CN113921275A - Plasma modified BOPE (biaxially-oriented polyethylene) capacitor film and preparation method thereof - Google Patents
Plasma modified BOPE (biaxially-oriented polyethylene) capacitor film and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 239000004698 Polyethylene Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title description 10
- -1 polyethylene Polymers 0.000 title description 4
- 229920000573 polyethylene Polymers 0.000 title description 3
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000009832 plasma treatment Methods 0.000 claims abstract description 12
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000002041 carbon nanotube Substances 0.000 claims description 26
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 26
- 239000000945 filler Substances 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 12
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229920001684 low density polyethylene Polymers 0.000 claims description 5
- 239000004702 low-density polyethylene Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 31
- 238000004146 energy storage Methods 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000010409 thin film Substances 0.000 abstract description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002048 multi walled nanotube Substances 0.000 description 8
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 7
- 229910002113 barium titanate Inorganic materials 0.000 description 7
- 239000002121 nanofiber Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000005495 cold plasma Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
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- 230000001360 synchronised effect Effects 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
Abstract
The invention relates to the technical field of capacitor films, and discloses a BOPE capacitor film modified by plasma, which is obtained by performing plasma treatment on a biaxially oriented composite laminated sheet and carbon tetrafluoride and oxygen serving as modified gases in a volume ratio of 2: 1. The BOPE capacitor film that this application obtained through plasma modification, can reduce the polarizability of the electron of polymer and ion to can reach and reduce polymer dielectric loss, improve breakdown strength's purpose, and then improve energy storage density, still handle through nanometer barium carbonate cladding simultaneously, can promote BOPE's dielectric constant, thereby obtain high breakdown strength and high energy storage density's thin film material.
Description
Technical Field
The invention relates to the technical field of capacitor films, in particular to a plasma modified BOPE capacitor film and a preparation method thereof.
Background
With the continuous innovation of microelectronic science and technology, the trend of high speed and miniaturization of various types of electronic devices is continuously strengthened, and materials with high temperature resistance and high breakdown strength are increasingly important. In recent years, polyimide-based materials with high temperature and high breakdown strength have been paid more attention to and widely applied to components in the fields of aviation, aerospace, electronics, transportation and telecommunications.
The inorganic particles have the characteristics of high dielectric constant and low dielectric strength, so that the inorganic particles and a polymer matrix are combined with each other to form a composite material, thereby meeting the requirement of high energy storage density. Currently, only inorganic particle fillers are used, and the improvement of the energy storage density is limited. Therefore, it is very important to find a way to further improve the compatibility between the inorganic filler and the polymer matrix.
Disclosure of Invention
< problems to be solved by the present invention >
The method is used for solving the problems that the compatibility of the current inorganic filler in a polymer matrix is not enough and the promotion effect is limited.
< technical solution adopted in the present invention >
In view of the above technical problems, the present invention is directed to a BOPE capacitor film modified with plasma and a method for preparing the same.
The specific contents are as follows:
the first aspect of the invention provides a plasma-modified BOPE capacitor film, which is obtained by performing plasma treatment on a biaxially oriented composite laminated sheet by using carbon tetrafluoride and oxygen as modified gases at a volume ratio of carbon tetrafluoride to oxygen of 2: 1.
The invention provides a preparation method of a plasma modified BOPE capacitor film, which is characterized by comprising the following steps:
s1, blending and extruding the raw materials of the second material layer by a double-screw extruder to obtain filler master batches;
s2, adding the filler master batch and the pure PE particles into a multi-layer extruder, and extruding into a sheet with the total thickness of 1 mm; adding the composite filler master batch into a feed port A, and adding the pure PE particles into a feed port B;
and S3, biaxially stretching the sheet material in the S2, and carrying out plasma treatment to obtain the BOPE capacitor film.
< technical mechanism and advantageous effects of the present invention >
(1) The gas discharge plasma is generated by radio frequency glow discharge (13.56MHz) (RF discharge for short), and the advantages of the gas discharge plasma for modifying the surface of the polymer are that the power intensity and the discharge efficiency are higher, the plasma reaction can be carried out on insulating substances, and the stable and uniform glow discharge can be maintained. An electric field is added under the low-pressure gas environment, and a small amount of free electrons existing in the gas are accelerated to obtain kinetic energy. Electrons in the plasma are continually accelerated in the presence of external stimuli. While lifting their own energy, they transform or transfer the energy by colliding with each other. When the plasma high-energy electrons impact the surface of the material, the energy of the plasma high-energy electrons is transferred to surface layer molecules, so that the material is subjected to complicated physical and chemical reactions such as thermal corrosion, evaporation, crosslinking, degradation, oxidation and the like.
