CN114249921B - Nanofiber filler for capacitor film, capacitor film comprising same, and method for producing capacitor film - Google Patents

Nanofiber filler for capacitor film, capacitor film comprising same, and method for producing capacitor film Download PDF

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CN114249921B
CN114249921B CN202111386044.9A CN202111386044A CN114249921B CN 114249921 B CN114249921 B CN 114249921B CN 202111386044 A CN202111386044 A CN 202111386044A CN 114249921 B CN114249921 B CN 114249921B
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filler
layer
capacitor film
nanofiber
nanofiber filler
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CN114249921A (en
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李姜
李美涵
郭少云
张先龙
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Sichuan University
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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
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    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32—LAYERED PRODUCTS
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/204—Di-electric
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Abstract

The invention relates to the technical field of capacitor films, and discloses a nanofiber filler for a capacitor film, which comprises nano silicon dioxide and nano barium titanate; the preparation method comprises the steps of preparing spinning solution by using a barium carbonate precursor, a silicon dioxide precursor, a chelating agent and a complexing agent as raw materials through a sol method, obtaining a spinning body through electrostatic spinning, and calcining and grinding the spinning body to obtain the nanofiber filler. The nanofiber filler of this application includes nanometer silica and nanometer barium titanate to the nanofiber filler that this raw materials preparation obtained can make barium titanate cladding nanometer silica, obtains the nanofiber filler of high draw ratio, and the structure of high draw ratio makes dielectric property more excellent, still can prevent simultaneously that nanometer silica from agglomerating, reduces dielectric loss, makes the filler disperse more evenly in the base member.

Description

Nanofiber filler for capacitor film, capacitor film comprising same, and method for producing capacitor film
Technical Field
The invention relates to the technical field of capacitor films, in particular to a nanofiber filler for a capacitor film, the capacitor film containing the nanofiber filler and a preparation method of the capacitor film.
Background
In recent years, in order to alleviate the problems of environmental pollution, energy shortage and the like caused by fossil energy, renewable energy technologies such as solar cells, lithium cells, capacitors and the like are rapidly developed, wherein the capacitors have the advantages of high charging and discharging speed, good stability, low cost and the like compared with energy storage devices such as lithium cells and the like, and are suitable for being applied to high-power electronic equipment. However, the high-power capacitor generally has the defect of low energy storage density. Therefore, how to increase the energy storage density of the capacitor is a bottleneck of research in the field.
To increase the energy storage density of a dielectric material, it is necessary to increase the relative permittivity and breakdown-resistant electric field value thereof. Inorganic fillers typically have high dielectric constants in the thousands, but have low breakdown fields, whereas polymers have high breakdown fields, but typically have dielectric constants as low as 10 or less, and it is clear that either single component inorganic fillers or polymers are not ideal dielectric materials. The inorganic filler/polymer dielectric composite material is considered to be one of the most potential dielectric materials at present due to the characteristics of the dielectric constant of the inorganic filler and the breakdown field resistance, low loss and flexibility of the polymer.
At present, after a high-content inorganic filler is added, the dielectric constant of the composite is obviously increased, but the inorganic filler not only introduces defects such as holes and cracks in the composite, but also destroys the flexibility of the composite, so that the high dielectric constant is usually at the expense of the breakdown-resistant electric field value of a sacrificial material, and the improvement of the energy storage density of the composite is limited; the existing capacitor film has the problems of poor dispersibility of the inorganic filler in a polymer matrix and poor processability, so that the energy storage density of the capacitor film is low.
Disclosure of Invention
< problems to be solved by the present invention >
The existing capacitor film has the problems of high addition amount of inorganic nano filler in a polymer matrix, poor dispersibility in the polymer matrix, poor processability and low energy storage density.
< technical solution adopted in the present invention >
In view of the above-described problems, an object of the present invention is to provide a nanofiber filler for a capacitor film, a capacitor film including the same, and a method for producing a capacitor film.
