CN117301674A - Five-layer composite film and preparation method and application thereof - Google Patents

Five-layer composite film and preparation method and application thereof Download PDF

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Publication number
CN117301674A
CN117301674A CN202311077531.6A CN202311077531A CN117301674A CN 117301674 A CN117301674 A CN 117301674A CN 202311077531 A CN202311077531 A CN 202311077531A CN 117301674 A CN117301674 A CN 117301674A
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film
layer
adhesive
composite film
layer composite
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郑明胜
王馨茉
查俊伟
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/16—Capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

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  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention provides five layersThe preparation method and application of the composite film comprise the following steps: uniformly coating the insulating nano sheet dispersion liquid on the first film layer by taking the insulating nano sheet dispersion liquid as a raw material to form a second film layer, thereby obtaining a double-layer film; and uniformly coating the adhesive on the second film layer by taking the adhesive solution as a raw material to form a third film layer, thereby obtaining the three-layer film. And attaching the second film layer of the obtained double-layer film to the third film layer of the obtained three-layer film. The invention adopts a polymer film with high breakdown strength as an upper film and a lower film, adopts an insulating nano sheet film layer with wide band gap as an electron blocking layer, and uses an adhesive in the middle to play a role of connecting the upper film and the lower film. The five-layer composite film has excellent energy storage property, and the maximum discharge energy density can reach 8.76J/cm 3 Meanwhile, the charge and discharge efficiency can reach 94 percent. The five-layer composite film provided by the invention has a good application prospect in the field of capacitor energy storage.

Description

Five-layer composite film and preparation method and application thereof
Technical Field
The invention relates to the field of materials, in particular to a five-layer composite film and a preparation method and application thereof.
Background
The polymer film capacitor has the characteristics of high power density, good cycle stability and strong self-healing property, and is widely applied to the fields of pulse power systems, hybrid electric vehicles, petroleum exploration and the like. Currently, with the development of continuous miniaturization and light weight of modern electronic power systems, higher requirements are also put on the energy storage performance of thin film capacitors. Most polymeric dielectric materials have a relatively low energy storage density, which greatly limits their use. Therefore, there is an urgent need to develop novel polymer dielectric materials having high energy storage and low loss characteristics.
Functional fillers are often combined with high breakdown strength polymer matrices and are a potential method to increase the energy storage density of the material. If the inorganic filler with high dielectric constant is introduced, the dielectric constant of the composite material can be improved, but the dielectric property and the electric conductivity between the inorganic filler and the organic matrix are obviously different, local electric field distortion is easy to generate, the breakdown strength is greatly reduced, and the energy storage property of the polymer is seriously affected. Broad band fillers (e.g., BN, siO) may also be added to the polymer matrix 2 、Al 2 O 3 Etc.) can inhibit the leakage current of the composite material while improving the breakdown strength, but the compatibility of the filler and the polymerPoor, easy agglomeration, and difficulty in further improving energy storage performance.
Disclosure of Invention
The present invention provides a five-layer composite film, and methods of making and using the same, in an effort to solve or at least alleviate at least one of the problems identified above.
The invention provides a preparation method of a five-layer composite film, which comprises the following steps:
uniformly coating the insulating nano sheet dispersion liquid on the first film layer by taking the insulating nano sheet dispersion liquid as a raw material to form a second film layer, thereby obtaining a double-layer film;
and uniformly coating the adhesive on the second film layer by taking the adhesive solution as a raw material to form a third film layer, thereby obtaining the three-layer film.
And attaching the second film layer of the obtained double-layer film to the third film layer of the obtained three-layer film.
In a preferred embodiment of the present invention, the second film layer of the obtained double-layer film is bonded to the third film layer of the obtained three-layer film, and then the heat pressing and curing operation is performed.
As a preferred embodiment of the present invention, the hot pressing operation conditions are as follows: the temperature is 65-75 ℃, the pressure is 10-20 Mpa, and the time is 20-30 min.
