CN115975234A - Preparation method of three-layer structured polyethersulfone-based high-temperature dielectric composite film - Google Patents
Preparation method of three-layer structured polyethersulfone-based high-temperature dielectric composite film Download PDFInfo
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- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 212
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 212
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229910052582 BN Inorganic materials 0.000 claims abstract description 96
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 62
- 239000011259 mixed solution Substances 0.000 claims abstract description 54
- 239000002135 nanosheet Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 239000002121 nanofiber Substances 0.000 claims abstract description 35
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 102
- 239000000243 solution Substances 0.000 claims description 71
- 239000005711 Benzoic acid Substances 0.000 claims description 51
- 235000010233 benzoic acid Nutrition 0.000 claims description 51
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 41
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 38
- 150000001412 amines Chemical class 0.000 claims description 38
- 239000000654 additive Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 34
- 230000000996 additive effect Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 67
- 239000006185 dispersion Substances 0.000 description 36
- 239000007788 liquid Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 6
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 3
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a three-layer structured polyethersulfone-based high-temperature dielectric composite film, which adopts a coating process to prepare a polyethersulfone-based three-layer film and comprises the following steps: s1, preparing boron nitride nanosheets and titanium dioxide nanofibers; s2, preparing a mixed solution; and S3, preparing the polyether sulfone three-layer film. According to the preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film, the three-layer-structure polyethersulfone-based high-temperature dielectric composite film prepared by the method has the following beneficial effects: not only can the nanosheets be effectively dispersed in the polyether sulfone matrix, but also has high temperature stability, high dielectric constant, high energy storage density and good comprehensive performance.
Description
Technical Field
The invention relates to the field of dielectric energy storage materials, in particular to a preparation method of a three-layer structured polyethersulfone-based high-temperature dielectric composite film.
Background
The poor high temperature stability of polymer dielectric materials limits their applications in electromagnetic catapulting, weapon systems, new energy vehicles, and the like. Currently, the operating temperature of commercial Biaxially oriented polypropylene BOPP (Biaxially oriented polypropylene) is 105 ℃, and when the temperature reaches 80 ℃, the dielectric properties thereof are drastically reduced. In order to continue to use the BOPP film in a high temperature environment, an additional cooling system is required to maintain the ambient temperature at 60-80 ℃. This will undoubtedly increase the quality of the overall system and increase costs. Therefore, the development of new high temperature dielectric materials is imminent. Compared with BOPP, the polyether sulfone has excellent high-temperature stability and higher dielectric constant, but the further application of the polyether sulfone in the field of high-temperature energy storage is limited by the larger dielectric loss of the polyether sulfone.
In the prior art, researches are mainly focused on reducing the leakage conduction loss of the polyether sulfone in a high-temperature state by adding a small amount of nano particles with high forbidden band width.
The prior art has the following defects: 1) The nano particles are difficult to uniformly disperse in the polyether sulfone matrix due to the large specific surface area, so that the improvement on the high-temperature energy storage performance of the polyether sulfone is limited; 2) Because the dielectric constant of the nano particles with high forbidden band width is small, the dielectric constant of the polyether sulfone is difficult to improve with a lower addition amount of the nano particles.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a three-layer-structure polyethersulfone-based high-temperature dielectric composite film with effective dispersion of nanosheets in a polyethersulfone matrix and good comprehensive properties (high-temperature stability, high dielectric constant and high energy storage density).
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention discloses a preparation method of a three-layer structured polyethersulfone-based high-temperature dielectric composite film, which adopts a coating process to prepare a polyethersulfone-based three-layer film and comprises the following steps:
s1, preparation of boron nitride nanosheet and titanium dioxide nanofiber
Adding h-BN into an organic solvent, and sequentially grinding by a sand mill and ultrasonically vibrating to obtain boron nitride nanosheets;
adding isopropyl titanate, glacial acetic acid and polyvinyl acetate into an organic solvent to form a titanium dioxide precursor spinning solution, and performing electrostatic spinning to obtain the titanium dioxide non-woven fabric. Sintering the obtained non-woven fabric in a high-temperature sintering furnace to obtain titanium dioxide nano-fibers;
s2, preparation of mixed solution
The preparation of the mixed solution comprises the preparation of a polyether sulfone/boron nitride/additive mixed solution and the preparation of a polyether sulfone/titanium dioxide mixed solution;
preparation of polyethersulfone/boron nitride/additive mixed solution: weighing boron nitride nanosheets and additives with fixed mass; mixing polyether sulfone with an organic solvent, and magnetically stirring under a water bath condition to obtain a transparent mixed solution A, wherein the water bath temperature is 50-70 ℃, and the water bath time is 3-5 hours; adding the boron nitride nanosheet and the additive into the mixed solution A, and uniformly stirring by ultrasonic to obtain a polyether sulfone/boron nitride/additive mixed solution;
preparation of polyether sulfone/titanium dioxide mixed solution: weighing titanium dioxide nanofibers with fixed mass; mixing polyether sulfone with an organic solvent, and magnetically stirring in a water bath condition to obtain a transparent mixed solution B, wherein the water bath temperature is 50-70 ℃, and the water bath time is 3-5 hours; adding the titanium dioxide nano-fibers into the mixed solution B, and uniformly stirring by ultrasonic to obtain a polyether sulfone/titanium dioxide mixed solution;
s3, preparation of polyether sulfone three-layer film
Uniformly coating the polyether sulfone/boron nitride/additive mixed solution on a substrate, and drying for 1-10h at 40-100 ℃ to obtain a polyether sulfone/boron nitride/additive composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/additive composite film, and drying for 1-10h at the temperature of 40-100 ℃ to obtain a polyether sulfone-based double-layer film; and coating the polyether sulfone/boron nitride/additive mixed solution on the polyether sulfone-based double-layer film, and drying for 1-10h at the temperature of 40-100 ℃ to obtain the polyether sulfone-based three-layer film.