The specific contents are as follows:
firstly, the invention provides a nanofiber filler for a capacitor film, which comprises nano silicon dioxide and nano barium titanate;
the preparation method comprises the steps of preparing spinning solution by using a barium titanate precursor, nano silicon dioxide, a chelating agent and a complexing agent as raw materials through a sol method, obtaining a spinning body through electrostatic spinning, and calcining and grinding the spinning body to obtain the nano fiber filler.
Secondly, the invention provides a capacitor film, which is obtained by mutually laminating and stretching a material layer A and a material layer B; the A material layer comprises a nano-fiber filler-LDPE blend, and the B material layer is a PE layer.
Thirdly, the invention provides a method for preparing a capacitor film, which is characterized by comprising the following steps:
s1, preparing a layer A, and blending and extruding raw materials of the layer A;
s2, respectively forming the layer A and the layer B to obtain sheets, and overlapping the sheets to obtain a composite sheet;
and S3, carrying out biaxial tension treatment on the composite sheet layer.
< technical mechanism and advantageous effects of the present invention >
(1) The nano-fiber filler comprises nano-silica and nano-barium titanate, and the nano-fiber filler prepared from the raw materials can enable the barium titanate to coat the nano-silica to obtain the nano-fiber filler with high length-diameter ratio, the structure with high length-diameter ratio enables the dielectric property to be better, meanwhile, the nano-silica can be prevented from agglomerating, the dielectric loss is reduced, and the filler is dispersed in a matrix more uniformly.
(2) The nano-fiber filler is ground and then added into the material layer A, so that the problem of agglomeration can be effectively avoided.
(3) Because the nanofiber filler/polymer has a low percolation threshold, the peak value of the dielectric constant can be reached only by adding a small amount of the nanofiber filler/polymer, and compared with the traditional inorganic nano filler, the nanofiber filler/polymer is easier to be uniformly dispersed in a polymer matrix, so that the advantage of high breakdown electric field resistance of the polymer matrix is kept.
(4) The high aspect ratio nanofiber filler has a larger dipole moment and can more effectively increase the dielectric constant of the composite under the same conditions.
(5) LDPE is selected from the capacitor film, so that the biaxial stretching process can be well realized, and compared with the traditional PE film, the BOPE film has higher mechanical property and material rigidity and better optical and printing properties.
Drawings
FIG. 1 is a transmission electron micrograph (100 nm) of the S-BT nanofiber filler obtained in example 1;
FIG. 2 is a polarization micrograph of the capacitor film prepared in example 1;
FIG. 3 is a graph showing the variation of the dielectric constant with frequency of the capacitor film prepared in example 1;
FIG. 4 is a graph showing the variation of dielectric loss with frequency of the capacitor film prepared in example 1;
FIG. 5 is a graph showing the energy storage density of the capacitor film 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 conventional products which are not indicated by manufacturers and are commercially available.
Firstly, the invention provides a nanofiber filler for a capacitor film, which comprises nano silicon dioxide and nano barium titanate;
the preparation method comprises the steps of preparing spinning solution by using a sol method by using a barium titanate precursor, a silicon dioxide precursor, a chelating agent and a complexing agent as raw materials, obtaining a spinning body through electrostatic spinning, and calcining and grinding the spinning body to obtain the nanofiber filler.
The nano-silica and the nano-barium titanate are prepared into the nano-fiber filler by adopting an electrostatic spinning method, and the barium titanate can coat the nano-silica by adopting a solution sol method to obtain the nano-fiber filler with high length-diameter ratio, so that the dielectric property is better due to the structure with high length-diameter ratio, and meanwhile, the nano-silica can be prevented from agglomerating, the dielectric loss is reduced, and the filler is more uniformly dispersed in a matrix.