As a preferred embodiment of the present invention, the method for preparing the insulating nanoplatelets comprises:
adding inorganic powder into a mixed solution of an organic solvent and water, performing water bath ultrasonic treatment, and centrifuging;
centrifuging the supernatant, precipitating and drying to obtain an insulating nano sheet;
wherein the inorganic powder comprises one or more of boron nitride, alumina, mica and montmorillonite; the organic solvent comprises one or more of isopropanol, dimethylformamide and N-methylpyrrolidone.
As a preferred embodiment of the present invention, the insulating nanoplatelets are two-dimensional nanoplatelets, and the insulating nanoplatelets have a size of 500 to 5000nm.
As a preferred embodiment of the present invention, the insulating nanoplatelets are boron nitride nanoplatelets.
As a preferred embodiment of the present invention, the method for preparing the adhesive solution includes:
and uniformly mixing a main agent of the bi-component adhesive and a curing agent of the bi-component adhesive, and then removing bubbles in vacuum to obtain the adhesive solution.
As a preferred embodiment of the invention, the dosage ratio of the main agent of the two-component adhesive to the curing agent of the two-component adhesive is (2.5-3.5): 1.
as a preferred embodiment of the present invention, the adhesive comprises one or more of a low viscosity epoxy adhesive and a polydimethylsiloxane.
As a preferred embodiment of the present invention, the time for removing bubbles in vacuum is 5 to 20 minutes.
As a more preferable embodiment of the invention, the time for removing bubbles in vacuum is 10-15 min.
As a preferred embodiment of the present invention, the first film layer and/or the third film layer is a polymer film, and the polymer film includes one or more of biaxially oriented polypropylene, biaxially oriented polyethylene terephthalate, polypropylene, polyethylene terephthalate, polycarbonate, polyimide, and polyvinylidene fluoride.
In a preferred embodiment of the present invention, the thickness of the first film layer is 5 μm to 6 μm.
As a preferred embodiment of the present invention, the total thickness of the second film layer and the third film layer is 0.5 μm to 3 μm.
The invention provides a five-layer composite film, which is prepared by the preparation method of the five-layer composite film.
As a preferred embodiment of the present invention, the five-layer composite film has a thickness of 10 μm to 15. Mu.m.
The invention provides application of a five-layer composite film in preparation of capacitors, electric automobiles and hybrid electric automobiles.
The invention has at least the following beneficial effects:
compared with the prior art, the invention adopts the polymer film with high breakdown strength as an upper film and a lower film, adopts the insulating nano sheet film layer with wide band gap as an electron blocking layer to block the transport of carriers and the propagation of breakdown paths, and uses the adhesive in the middle to play a role of connecting the upper film and the lower film and can also construct a good interface between layers. The five-layer composite film has excellent energy storage property, and the maximum discharge energy density can reach 8.76J/cm 3 Meanwhile, the charge and discharge efficiency can reach 94 percent. Therefore, the polymer five-layer composite film provided by the invention has a good application prospect in the field of capacitor energy storage.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention.
FIG. 1 is a sectional scanning electron microscope image of a five-layer composite film PBEBP-4 of example 4;
FIG. 2 is a graph showing the dielectric constants and dielectric losses of five-layer composite films prepared in examples 1 to 6 and comparative example 1 as a function of frequency;
FIG. 3 is a Weibull plot of the breakdown field strength of the five-layer composite films prepared in examples 1-6 and comparative example 1;
fig. 4 is a graph showing changes in discharge energy density and charge-discharge efficiency with field intensity at room temperature of the five-layer composite films prepared in examples 1 to 6 and comparative example 1.
Detailed Description
Exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The embodiment of the invention provides a preparation method of a five-layer composite film, which comprises the following steps:
(1) 2.5g of hexagonal boron nitride (h-BN) powder was dispersed in a mixed solution of 100ml of deionized water and 100ml of isopropyl alcohol and placed in a water bath under ultrasonic agitation for 12 hours. Centrifuging the obtained solution at 6000rpm for 15min, collecting supernatant, centrifuging at 11000rpm for 10min, drying the obtained precipitate in oven at 70deg.C for 12 hr, and removing solvent to obtain BNSS.