On the basis of the above scheme and as a preferable scheme of the above scheme, the grinding speed for preparing the boron nitride nanosheet is 3000r/min, the grinding medium used is zirconium beads, the grinding times are 2 times, the first grinding time is 2 hours, the diameter of the zirconium beads is 0.5mm, the second grinding time is 2 hours, and the diameter of the zirconium beads is 0.1mm; the power of ultrasonic vibration is 1000-1400W, the ultrasonic time is 2h, and the temperature is 30 ℃.
On the basis of and as a preferred embodiment of the above embodiment, the proportions of isopropyl titanate, glacial acetic acid, polyvinyl acetate and N-methylpyrrolidone, which are raw materials for preparing the titanium dioxide nanofiber, are 15%, 7%, 8% and 70%.
On the basis of the scheme, the preferred scheme of the scheme is that the speed of the electrostatic spinning of the titanium dioxide precursor is 0.15mm/min, the positive voltage is 5kV, and the negative voltage is-4 kV.
On the basis of the scheme, as a preferable scheme of the scheme, the sintering temperature for preparing the titanium dioxide nano-fiber is 450 ℃, and the sintering time is 30min.
On the basis of the scheme and as a preferable scheme of the scheme, the polyether sulfone accounts for 20-40% of the organic solvent by mass percent.
Based on and as a preferred aspect of the above aspect, the additive is a low molecular weight acid (molecular weight 100-1000) formulated with a non-electrolytic polymeric dispersant.
On the basis of the scheme, the additive is compounded by benzoic acid and polyoxyethylene amine, wherein the proportion of the benzoic acid is 50%.
On the basis of the above scheme and as a preferable scheme of the above scheme, the doping amount of the additive is 0.1 to 0.5vol% of the polyethersulfone/boron nitride/additive composite film, the doping amount of the boron nitride nanosheet is 1 to 10vol% of the volume of the polyethersulfone/barium titanate/additive composite material, and the doping amount of the titanium dioxide nanofiber is 1 to 7vol% of the volume of the polyethersulfone/silicon oxide composite material.
On the basis of the above scheme and as a preferable scheme of the above scheme, the thickness of the boron nitride nanosheet is 20-50nm, and the width is 100-300nm; the length-diameter ratio of the titanium dioxide nano-fiber is 8-12..
On the basis of and as a preferred mode of the above mode, the organic solvent is one or more of N-methylpyrrolidone, dimethylacetamide and dimethylformamide.
On the basis of the scheme, the ultrasonic power for preparing the polyether sulfone/boron nitride/additive mixed solution is 900W-1200W, the ultrasonic time is 15min, and the temperature is 30 ℃.
The invention has the beneficial effects that:
1) The three-layer structured polyethersulfone-based high-temperature dielectric composite film provided by the invention comprises an upper layer of polyethersulfone/silicon nitride/additive layer with high breakdown field strength and a middle layer of polyethersulfone/titanium dioxide layer with high polarization strength. Compared with a commercial biaxially oriented polypropylene film or a single-layer polyether sulfone and polyether sulfone based composite film, the film has excellent dielectric property and high-temperature energy storage property;
2) The additive can be adsorbed on the surface of the boron nitride nanosheet to generate a steric hindrance effect, so that the dispersibility of the nanosheet in a polyether sulfone matrix is improved; trace benzoic acid and polyoxyethyleneamine can be adsorbed on the surface of the nanosheet, and the dispersibility of the boron nitride nanosheet in the polyether sulfone matrix is improved, so that the movement of current carriers is effectively hindered, the leakage loss is further reduced, and the high-temperature energy storage performance is improved;
3) The method for preparing the three-layer-structure polyethersulfone-based high-temperature dielectric composite film has the advantages of simple process, low production cost and high continuous production potential, and can be applied to industrialization.