The nano-silicon dioxide and the nano-barium titanate are combined to form the nano-fiber filler, and the nano-fiber filler is added into the BOPE to form a material layer A, so that the material layer A not only has good tensile strength, high breakdown strength, low electricity and other properties, but also can improve electric field distribution and inhibit the growth of electric branches; meanwhile, the dielectric constant and the thermal stability of the BOPE can be improved, so that the electrical, mechanical and mechanical properties of the BOPE are improved.
In the invention, in the nanofiber filler, the nano silicon dioxide accounts for 5-15% of the total weight of the nanofiber filler.
In the present invention, the sol includes barium acetate, tetrabutyl titanate, and a chelating agent, and the ratio of the amounts of the barium acetate, tetrabutyl titanate, and the chelating agent is 1.
In the invention, the chelating agent is acetylacetone, and the complexing agent is polyvinylpyrrolidone.
The preparation method of the spinning solution comprises the steps of sequentially adding acetic acid, barium acetate, chelating agent, tetrabutyl titanate, absolute ethyl alcohol, nano silicon dioxide and complexing agent into a container, and keeping constant temperature and stirring to obtain the spinning solution each time the materials are added.
The specific operation steps are that the components are weighed according to the mass,
(1) 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;
(2) adding barium acetate into hot acetic acid under stirring, heating in 40 deg.C water bath, and stirring for 30min to dissolve barium acetate completely;
(3) and (3) adding acetylacetone into the flask in the step (2), and fully stirring for 30min under the heating of a water bath at 40 ℃ to fully and uniformly mix the acetylacetone with the solution.
(4) Adding tetrabutyl titanate and absolute ethyl alcohol into the flask obtained in the step (3), and fully stirring for 2 hours under the water bath heating at 25 ℃ to fully and uniformly mix tetrabutyl titanate and the solution;
(5) adding nano silicon dioxide 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.
(6) Adding polyvinylpyrrolidone, adjusting the viscosity of the solution, and preparing the sol.
In the invention, the electrostatic spinning is carried out by adopting a common electrostatic spinning device. And (4) carrying out grounding treatment by using aluminum foil and collecting by using silicone oil paper. 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 20kV.
In the invention, the spinning body is prepared by a segmented gradient heating method when being calcined.
In the present invention, in N 2 Under protection, the temperature is raised to 550-600 ℃ at a first heating rate and is preserved for 0.5-2 h, and then the temperature is raised to 650-700 ℃ at a second heating rate and is preserved for 1-3 h.
Secondly, the invention provides a capacitor film, which is obtained by mutually laminating and stretching a material layer A and a material layer B; the A material layer comprises a nano-fiber filler-LDPE blend, and the B material layer is a PE layer.
The coating structure formed by coating the nano-silica with the barium titanate is added into the LDPE by grinding, and a material layer A is obtained by melting, so that the problems of uneven dispersion and easy agglomeration caused by directly adding the nano-silica and the nano-barium titanate can be effectively avoided.
In particular LDPE, dow chemical production, designation XUS 59910.08, density 0.926g/cm 3 Melt index 1.7g/10min (190 ℃,2.16 kg).
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.
In the invention, the nano-fiber filler accounts for 0.04-0.06% of the total amount of the A material layer.
Thirdly, the invention provides a preparation method of a capacitor film, which comprises the following steps:
s1, preparing a layer A, and blending and extruding raw materials of the layer A;
s2, respectively forming the layer A and the layer B to obtain sheets, and overlapping the sheets to obtain a composite sheet;
and S3, carrying out biaxial tension treatment on the composite sheet layer.
In the present invention, the number of layers of the capacitor film is 4.
The capacitor film adopts a multilayer structure design, and the formed multilayer film structure has the advantages of high energy storage density, high temperature resistance, low loss and the like. One layer of the multilayer film is a polymer with high dielectric constant, and the other layer is a polymer with higher breakdown strength. 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.
Specifically, the molding treatment is to obtain the sheet material by cold press molding and hot pressing into the sheet in a flat vulcanizing machine.