(2) Weighing 10mg of BNSs powder obtained in the step (1) into 10ml of isopropanol, preparing 1mg/ml BNSs dispersion liquid, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading 6 μm dried polyethylene terephthalate (BOPET) film on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on the bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.2g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the proportion of 3:1, and then placed in a vacuum drying oven for air suction and bubble for 15min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (2) taking the double-layer film obtained in the step (2), slowly attaching the BNSs layer downwards to the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 30min at 70 ℃ and 20MPa, and then placing the film into a baking oven at 70 ℃ to cure for 24h, thus obtaining the five-layer composite film PBEBP-1.
Example 2
(1) As in example 1.
(2) Weighing 20mg of BNSs powder obtained after stripping in the step (1) into 10ml of isopropanol, preparing BNSs dispersion liquid with the concentration of 2mg/ml, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading a BOPET film with the thickness of 6 μm on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on a bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.4g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the ratio of 3.5:1, and then placed in a vacuum drying oven for air suction and bubbling for 10min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (2) taking the double-layer film obtained in the step (2), slowly attaching the BNSs layer downwards to the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 20min at 65 ℃ and 10MPa, and then placing the film into a baking oven at 75 ℃ to be cured for 24h, thus obtaining the five-layer composite film PBEBP-2.
Example 3
(1) As in example 1.
(2) Weighing 30mg of BNSs powder obtained after stripping in the step (1) into 10ml of isopropanol, preparing 3mg/ml BNSs dispersion liquid, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading a BOPET film with the thickness of 6 μm on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on a bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.0g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the proportion of 2.5:1, and then placed in a vacuum drying oven for air suction and bubbling for 8min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (3) taking the double-layer film obtained in the step (2), bonding the BNSs layer downwards slowly with the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 25min at 75 ℃ and 15MPa, and then placing the film into a drying oven at 65 ℃ to be cured for 24h, thus obtaining the five-layer composite film PBEBP-3.
Example 4
(1) As in example 1.
(2) Weighing 40mg of BNSs powder obtained after stripping in the step (1) into 10ml of isopropanol, preparing 4mg/ml BNSs dispersion liquid, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading a BOPET film with the thickness of 6 μm on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on a bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.2g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the proportion of 3:1, and then placed in a vacuum drying oven for air suction and bubbling for 5min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (2) taking the double-layer film obtained in the step (2), slowly attaching the BNSs layer downwards to the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 30min at 70 ℃ and 20MPa, and then placing the film into a baking oven at 70 ℃ to cure for 24h, thus obtaining the five-layer composite film PBEBP-4.
Example 5
(1) As in example 1.
(2) Weighing 50mg of BNSs powder obtained after stripping in the step (1) into 10ml of isopropanol, preparing BNSs dispersion liquid with the concentration of 5mg/ml, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading a BOPET film with the thickness of 6 μm on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on a bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.2g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the proportion of 3:1, and then placed in a vacuum drying oven for air suction and bubbling for 20min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (2) taking the double-layer film obtained in the step (2), slowly attaching the BNSs layer downwards to the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 30min at 70 ℃ and 20MPa, and then placing the film into a baking oven at 70 ℃ to cure for 24h, thus obtaining the five-layer composite film PBEBP-5.
Example 6
(1) As in example 1.
(2) Weighing 60mg of BNSs powder obtained after stripping in the step (1) into 10ml of isopropanol, preparing BNSs dispersion liquid with the concentration of 6mg/ml, and carrying out ultrasonic treatment for 2-3 hours to obtain a uniform mixed solution. Spreading a BOPET film with the thickness of 6 μm on a clean glass plate, dripping 2ml of the solution on the surface of the film, adjusting the height of a scraper to 400 μm, uniformly coating the solution on a bottom BOPET film by using a tape casting method, and transferring to a 70 ℃ oven for evaporating the solvent for 5min to obtain the double-layer film.
(3) 1.2g of the low-viscosity epoxy adhesive a component and 0.4g of the low-viscosity epoxy adhesive b component are weighed, mixed and stirred for 10min according to the proportion of 3:1, and then placed in a vacuum drying oven for air suction and bubbling for 13min. And (3) spreading the double-layer film obtained in the step (2) on a clean glass plate, dripping 2ml of adhesive on the surface of the double-layer film, and adjusting the height of a scraper to be 100 mu m to uniformly coat the adhesive on the double-layer film to obtain the three-layer film. And (2) taking the double-layer film obtained in the step (2), slowly attaching the BNSs layer downwards to the adhesive on the uppermost layer in the three-layer film to cover the film, hot-pressing for 30min at 70 ℃ and 20MPa, and then placing the film into a baking oven at 70 ℃ to cure for 24h, thus obtaining the five-layer composite film PBEBP-6.
