CN114559721A - Sandwich-structure high-energy-storage-density polyimide-based composite film and preparation method thereof - Google Patents
Sandwich-structure high-energy-storage-density polyimide-based composite film and preparation method thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000004642 Polyimide Substances 0.000 title claims abstract description 59
- 238000004146 energy storage Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005266 casting Methods 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 15
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 9
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 36
- 229920001690 polydopamine Polymers 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 18
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000002356 single layer Substances 0.000 abstract description 5
- 239000011256 inorganic filler Substances 0.000 abstract description 4
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 15
- 238000001000 micrograph Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 3
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- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical group CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021523 barium zirconate Inorganic materials 0.000 description 1
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000013339 polymer-based nanocomposite Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- 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
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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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The invention provides a sandwich-structure high-energy-storage-density polyimide-based composite film and a preparation method thereof. The composite film is used as an intermediate layer, the pure polymer is used as an outer layer, and the composite film is obtained by a one-layer solution casting method and high-temperature annealing treatment. The invention adopts polydopamine as a surface modifier, so that the compatibility of barium titanate and a polymer matrix is enhanced; improving the dispersibility of barium titanate in the matrix; the dielectric constant is improved by introducing the modified barium titanate/polymer composite film as the middle layer, and the breakdown strength is improved by the pure polymer layers on the upper and lower outer layers; the sandwich structure enables the amount of high dielectric inorganic filler particles contained in the single-layer film to be controlled, and the single-layer film is not easy to agglomerate or settle.
Description
Technical Field
The invention relates to a polyimide-based composite film with a sandwich structure and high energy storage density and a preparation method thereof, belonging to the technical field of preparation of dielectric polymer films.
Background
With the increasing energy crisis facing human beings, the development of a dielectric capacitor with ultra-fast charge and discharge and high power density is one of the research hotspots in the commercial and scientific communities. In the application of the fields of hybrid electric vehicles, aerospace and the like, the dielectric medium is required to be as light and small as possible, but the ceramic capacitor with larger volume cannot meet the requirement of the high-energy-storage-density dielectric capacitor with light and small size. Applications in the field of avionics and automotive industry, the underground oil and gas exploration industry, and advanced propulsion systems require long-term operation of dielectric materials at temperatures of 150 ℃ and even higher. Among the various types of dielectric capacitor materials, flexible polymer-based nanocomposites hold the most promise to meet the above needs. Polyimides (PI) are used for their unique properties, such as: mechanical flexibility, low density, good thermal stability and the like, and is widely applied to the research of dielectric films; the working temperature of the common polymer dielectric material, namely biaxial stretching polypropylene (BOPP), is below 105 ℃, and the long-term use temperature range of the polyimide is-200-300 ℃, so that the high-temperature resistance of the polyimide is much better than that of the BOPP. Therefore, the polyimide-based composite film prepared by taking polyimide as a polymer matrix and adding the inorganic filler with high dielectric constant into the matrix has the potential of meeting the current technical development requirements, namely high temperature resistance, low loss and high energy storage density.
However, the polyimide film has a low dielectric constant, which affects its energy storage performance, and thus its application in the direction of high energy density dielectrics is limited. Ceramic particles with high dielectric constant such as Barium Titanate (BT), Barium Zirconate Titanate (BZT), Copper Calcium Titanate (CCTO) and the like are used as inorganic fillers, and the method is the simplest and most effective method for improving the dielectric property of the polymer-based material. In order to avoid the agglomeration of the nanofiller to form pores and to maintain the breakdown strength of the polymer nanocomposite, it is necessary to improve the compatibility between the filler and the matrix by means of surface modification of the filler. In addition, a plurality of performances of the polymer can be effectively improved by constructing a multi-layer composite and small-amount doping form, wherein the research on the composite film with a symmetrical sandwich structure is more, namely the components of the upper and lower outer layers of the composite film are the same.
Disclosure of Invention
The invention aims to provide a polyimide-based composite film with a sandwich structure and high energy storage density and a preparation method thereof. The polymer-based composite film with the sandwich structure is prepared by taking PI with excellent heat resistance as a matrix and BT @ PDA nano-particles as a filler through a one-layer solution casting method and performing high-temperature thermal imidization.
The technical scheme of the invention is as follows: firstly, coating BT nano particles by using dopamine hydrochloride solution to prepare organically modified barium titanate nano particles (BT @ PDA) with a core-shell structure, mechanically blending the barium titanate nano particles with polyamide acid solution (PAA), removing bubbles in a blending polymerization system in vacuum, casting to form a film, and then performing high-temperature thermal imidization to obtain a single-layer polymer-based composite film (BT @ PDA/PI). The composite film is used as an intermediate layer, pure polyimide is used as an outer layer, and the polyimide-based composite film with a sandwich structure and high energy storage density is obtained through a layer-by-layer solution casting method and high-temperature annealing treatment.