In the invention, the temperature of each section of the double-screw extruder is respectively 190 ℃ of feeding port, 190 ℃ of conveying section, 195 ℃ of melting section, 195 ℃ of homogenizing section and 195 ℃ of extrusion opening mold.
In the invention, the nano-fiber filler and the LDPE are respectively preheated for 3-5 min at 180 ℃, exhausted for 10-15 times, hot-pressed for 5-7 min at 1-2s and 10MPa, cold-pressed for 3-5 min, and hot-pressed into sheets with the thickness of 250-300 mu m; and overlapping the sheets in an ABAB form, and then carrying out hot pressing for 5-7 min under 10 MPa.
In the present invention, the biaxial stretching was carried out at 110 ℃ under the process parameters of a stretching ratio of 5X 5 and a stretching rate of 50%/s.
< example >
Example 1
A preparation method of a capacitor film comprises the following steps:
(1) Preparation of nanofiber Filler
(1) 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 hot acetic acid which is stirred, and the mixture is fully stirred for 30min under the heating of water bath at the temperature of 40 ℃ so that the barium acetate is completely dissolved;
(3) adding 1.5g of acetylacetone into the flask in the step (2), and fully stirring for 30min under heating in a water bath at 40 ℃ to fully and uniformly mix the acetylacetone and the solution.
(4) Adding 2.88g of tetrabutyl titanate and 4.5g of absolute ethyl alcohol into the flask in the step (3), and fully stirring for 2 hours under the condition of heating in a water bath at 25 ℃ to fully and uniformly mix the tetrabutyl titanate and the solution;
(5) and adding 0.1165g of the solution after the reaction, and putting the solution into an ultrasonic instrument for dispersing for 2 hours to ensure that the solution is uniformly dispersed.
(6) Adding 2.15g of polyvinylpyrrolidone, adjusting the viscosity of the solution and preparing the sol.
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 20kV.
Calcining the collected spinning mass, 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 (the nano silicon dioxide accounts for 5 percent of the total weight of the nano fiber filler).
(2) Preparation of sheet
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 die) 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 S-BT/PE blend with the mass fraction of the nano-fiber filler (S-BT) of 0.4 percent is blended and extruded.
Using a plate vulcanizing machine to preheat pure PE and S-BT/PE master batches (mBOPE) for 3-5 min at 180 ℃, exhausting for 10-15 times, wherein the exhausting time is 1-2s, the hot pressing time is 5-7 min at 10MPa, the cold press molding time is 3-5 min, and the pure PE and the S-BT/PE master batches (mBOPE) are hot pressed into sheets (the size is 100mm multiplied by 100 mm), and the thickness is 280 mu m. And overlapping the sheets in an ABAB form for hot pressing, wherein the hot pressing time is 5-7 min under 10 MPa.
(3) Biaxial tension
The film stretching forming adopts a Karo IV type film biaxial stretching experimental machine of German Brukner company. First, preheating 100 ℃ for 100s, synchronously stretching at 110 ℃ in two directions with the stretching ratio of 5 multiplied by 5, and then cooling at room temperature with the stretching rate of 50%/s to obtain the film.
Example 2
The difference between this embodiment and embodiment 1 is that the proportion of the spinning solution is different, so that the nano-silica accounts for 15% of the total weight of the nano-silica-nano barium titanate composite. Specifically, 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 nano titanium dioxide and 4.223g of polyvinylpyrrolidone.
Example 3
The present example is different from example 1 in that the mass fraction of S-BT in (4) is 0.6%.
< comparative example >
Comparative example 1
The difference between the comparative example and the example 1 is that the mBOPE prepared in the step (4) is placed in a plate vulcanizing machine, cold press molding is carried out, and hot pressing is carried out on the finished product in an AAAA mode. The hot and cold pressing parameters were the same as in example 1.
Comparative example 2
The comparative example is different from example 1 in that nano barium titanate, nano silica and PE are put into a twin-screw extruder in a mass ratio of 1.