Comparative example 1
BOPET at 6 μm.
Test example 1
Scanning Electron Microscope (SEM): the five-layer composite film is cooled by liquid nitrogen and then brittle broken, after the metal spraying treatment is carried out on the sample, the surface morphology of the brittle fracture surface is observed by using a field emission scanning electron microscope (Hitachi, SU 8010) with the accelerating voltage of 3 kV.
Dielectric property test: copper electrodes are respectively evaporated on two sides of a film by a high vacuum resistance evaporation coating machine, and then the film coated with the copper electrodes is put into a precise impedance analyzer (Novoco)ntrol Technologies BDS 40) the copper electrode was clamped by a jig, and the multilayer composites prepared in examples 1 to 6 and comparative example 1 were tested at room temperature at 1Hz to 10 6 Dielectric properties in the Hz range.
Breakdown field strength test: five-layer composite films prepared in examples 1 to 6 and comparative example 1 were sandwiched between two electrodes using an RK2674A type withstand voltage tester, and the electrodes together with the films were immersed in insulating oil (simethicone) to continuously increase the voltage until the voltage value was instantaneously lowered, and the maximum value of the voltage was recorded. The ratio of the maximum voltage value to the film thickness is the breakdown field intensity value.
And (3) energy storage density testing: copper electrodes were first vapor-deposited on both sides of the five-layer composite films prepared in examples 1 to 6 and comparative example 1, respectively, using a high vacuum resistance vapor-deposition coater, and then the copper-plated films were placed between two electrodes in a ferroelectric tester (U.S. radio company, precision Multiferroic), the electrodes together with the films were immersed in insulating oil (simethicone), the frequency was set to 10Hz, and the electric displacement-electric field strength (D-E) curves thereof were tested at different voltages. And obtaining the required energy storage density on the Y axis of the coordinate axis by using the D-E curve.
FIG. 1 is a scanning electron microscope image of a cross section of a five-layer composite film obtained in example 4, which shows that the successful construction of a multilayer structure has a good interlayer interface and can effectively inhibit propagation of an electric tree.
FIG. 2 is a graph showing the variation of dielectric constants and dielectric losses with frequency of five-layer composite films (PBEBP-1, PBEBP-2, PBEBP-3, PBEBP-4, PBEBP-5, PBEBP-6, BOPET) prepared in examples 1 to 6 and comparative example 1. As can be seen from the graph, at 1KHz, the dielectric constants of PBEBP-1, PBEBP-2, PBEBP-3, PBEBP-4, PBEBP-5, PBEBP-6 and BOPET were 3.40, 3.37, 3.36, 3.37, 3.32, 3.43 and 3.27, respectively, indicating that the dielectric constants of examples 1 to 6 and comparative example 1 were substantially stable at 3.25 to 3.45, and that the influence of the construction of the multilayer structure and the introduction of BNSs was small. At 1KHz, the dielectric losses of PBEBP-1, PBEBP-2, PBEBP-3, PBEBP-4, PBEBP-5, PBEBP-6, BOPET are 0.00463, 0.00469, 0.00494, 0.00470, 0.00493, 0.00493, 0.00565, respectively, all after modificationThe multilayer films of (a) all had lower dielectric loss than the BOPET film of comparative example 1. With increasing BNSs content, dielectric loss has smaller variation range and lower level, 1-10 6 Within the frequency range of Hz<0.03。
FIG. 3 is a Weibull plot of breakdown field strengths of five-layer composite films (PBEBP-1, PBEBP-2, PBEBP-3, PBEBP-4, PBEBP-5, PBEBP-6, BOPET) prepared in examples 1 to 6 and comparative example 1. From the graph, the construction of the multi-layer structure and the introduction of the BNSs layer improve the breakdown strength, and the breakdown strength of the multi-layer film tends to be increased and then decreased with the increase of the thickness of the BNSs layer. The breakdown of the multilayer film PBEBP-4 in example 4 was at most 739MV/m, while the breakdown of the BOPET film in comparative example 1 was 635MV/m. Since BNSS is most densely arranged on the BOPET film in the embodiment 4, the BNSS can be better used as an electron blocking layer to inhibit the formation of a conductive path.