(2) Using carbon tetrafluoride (CF)4) And oxygen (O)2) And introducing fluorine-containing groups on the surface of the BOPE film by plasma treatment. Because the fluorine atoms have stronger electronegativity, the polarizability of electrons and ions of macromolecules can be reduced, so that the aims of reducing the dielectric loss of the macromolecules and improving the breakdown strength can be fulfilled, and the energy storage density is further improved.
(3) The surface modification treatment is carried out on the polymer/inorganic filler by the plasma, the compatibility of the polymer/inorganic filler can be improved, the interaction force between the polymer and the inorganic filler is enhanced, the volume fraction of the interface in the capacitor film is increased, the dielectric double-layer structure in the interface region is overlapped, and the dielectric constant of the film is improved.
Drawings
FIG. 1 is an infrared spectrum of BT nanofibers;
FIG. 2 is an infrared spectrum of the BT-MWCNT nanofiber obtained in example 1;
FIG. 3 is a transmission electron micrograph (100nm) of the BT-MWCNT nanofiber obtained in example 1;
FIG. 4 is a polarization micrograph of a capacitor film (32 layers) prepared in example 1;
fig. 5 is a polarization micrograph of the capacitor film (128 layers) prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The first aspect of the invention provides a plasma-modified BOPE capacitor film, which is obtained by performing plasma treatment on a biaxially oriented composite laminated sheet by using carbon tetrafluoride and oxygen as modified gases at a volume ratio of carbon tetrafluoride to oxygen of 2: 1.
In the invention, the plasma treatment process comprises the steps of radio frequency power of 100W, treatment time of 90s, discharge time of 15s and interval time of 10 s.
According to the invention, the composite laminated sheet is obtained by alternately laminating PE (polyethylene) serving as a first material layer and a composite filler layer serving as a second material layer, and the number of layers of the capacitor film is 38-128; the composite filler layer comprises LDPE and a nano barium titanate-carbon nanotube composite.
LDPE, Dow chemical production, designation XUS 59910.08, density 0.926g/cm3Melt index 1.7g/10min (190 ℃, 2.16 kg).
In the nano barium titanate-carbon nanotube composite, the carbon nanotubes account for 5-15% of the total weight of the composite.
The carbon nano tube and the nano barium titanate are combined to form the composite filler, and the composite filler is added into the BOPE to form the composite filler layer, so that the composite filler has good tensile strength, high dielectric property and the like, can improve electric field distribution, inhibit electric tree growth, improve breakdown strength and improve the dielectric constant and thermal stability of the BOPE, and further improves the electrical, mechanical and mechanical properties of the BOPE.
In the invention, the composite filler layer comprises 99.6-99.9 wt% of LDPE and 0.01-0.04 wt% of nano barium titanate-carbon nanotube composite.
The preparation method of the nano barium titanate-carbon nanotube composite comprises the steps of preparing a spinning solution by a sol method, carrying out electrostatic spinning on the spinning solution to obtain a spinning body, calcining and grinding the spinning body to obtain the nano barium titanate-carbon nanotube composite;
the sol comprises barium acetate, tetrabutyl titanate and a chelating agent, and the mass ratio of the barium acetate, the tetrabutyl titanate and the chelating agent is 1:1: 1-2.
The chelating agent is acetylacetone, and the complexing agent is polyvinylpyrrolidone.
In the invention, the preparation method of the spinning solution comprises the following steps,
and adding acetic acid, barium acetate, a chelating agent, tetrabutyl titanate, absolute ethyl alcohol, a carbon nano tube and a complexing agent into the container in sequence, and keeping the constant temperature and stirring to obtain the spinning solution each time.