The invention provides a method for preparing a polyimide-based composite film with a sandwich structure and high energy storage density, which comprises the following steps:
s1, dispersing the modified BT particles in a proper amount of organic solvent, and carrying out ultrasonic treatment for 10min to obtain a modified BT particle suspension;
s2, synthesizing polyimide precursor solution polyamic acid (PAA) by respectively taking pyromellitic dianhydride (PMDA) and 4, 4-diaminodiphenyl ether (ODA) as dianhydride and diamine monomers;
s3, adding the modified BT particle suspension into the PAA solution, and mechanically stirring for 2-3 hours to form uniformly mixed suspension which is modified barium titanate/polyimide;
s4, preparing a first layer of film by using the modified barium titanate/polyimide obtained in the step S3 through a tape casting method, paving a second layer of film on the first layer of film after drying, and paving a third layer of film after drying; performing high-temperature thermal imidization to obtain a composite film;
the composite film is used as an intermediate layer, pure polyimide is used as an outer layer, and the polyimide-based composite film with a sandwich structure and high energy storage density is obtained through a layer-by-layer solution casting method and high-temperature annealing treatment.
In step S1, the organic solvent is a nitrogen methyl pyrrolidone solvent NMP.
In the step S2, dissolving ODA by using NMP as a solvent, stirring for 30min until ODA is completely dissolved, slowly adding a proper amount of PMDA monomer for 3 times, and stirring for 8-10 h to obtain a PAA solution.
The content of the modified BT particles in the step S3 accounts for 1 wt% -40 wt% of the total mass of the solids in the composite film, and the total mass of the solids is the sum of the modified BT particles and the mass of the solids in the PAA solution.
In step S4, before the film is formed by casting, the suspension is vacuumed to remove air bubbles.
The drying temperature of each layer in the step S4 is 250-300 ℃, and the drying time is 6-10 hours.
The thickness of the upper and lower pure polymer films of the sandwich structure is 15-20 um respectively, and the thickness of the middle layer modified barium titanate/polyimide film is 15-20 um.
The preparation method of the modified BT particle comprises the following steps:
(1) under the shading condition, BaTiO is added3Dispersing in a proper amount of 0.01mL dopamine hydrochloride solution;
(2) placing the reaction vessel into a constant-temperature magnetic stirring oil bath kettle, wherein the oil bath temperature of the oil bath kettle is 60 ℃;
(3) after stirring is started, adding the dopamine hydrochloride aqueous solution into the barium titanate particle suspension for multiple times, and transferring all residual dopamine into a reaction container by using a small amount of ultrapure water;
(4) stirring at 60 ℃ for 24h, centrifuging the obtained dispersion at high speed to obtain surface-modified barium titanate nanoparticles, then centrifugally cleaning with ethanol for 2 times, and collecting the lower-layer precipitate; and (3) drying the mixture for 24 hours in vacuum at the temperature of 80 ℃ to obtain organically modified BT @ PDA nano particles, namely modified BT particles.
The particle size of the barium titanate particles is less than 100 nm.
In the dopamine hydrochloride aqueous solution, the ratio of dopamine hydrochloride: h2O＝0.3g：50mL。
The invention has the following technical effects:
(1) the poly-dopamine is used as a surface modifier, so that the compatibility of barium titanate and a polymer matrix is enhanced; improve the dispersibility of barium titanate in the matrix.
(2) The dielectric constant is improved by introducing the modified barium titanate/polymer composite film as the middle layer, and the breakdown strength is improved by the pure polymer layers on the upper and lower outer layers; the designed sandwich structure ensures that the amount of high-dielectric inorganic filler particles contained in the single-layer film is controlled and the single-layer film is not easy to agglomerate or settle.
(3) And barium titanate fillers with different contents are added to study the influence of different filler contents on the dielectric property of the composite material. And optimizing the content of the filler to prepare the barium titanate/polyimide composite film with the sandwich structure and the optimal comprehensive dielectric property.
(4) Polyimide is adopted as a polymer matrix material, so that the defect that the heat resistance of the polymer dielectric film capacitor is low is overcome.