FIG. 4 is a graph showing changes in discharge energy density and charge-discharge efficiency with field intensity at room temperature of five-layer composite films (PBEBP-1, PBEBP-2, PBEBP-3, PBEBP-4, PBEBP-5, PBEBP-6, BOPET) prepared in examples 1 to 6 and comparative example 1. As can be seen from the figure, the sample PBEBP-4 of example 4 had a J/cm of 8.76 3 High discharge energy density of (c) and high charge-discharge efficiency of 94%.
It should be appreciated that in the above description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the method of the invention should not be interpreted as reflecting the intention: i.e., the claimed invention requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
Furthermore, those skilled in the art will appreciate that while some embodiments described herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims, any of the claimed embodiments may be used in any combination.
The foregoing is merely illustrative of the embodiments of the present invention and is not intended to be limiting in any way or nature, and it should be noted that modifications and additions to the ordinary skill in the art without departing from the method of the present invention are also contemplated as falling within the scope of the present invention; equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, and modifications, to which the invention pertains; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the protection scope of the present invention.

Claims (10)

1. A method for preparing a five-layer composite film, which is characterized by comprising the following steps:
uniformly coating the insulating nano sheet dispersion liquid on the first film layer by taking the insulating nano sheet dispersion liquid as a raw material to form a second film layer, thereby obtaining a double-layer film;
and uniformly coating the adhesive on the second film layer by taking the adhesive solution as a raw material to form a third film layer, thereby obtaining the three-layer film.
And attaching the second film layer of the obtained double-layer film to the third film layer of the obtained three-layer film to obtain a five-layer composite film.
2. The method for preparing a five-layer composite film according to claim 1, wherein the method for preparing the insulating nanoplatelets comprises:
adding inorganic powder into a mixed solution of an organic solvent and water, performing water bath ultrasonic treatment, and centrifuging;
centrifuging the supernatant, precipitating and drying to obtain an insulating nano sheet;
wherein the inorganic powder comprises one or more of boron nitride, alumina, mica and montmorillonite; the organic solvent comprises one or more of isopropanol, dimethylformamide and N-methylpyrrolidone.
3. The method for preparing a five-layer composite film according to claim 1, wherein the insulating nano-sheets are two-dimensional nano-sheets, and the size of the insulating nano-sheets is 500-5000 nm.
4. The method for preparing a five-layer composite film according to claim 1, wherein the method for preparing the adhesive solution comprises:
uniformly mixing a main agent of the bi-component adhesive and a curing agent of the bi-component adhesive, and then removing bubbles in vacuum to obtain an adhesive solution; wherein the adhesive comprises one or more of low-viscosity epoxy adhesive and polydimethylsiloxane.
5. The method for preparing a five-layer composite film according to claim 1, wherein the first film layer and/or the third film layer is a polymer film, and the polymer film comprises one or more of biaxially oriented polypropylene, biaxially oriented polyethylene terephthalate, polypropylene, polyethylene terephthalate, polycarbonate, polyimide, and polyvinylidene fluoride.
6. The method of claim 1, wherein the first film layer has a thickness of 5 μm to 6 μm.
7. The method of producing a five-layer composite film according to claim 1 to 6, wherein the total thickness of the second film layer and the third film layer is 0.5 μm to 3 μm.
8. A five-layer composite film, characterized in that the five-layer composite film is prepared by the preparation method of the five-layer composite film according to any one of claims 1 to 7.
9. The five-layer composite film according to claim 8, wherein the thickness of the five-layer composite film is 10 μm to 15 μm.
10. Use of a five-layer composite film according to any one of claims 8 to 9 for the production of capacitors, electric vehicles, hybrid vehicles.
CN202311077531.6A 2023-08-25 2023-08-25 Five-layer composite film and preparation method and application thereof Pending CN117301674A (en)

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