The specific operation is that the components are weighed according to the mass,
adding acetic acid into a flask by using a disposable dropper, putting the flask into a heat collection type constant temperature heating magnetic stirrer, heating and stirring at 40 ℃ for 10min, and enabling the temperature of the acetic acid to reach the required 40 ℃; the purpose of the acetic acid addition is to slow down the hydrolysis;
adding barium acetate into hot acetic acid while stirring, and fully stirring for 30min under the heating of water bath at 40 ℃ to completely dissolve the barium acetate;
and thirdly, adding acetylacetone into the flask in the second step, and fully stirring for 30min under the heating of water bath at 40 ℃ to fully and uniformly mix the acetylacetone and the solution.
Adding tetrabutyl titanate and absolute ethyl alcohol into the flask in the third step, and fully stirring for 2 hours under the heating of water bath at 25 ℃ to fully and uniformly mix the tetrabutyl titanate and the solution;
fifthly, adding the carbon nano tube into the reacted solution, and putting the solution into an ultrasonic instrument for dispersing for 2 hours to ensure that the solution is uniformly dispersed.
Sixthly, adding polyvinylpyrrolidone, adjusting the viscosity of the solution and preparing sol.
In the invention, the electrostatic spinning is carried out by adopting a common electrostatic spinning device. Aluminum foil is used for grounding treatment, and silicone oil paper is used for collection. And (3) carrying out a spinning experiment on the prepared spinning solution at a distance of 15cm between a needle head and a collecting plate by adopting a 5mL needle tube (with the needle head), wherein the voltage is 20 kV.
The composite filler is prepared from the carbon nano tube and the nano barium titanate by an electrostatic spinning method, the barium titanate can coat the carbon nano tube by a solution sol method, and the barium titanate and the carbon nano tube form nano fibers by the electrostatic spinning method, so that the high length-diameter ratio is maintained, the dielectric property is better, the high-content barium titanate more effectively prevents the carbon nano tube from agglomerating, and a conductive path is prevented from being formed. The dielectric constant can be improved, the loss can be reduced, and the breakdown strength can be improved. The addition of the filler is reduced, the structural defects are reduced, and the long fiber structure has a smaller size than a three-phase system which has more uniform dispersion and improved dispersibility, so that the interaction between the filler and a matrix is better, and the dielectric loss is reduced. The formed coating structure is added into PE by grinding, and a composite filler layer is obtained by melting, so that the problems of uneven dispersion and easy agglomeration caused by directly adding the carbon nano tube and the nano barium titanate can be effectively avoided.
The invention provides a preparation method of a plasma modified BOPE capacitor film, which is characterized by comprising the following steps:
s1, blending and extruding the raw materials of the second material layer by a double-screw extruder to obtain filler master batches;
s2, adding the filler master batch and the pure PE particles into a multi-layer extruder, and extruding into a sheet with the total thickness of 1 mm; adding the composite filler master batch into a feed port A, and adding the pure PE particles into a feed port B;
and S3, biaxially stretching the sheet material in the S2, and carrying out plasma treatment to obtain the BOPE capacitor film.
In the invention, in S1, the temperatures of all sections of the double-screw extruder are respectively 190 ℃ at a feed inlet, 190 ℃ at a conveying section, 195 ℃ at a melting section, 195 ℃ at a homogenizing section and 195 ℃ at an extrusion opening die;
in the invention, in S2, the temperatures of all sections of the multilayer extruder are respectively 190 ℃ at a feed inlet, 190 ℃ at a conveying section, 195 ℃ at a melting section, 195 ℃ at a homogenizing section and 195 ℃ at an extrusion opening die.
In the present invention, in S3, the biaxial stretching was carried out at 110 ℃ at a stretching ratio of 4X 4 and a stretching rate of 50%/S.
The conventional PE film is used as an energy storage medium in a capacitor, but the PE film has a regular structure and cannot realize biaxial stretching.
The capacitor film is designed in a multilayer structure, and the formed multilayer film structure has the advantages of high energy storage density, high temperature resistance, low loss and the like. One of the layers in the multilayer film is a high dielectric constant polymer and the other layer is a higher breakdown strength polymer. When an electric field is applied to the multilayer material, ions and free electrons in the high dielectric constant layer migrate and gather at the interface, so that an effective blocking effect exists at the interface of adjacent layers, the formation of a conductive channel in the insulating layer can be inhibited, and due to the difference of dielectric constants of different layers, an applied voltage is more concentrated on the low dielectric constant layer, so that the high dielectric constant layer can be effectively protected from being prematurely broken down.