< test example >
The capacitor films obtained in examples 1 to 3 and comparative examples 1 to 2 were used as samples for performance tests, and the dielectric properties and the energy storage density of the samples were measured.
Dielectric testingIs to a film sampleThe test is carried out, the surface of the sample is cleaned by ethanol, gold (gold ion sputtering) is sprayed on the surface, the dielectric property measurement is carried out at room temperature (25 ℃), and the test frequency is 0.1-1 multiplied by 10 7 Hz, the dielectric constant (. Epsilon.) and the dielectric loss (. Di-elect cons.) of the sample were measured as a function of frequency.
Energy storage density testThe sample preparation mode is the same as that of the sample for testing the dielectric property. 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 tables 1 and 2.
TABLE 1 dielectric constant and energy storage Density of different samples (dielectric constant at 1000Hz frequency; energy storage Density at an electric field of 225KV/mm and a draw ratio of 5X 5)
Figure GDA0003967056400000091
The S-BT obtained in example 1 was observed under a transmission electron microscope to obtain FIG. 1.
The dielectric properties of the capacitor films prepared in the examples are shown in FIGS. 2 to 5, respectively.
Fig. 2 is a polarization micrograph of the capacitor film prepared in example 1.
Fig. 3 and 4 are graphs showing the dielectric constant and dielectric loss of the capacitor film prepared in example 1 as a function of frequency, respectively.
FIG. 5 is a graph showing the energy storage density of the capacitor films prepared in examples 1 to 3.
Note: the preparation method of the BOPE sample in fig. 3-5 is that pure PE particles are melt extruded, hot pressed to obtain a final 4-layer thickness of 300 μm, and then the sheet is biaxially stretched to obtain the BOPE. And when the dielectric property and the energy storage density are measured, the measurement is carried out by keeping the same thickness of each test sample.
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 (8)

1. The nanofiber filler for the capacitor film is characterized by comprising nano silicon dioxide and nano barium titanate;
the preparation method comprises the steps of preparing spinning solution by using a sol method by using a barium titanate precursor, a silicon dioxide precursor, a chelating agent and a complexing agent as raw materials, obtaining a spinning body through electrostatic spinning, and calcining and grinding the spinning body to obtain the nanofiber filler.
2. The nanofiber filler for capacitor films according to claim 1, wherein the sol comprises barium acetate, tetrabutyl titanate and a chelating agent, and the ratio of the amounts of the barium acetate, tetrabutyl titanate and chelating agent is 1.
3. The nanofiber filler for capacitor films according to claim 1 or 2, wherein the spinning solution is prepared by sequentially adding acetic acid, barium acetate, chelating agent, tetrabutyl titanate, absolute ethyl alcohol, nanosilicon dioxide and complexing agent into a container, and stirring while maintaining a constant temperature every time the addition is made to obtain the spinning solution.
4. The nanofiber filler for capacitor films as claimed in claim 3, wherein the spun fiber is prepared by a stepwise gradient heating method during calcination.
5. The nanofiber filler for capacitor film as claimed in claim 4, wherein N is 2 Under protection, the temperature is raised to 550-600 ℃ at a first heating rate and is preserved for 0.5-2 h, and then raised to 650-700 ℃ at a second heating rate and is preserved for 1-3 h.
6. A capacitor film is characterized in that the capacitor film is obtained by mutually laminating and stretching a material layer A and a material layer B; the layer A comprises a blend of nanofiber filler-LDPE, the layer B is a PE layer and the nanofiber filler is as in any one of claims 1 to 5.
7. The capacitive film of claim 6 wherein the nanofiber filler comprises 0.04 to 0.06% of the total amount of the A layer.
8. A method for preparing the capacitor film according to claim 6 or 7, comprising the steps of:
s1, preparing a layer A, and blending and extruding raw materials of the layer A;
s2, respectively forming the layer A and the layer B to obtain sheets, and overlapping the sheets to obtain a composite sheet;
and S3, carrying out biaxial tension treatment on the composite sheet layer.
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