Drawings
FIG. 1a is a transmission electron microscope photograph of barium titanate having a particle size of 100 nm;
FIG. 1b is a TEM image of barium titanate (core-shell structure) coated with poly-dopamine and having a particle size of 100 nm;
FIG. 2a is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with a 0 wt% content of BT @ PDA filler;
FIG. 2b is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with a 1 wt% content of BT @ PDA filler;
FIG. 2c is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with 10 wt% of BT @ PDA filler;
FIG. 2d is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with a 20 wt% content of BT @ PDA filler;
FIG. 2e is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with a 30 wt% content of BT @ PDA filler;
FIG. 2f is a scanning electron microscope image of a cross section of a sandwich-structured high energy storage density polyimide-based composite film with a 40 wt% content of BT @ PDA filler;
FIG. 3 is a graph showing the change of dielectric constant with temperature of a polyimide-based composite film with a sandwich structure and high energy storage density at 1 kHz.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
In the embodiment, barium titanate with the particle size not greater than 100nm is selected to be compounded with polyimide, the upper outer layer and the lower outer layer are pure polymers, and the middle layer is a sandwich structure film of a modified barium titanate/polymer film. The mass fraction of the filler is changed, the polyimide-based composite film with the sandwich structure and the high energy storage density is prepared, wherein the filler content is 1 wt%, 10 wt%, 20 wt%, 30 wt% and 40 wt%, and the dielectric constant, the dielectric loss and the temperature stability of a sample are tested.
Preparing modified BT particles, namely core-shell poly-dopamine coated nano particles:
(1) under the shading condition, BaTiO is added3(100 nm) is dispersed in a proper amount of 0.01mol/L dopamine hydrochloride solution;
(2) placing the reaction vessel into a constant-temperature magnetic stirring oil bath kettle, wherein the oil bath temperature of the oil bath kettle is 60 ℃;
(3) after stirring is started, adding the dopamine hydrochloride aqueous solution into the barium titanate particle suspension for multiple times, and transferring all residual dopamine into a reaction container by using a small amount of ultrapure water;
(4) stirring at 60 ℃ for 24h, centrifuging the obtained dispersion at high speed to obtain surface-modified barium titanate nanoparticles, then centrifugally cleaning with ethanol for 2 times, and collecting the lower-layer precipitate; and (3) drying for 24h in vacuum at 80 ℃ to obtain modified BT nano particles (BT @ PDA) coated by Polydopamine (PDA).
BaTiO3(-100 nm) and polyatomicTransmission electron microscopy of the bamine coated modified BT nanoparticles, as shown in fig. 1a and 1 b.
The preparation method of the polyimide-based composite film with the sandwich structure and high energy storage density comprises the following steps:
s1, dispersing the modified BT particles in a proper amount of organic solvent N-methyl pyrrolidone (NMP), and carrying out ultrasonic treatment for 10min to obtain modified BT particle suspension;
s2, dissolving 4, 4-diaminodiphenyl ether (ODA) by taking NMP as a solvent, stirring for 30min until the ODA is completely dissolved, slowly adding a proper amount of pyromellitic dianhydride (PMDA) for 3 times, and stirring for 8-10 h to obtain a polyamide acid solution (PAA).
S3, adding the modified BT particle suspension into the PAA solution, and mechanically stirring for 2-3 hours to form a uniformly mixed suspension;
s4, removing bubbles from the suspension in vacuum, preparing a first layer of film by using the modified barium titanate/polyimide obtained in S3 through a tape casting method, spreading a second layer of film on the first layer of film after drying, and spreading a third layer of film after drying; performing high-temperature thermal imidization to obtain a composite film;
the composite film is used as an intermediate layer, the pure polymer is used as an outer layer, and the polyimide-based composite film with the sandwich structure and the high energy storage density is obtained after high-temperature annealing treatment by a one-layer-by-one-layer solution casting method.
After 3 times of high-temperature thermal imidization, the sandwich-structure high-energy-storage-density polyimide-based composite film with the thicknesses of the upper and lower pure polymer films of 10-15um and the middle modified barium titanate/polyimide film of 10-15um is obtained. The composite films were represented as 0-0-0, 1-0-1, 10-0-10, 20-0-20, 30-0-30, 40-0-40, respectively, depending on the amount of the filler BT @ PDA.
The cross-sectional scanning electron microscope of the prepared polyimide-based composite film with different contents and sandwich structure and high energy storage density is shown in fig. 2a to 2 f.
Table 1 dielectric property table of sandwich structure high energy storage density polyimide based composite film with different contents.
The specific changes in dielectric properties of the composite films obtained with modified BT particle content (0 wt%, 1 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%) are shown in table 1. As can be seen from the table, the dielectric constant of the sandwich structure modified barium titanate/polyimide composite material is higher than that of pure polyimide at 1 kHz. And, as the content of the BT @ PDA nanoparticles increases, the dielectric constant of the multilayer BT @ PDA/polyimide composite film also gradually increases.