< example >
Example 1
The preparation method of the BOPE capacitor film modified by the plasma comprises the following steps:
(1) preparing spinning solution (carbon nano tube accounts for 5% of the total weight of the nano barium titanate-carbon nano tube compound)
Adding 9.5g of acetic acid into a flask by using a disposable dropper, putting the flask into a heat collection type constant temperature heating magnetic stirrer, heating and stirring at 40 ℃ for 10min, and enabling the temperature of the acetic acid to reach the required 40 ℃; the purpose of the acetic acid addition is to slow down the hydrolysis;
② 2.55g of barium acetate is added into the hot acetic acid during stirring, and the mixture is fully stirred for 30min under the water bath heating of 40 ℃ to ensure that the barium acetate is completely dissolved;
③ 1.5g of acetylacetone is added into the flask in the second step, and the mixture is fully stirred for 30min under the heating of water bath at 40 ℃ to ensure that the acetylacetone and the solution are fully and evenly mixed.
Fourthly, 2.88g of tetrabutyl titanate and 4.5g of absolute ethyl alcohol are added into the flask in the third step, and the mixture is fully stirred for 2 hours under the heating of water bath at 25 ℃ so that the tetrabutyl titanate and the solution are fully and uniformly mixed;
adding 0.1165g carbon nano tube into the reacted solution, and putting the solution into an ultrasonic instrument for dispersing for 2h to ensure that the solution is uniformly dispersed.
Sixthly, adding 2.15g of polyvinylpyrrolidone, adjusting the viscosity of the solution and preparing the sol.
(2) Carrying out electrostatic spinning
The electrostatic spinning is carried out by adopting a common electrostatic spinning device. Aluminum foil is used for grounding treatment, and silicone oil paper is used for collection. And (3) carrying out a spinning experiment on the prepared spinning solution at a distance of 15cm between a needle head and a collecting plate by adopting a 5mL needle tube (with the needle head), wherein the voltage is 20 kV.
(3) Calcination of
Calcining the collected spinning body, adopting nitrogen protection, heating to 600 ℃ at the speed of 10 ℃/min, keeping the temperature for 1h, heating to 700 ℃ at the speed of 10 ℃/min, keeping the temperature for 2h to obtain a solid, and grinding the solid into powder by a mortar.
(4) Preparation of multilayer Material
Firstly, a double-screw extruder is used, the temperature of each section (a feed inlet, a conveying section, a melting section, a homogenizing section and an extrusion opening mould) of the double-screw extruder is 190 ℃, 195 ℃ and 195 ℃, the rotating speed of a feeding screw is 70rpm, the rotating speed of an extrusion screw is 150rpm, and the BT-MWCNT/PE blend with the mass fraction of 0.2 percent of the nano barium titanate-carbon nano tube composite (BT-MWCNT) is blended and extruded. A multi-layer extruder was used, and the temperatures of the extruder sections were 190 ℃, 195 ℃ and 195 ℃. The temperature of a co-extrusion die is 195 ℃, uniformly mixed BT-MWCNT/PE master batch (mBOPE) is added into a feed inlet A, pure PE granules are added into a feed inlet B, and the mixture is extruded into sheets with the total thickness of 1mm, wherein the number of layers is 32,128 respectively.
(5) Biaxial tension
The film stretching forming adopts a Karo IV type film biaxial stretching experimental machine of German Brukner company. Preheating at 100 deg.C for 100s, synchronous biaxial stretching at 110 deg.C at a stretch ratio of 4 × 4, and cooling at room temperature at a stretch rate of 50%/s.
(6) Plasma treatment
And modifying the biaxially oriented composite film by using a cold plasma modification processor, wherein carbon tetrafluoride and oxygen are used as modified gases, the volume ratio of the carbon tetrafluoride to the oxygen is 2:1, the radio frequency power is 100W, the processing time is 90s, the discharge time is 15s, and the interval time is 10 s.
