coating technology prepares the method and its application of high-performance inorganic/organic composite multilayer dielectric thin film |
| CN111234424A (en) * | 2020-03-10 | 2020-06-05 | 陕西科技大学 | Flaky boron nitride/polyvinylidene fluoride composite material and preparation method thereof |
| CN111892730A (en) * | 2020-08-12 | 2020-11-06 | 南通洪明电工科技有限公司 | Method for preparing inorganic/organic composite dielectric medium ultrathin film in large scale and inorganic/organic composite dielectric medium ultrathin film |
| CN112920531A (en) * | 2021-02-18 | 2021-06-08 | 西安交通大学 | High energy storage density polymer and method for preparing same based on field arrangement |
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| CN108456324A (en) * | 2018-04-09 | 2018-08-28 | 南通洪明电工科技有限公司 | A kind of surface coating technology prepares the method and its application of high-performance inorganic/organic composite multilayer dielectric thin film |
| CN111234424A (en) * | 2020-03-10 | 2020-06-05 | 陕西科技大学 | Flaky boron nitride/polyvinylidene fluoride composite material and preparation method thereof |
| CN111892730A (en) * | 2020-08-12 | 2020-11-06 | 南通洪明电工科技有限公司 | Method for preparing inorganic/organic composite dielectric medium ultrathin film in large scale and inorganic/organic composite dielectric medium ultrathin film |
| CN112920531A (en) * | 2021-02-18 | 2021-06-08 | 西安交通大学 | High energy storage density polymer and method for preparing same based on field arrangement |
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