For polymer dielectrics, the temperature stability is an especially important parameter. FIG. 3 shows the temperature dependence of the dielectric properties of pure polyimide, x-0-x sandwich BT @ PDA/PI composite films measured at 100Hz, 1kHz, 10kHz, 100kHz and 1MHz respectively. The dielectric constant of all samples decreased by no more than 1.1 when the temperature increased from 25 ℃ to 160 ℃ at the selected 5 frequency points; the dielectric loss of the same sample at the same frequency point has little change, and the fluctuation value is not more than 0.04. The change of the temperature can be seen to have no obvious influence on the dielectric property of the sandwich BT @ PDA/polyimide composite film, and the characteristic has important significance on the application of the composite material in a high-temperature environment.
Claims (10)
1. The preparation method of the polyimide-based composite film with the sandwich structure and high energy storage density is characterized by comprising the following steps:
s1, dispersing the modified BT particles in a proper amount of organic solvent, and carrying out ultrasonic treatment for 10min to obtain a modified BT particle suspension;
s2, synthesizing polyimide precursor solution polyamide acid PAA by respectively taking pyromellitic dianhydride and 4, 4-diaminodiphenyl ether as dianhydride and diamine monomers;
s3, adding the modified BT particle suspension into the PAA solution, and mechanically stirring for 2-3 hours to form uniformly mixed suspension which is modified barium titanate/polyimide;
s4, preparing a first layer of film by using the modified barium titanate/polyimide obtained in the step S3 through a tape casting method, paving a second layer of film on the first layer of film after drying, and paving a third layer of film after drying; performing high-temperature thermal imidization to obtain a composite film;
the composite film is used as an intermediate layer, the pure polyimide is used as an outer layer, and the polyimide-based composite film with the sandwich structure and the high energy storage density is obtained through a layer-by-layer solution casting method and high-temperature annealing treatment.
2. The method for preparing the polyimide-based composite film with the sandwich structure and the high energy storage density according to claim 1, wherein the organic solvent in step S1 is N-methylpyrrolidone solvent NMP.
3. The preparation method of the sandwich structure high energy storage density polyimide-based composite film according to claim 1, wherein in step S2, 4-diaminodiphenyl ether ODA is dissolved by using NMP as a solvent, and after the ODA is completely dissolved, a proper amount of pyromellitic dianhydride PMDA is slowly added for 3 times, and the mixture is stirred for 8-10 hours to obtain a polyamic acid solution.
4. The method for preparing the polyimide-based composite film with the sandwich structure and the high energy storage density according to claim 1, wherein the modified BT particle accounts for 1-40 wt% of the total solid mass of the composite film in step S3, and the total solid mass is the sum of the modified BT particles and the solid mass in the PAA solution.
5. The method for preparing a polyimide-based composite film with a sandwich structure and a high energy storage density according to claim 1, wherein bubbles are removed from the suspension in vacuum before the step S4 of casting the film.
6. The method for preparing polyimide-based composite film with sandwich structure and high energy storage density as claimed in claim 1, wherein the drying temperature of each film in step S4 is 250-300 deg.C, and the drying time is 6-10 hours.
7. The sandwich-structured high energy storage density polyimide-based composite film according to claim 1, wherein: the thicknesses of the pure polymer films of the first layer and the third time are 10-100 um respectively, and the thickness of the middle layer modified barium titanate/polyimide film is 10-100 um.
8. The preparation method of the sandwich structure high energy storage density polyimide-based composite film according to any one of claims 1 to 7, wherein the preparation method of the modified BT particles comprises the following steps:
(1) under the shading condition, BaTiO is added3Dispersing in a proper amount of 0.01mol/L dopamine hydrochloride solution;
(2) placing the reaction vessel into a constant-temperature magnetic stirring oil bath kettle, wherein the oil bath temperature of the oil bath kettle is 60 ℃;
(3) after stirring is started, adding dopamine hydrochloride aqueous solution into barium titanate particle suspension for multiple times, and transferring all residual dopamine into a reaction container by using ultrapure water;
(4) stirring at 60 ℃ for 24h, centrifuging the obtained dispersion at high speed to obtain surface-modified barium titanate nanoparticles, then centrifugally cleaning with ethanol for 2 times, and collecting the lower-layer precipitate; vacuum drying at 80 ℃ for 24h to obtain the organically modified BT @ PDA nano particles, namely modified BT particles.
9. The method for preparing the polyimide-based composite film with the sandwich structure and the high energy storage density according to claim 8, wherein the particle size of the barium titanate particles is less than 100 nm.
10. The sandwich-structured high energy storage density polyimide-based composite film obtained by the preparation method according to any one of claims 1 to 9.
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