Example 2
The present example is different from example 1 in that the mixture ratio of the spinning solution is different, so that the carbon nanotubes account for 15% of the total weight of the nano barium titanate-carbon nanotube composite. Specifically, the paint comprises 18g of acetic acid, 5.16g of barium acetate, 2.022g of acetylacetone, 6.91g of tetrabutyl titanate, 10.675g of absolute ethyl alcohol, 0.699g of carbon nano tube and 4.223g of polyvinylpyrrolidone.
Example 3
This example is different from example 1 in that the mass fraction of BT-MWCNT in (4) is 0.4%.
< comparative example >
Comparative example 1
This comparative example differs from example 1 in that the mBOPE prepared in (4) was placed in a multi-layer extruder and extruded into a sheet having a total thickness of 1mm and having 32,128 in each of the layer numbers.
Comparative example 2
The comparative example is different from example 1 in that nano barium titanate, carbon nanotubes and PE were put into a twin-screw extruder in a mass ratio of 1:0.05:98.95 to be co-extruded.
Comparative example 3
This comparative example differs from example 1 in that no plasma treatment was performed.
< test example >
The capacitor films obtained in examples 1 to 2 and comparative examples 1 to 3 were used as samples for performance tests, and the dielectric properties and the energy storage density of the samples were measured.
Dielectric testingThe method comprises the steps of testing a thin film sample, cleaning the surface of the sample by using ethanol, spraying gold (gold ion sputtering) on the surface of the sample, measuring the dielectric property at room temperature (25 ℃), measuring the test frequency of 0.1-1 multiplied by 107Hz, and measuring the curves of the dielectric constant (epsilon) and the dielectric loss (D) of the sample along with the change of the frequency.
Energy storage density testThe sample preparation mode is the same as that of a sample for dielectric property test. The energy storage density of the material can be calculated according to the D-E loop measured by an experimental instrument.
The dielectric constant and energy storage density results for the samples are shown in table 1.
TABLE 1 dielectric constant and energy storage Density for different samples
(dielectric constant at 1000 Hz; energy storage density at an electric field of 225KV/mm and a draw ratio of 4X 4.)
The BT nanofibers and the BT-MWCNT nanofibers obtained in example 1 were subjected to infrared spectroscopy, resulting in fig. 1 and fig. 2.
In fig. 2, the results show that the ir peak assignment:
557 Ti-O bond, 864-CH deforming vibration, 1055-C-O-C-, 1436 CO in BaCO3 3 2-1635 carbon-carbon double bond carbon nanotube-COO, 1751-COOH, 2925 CH2 symmetric stretching vibration, 2975-CH stretching vibration, 3422-OH stretching vibration.
The BT-MWCNT nanofibers obtained in example 1 were observed under a transmission electron microscope to obtain fig. 3.
The dielectric properties of the capacitor films prepared in example 1 are shown in FIGS. 4 to 5, respectively.
Fig. 4 and 5 are polarization micrographs of the capacitor film prepared in example 1.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The BOPE capacitor film modified by utilizing plasma is characterized in that a biaxially oriented composite laminated sheet is subjected to plasma treatment by taking carbon tetrafluoride and oxygen as modified gases, wherein the volume ratio of the carbon tetrafluoride to the oxygen is 2: 1.
2. The plasma modified BOPE capacitive film of claim 1, wherein the plasma treatment process is a rf power of 100W, a treatment time of 90s, a discharge time of 15s, and an interval time of 10 s.
3. The plasma modified BOPE capacitor film according to claim 1 or 2, wherein the composite laminated sheet is obtained by alternately laminating a first material layer of PE and a second material layer of a composite filler layer, and the number of layers of the capacitor film is 38-128; the composite filler layer comprises LDPE and a nano barium titanate-carbon nanotube composite.
4. The plasma modified BOPE capacitor film as claimed in claim 3, wherein the composite filler layer comprises 99.6-99.9 wt% of LDPE and 0.01-0.04 wt% of nano barium titanate-carbon nanotube composite.
5. The plasma modified BOPE capacitor film as claimed in claim 4, wherein the nano barium titanate-carbon nanotube composite is prepared by preparing a spinning solution by a sol-gel method, subjecting the spinning solution to electrostatic spinning to obtain a spinning body, calcining the spinning body, and grinding to obtain the nano barium titanate-carbon nanotube composite;
the sol comprises barium acetate, tetrabutyl titanate and a chelating agent, and the mass ratio of the barium acetate, the tetrabutyl titanate and the chelating agent is 1:1: 1-2.
6. The plasma modified BOPE capacitor film as claimed in claim 5, wherein the spinning solution is prepared by the steps of,
and adding acetic acid, barium acetate, a chelating agent, tetrabutyl titanate, absolute ethyl alcohol, a carbon nano tube and a complexing agent into the container in sequence, and keeping the constant temperature and stirring to obtain the spinning solution each time.
7. A method of preparing a plasma modified BOPE capacitor film as claimed in any one of claims 1 to 6, comprising the steps of:
s1, blending and extruding the raw materials of the second material layer by a double-screw extruder to obtain filler master batches;
s2, adding the filler master batch and the pure PE particles into a multi-layer extruder, and extruding into a sheet with the total thickness of 1 mm; adding the composite filler master batch into a feed port A, and adding the pure PE particles into a feed port B;
and S3, biaxially stretching the sheet material in the S2, and carrying out plasma treatment to obtain the BOPE capacitor film.
8. The method of claim 7, wherein the step of forming the plasma modified BOPE capacitor film,
in S1, the temperatures of all sections of the double-screw extruder are respectively 190 ℃ at a feed inlet, 190 ℃ at a conveying section, 195 ℃ at a melting section, 195 ℃ at a homogenizing section and 195 ℃ at an extrusion opening die.
9. The method of claim 7, wherein the step of forming the plasma modified BOPE capacitor film,
in S2, the temperatures of all sections of the multilayer extruder are respectively 190 ℃ at a feed inlet, 190 ℃ at a conveying section, 195 ℃ at a melting section, 195 ℃ at a homogenizing section and 195 ℃ at an extrusion opening die.
10. The method of any one of claims 7 to 9, wherein in S3, the biaxial stretching is performed at 110 ℃ at a stretching ratio of 4 x 4 and a stretching rate of 50%/S.
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| EP0574588A1 (en) * | 1991-12-27 | 1993-12-22 | Mitsui Petrochemical Industries, Ltd. | Biaxially oriented high-molecular polyethylene film and production thereof, and surface-modified, biaxially oriented high-molecular polyethylene film and production thereof |
| JPH10235813A (en) * | 1997-02-25 | 1998-09-08 | Toppan Printing Co Ltd | Laminate and its manufacture |
| JP2004269772A (en) * | 2003-03-11 | 2004-09-30 | Konica Minolta Holdings Inc | Optical film, manufacturing method therefor, and display device using the same optical film |
| WO2008092328A1 (en) * | 2007-01-26 | 2008-08-07 | Guangdong Decro Package Films Co., Ltd. | A biaxially orientated polypropylene film for combining paper and plastic without adhesive and a preparation method thereof |
| US20100246094A1 (en) * | 2009-03-31 | 2010-09-30 | General Electric Company | Methods for improving the dielectric properties of a polymer, and related articles and devices |
| CN111916807A (en) * | 2020-07-16 | 2020-11-10 | 苏州科润新材料股份有限公司 | Ultrathin enhanced composite proton exchange membrane, preparation method and application |
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| EP0574588A1 (en) * | 1991-12-27 | 1993-12-22 | Mitsui Petrochemical Industries, Ltd. | Biaxially oriented high-molecular polyethylene film and production thereof, and surface-modified, biaxially oriented high-molecular polyethylene film and production thereof |
| JPH10235813A (en) * | 1997-02-25 | 1998-09-08 | Toppan Printing Co Ltd | Laminate and its manufacture |
| JP2004269772A (en) * | 2003-03-11 | 2004-09-30 | Konica Minolta Holdings Inc | Optical film, manufacturing method therefor, and display device using the same optical film |
| WO2008092328A1 (en) * | 2007-01-26 | 2008-08-07 | Guangdong Decro Package Films Co., Ltd. | A biaxially orientated polypropylene film for combining paper and plastic without adhesive and a preparation method thereof |
| US20100246094A1 (en) * | 2009-03-31 | 2010-09-30 | General Electric Company | Methods for improving the dielectric properties of a polymer, and related articles and devices |
| CN111916807A (en) * | 2020-07-16 | 2020-11-10 | 苏州科润新材料股份有限公司 | Ultrathin enhanced composite proton exchange membrane, preparation method and application |
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