Detailed Description
The present invention will be further described with reference to specific examples, which are intended to clearly and completely describe the technical solutions in the examples of the present invention, and it should be understood that the described examples are only a part of the examples of the present invention, and not all of the examples. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
(1) Preparing a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethyleneamine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 1% of boron nitride nanosheet, 0.25% of benzoic acid, 0.25% of polyoxyethylene amine and 78.5% of N-methyl pyrrolidone; magnetically stirring for 3 hours under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on a substrate, and drying for 2 hours at the temperature of 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Example 2
(1) Preparing a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethyleneamine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of boron nitride nanosheet, 0.25% of benzoic acid, 0.25% of polyoxyethylene amine and 76.5% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3 hours under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on a substrate, and drying for 2 hours at the temperature of 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Example 3
(1) Preparing a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethylene amine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 5% of boron nitride nanosheet, 0.25% of benzoic acid, 0.25% of polyoxyethylene amine and 74.5% of N-methylpyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid/polyoxyethylenamine solution on a substrate, and drying for 2 hours at 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid/polyoxyethylenamine composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyethersulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyethersulfone-based three-layer polyethersulfone film.
Example 4
(1) Preparing a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethyleneamine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 7% of boron nitride nanosheet, 0.25% of benzoic acid, 0.25% of polyoxyethylene amine and 72.5% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3 hours under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on a substrate, and drying for 2 hours at the temperature of 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Comparative example 1
(1) Preparing a polyether sulfone solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; wherein the weight ratio is as follows: 20% of polyether sulfone and 80% of N-methylpyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) And (3) coating the solution on a glass plate, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone film.
Comparative example 2
(1) Preparing a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethylene amine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 5% of boron nitride nanosheet, 0.25% of benzoic acid, 0.25% of polyoxyethylene amine and 74.5% of N-methylpyrrolidine; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; wherein the weight ratio is as follows: 20% of polyether sulfone and 80% of N-methyl pyrrolidone; magnetically stirring for 3 hours under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on a substrate, and drying for 2 hours at the temperature of 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film; coating a layer of polyether sulfone solution on the surface of the polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; coating a layer of polyether sulfone/boron nitride/benzoic acid/polyoxyethylene amine solution on the surface of the polyether sulfone-based double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Comparative example 2 is a three-layer film with no silica nanofibers added in the middle layer compared to example 3.
Comparative example 3
(1) Preparing a polyether sulfone solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; wherein the weight ratio is as follows: 20% of polyether sulfone and 80% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone solution on a substrate, and drying for 2 hours at 50 ℃ to obtain a polyether sulfone film; coating a layer of polyether sulfone/titanium dioxide solution on the surface of the polyether sulfone film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyether sulfone solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Comparative example 3 is a three-layer film without boron nitride nanosheets and additives added to the upper and lower layers as compared to examples 1-4.
Comparative example 4
(1) Preparing a polyether sulfone/boron nitride solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid and a boron nitride nanosheet into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 5% of boron nitride nanosheet and 75% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride solution on a substrate, and drying for 2h at 50 ℃ to obtain a polyether sulfone/boron nitride composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; and coating a layer of polyether sulfone/boron nitride solution on the surface of the double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Comparative example 4 is a three-layer film with no additive added to the upper and lower layers compared to example 3.
Comparative example 5
(1) Preparing a polyether sulfone/boron nitride/benzoic acid solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a mixed solution from the pre-dispersion liquid, the boron nitride nanosheets and benzoic acid; wherein the weight ratio is as follows: 20% of polyether sulfone, 5% of boron nitride nanosheet, 0.5% of benzoic acid and 74.5% of N-methylpyrrolidine; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/benzoic acid solution on a substrate, and drying for 2h at 50 ℃ to obtain a polyether sulfone/boron nitride/benzoic acid composite film; coating a layer of polyether sulfone solution on the surface of the polyether sulfone/boron nitride/benzoic acid composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone based double-layer film; coating a layer of polyether sulfone/boron nitride/benzoic acid solution on the surface of the polyether sulfone-based double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
In comparative example 5, no polyoxyethyleneamine was added to the upper and lower layers compared to example 3.
Comparative example 6
(1) Preparing a polyether sulfone/boron nitride/polyoxyethylene amine solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion liquid, boron nitride nanosheets, benzoic acid and polyoxyethyleneamine into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 5% of boron nitride nanosheet, 0.5% of polyoxyethylene amine and 74.5% of N-methylpyrrolidine; magnetically stirring for 3h under the condition of water bath at 60 ℃ to obtain a transparent solution;
(2) Preparing a polyether sulfone/titanium dioxide solution: dispersing polyether sulfone particles in N-methyl pyrrolidone to obtain a pre-dispersion liquid; preparing a pre-dispersion solution and titanium dioxide nano fibers into a mixed solution; wherein the weight ratio is as follows: 20% of polyether sulfone, 3% of titanium dioxide nanofiber and 77% of N-methyl pyrrolidone; magnetically stirring for 3 hours under the condition of water bath at 60 ℃ to obtain a transparent solution;
(3) Uniformly coating a polyether sulfone/boron nitride/polyoxyethylene amine solution on a substrate, and drying for 2h at 50 ℃ to obtain a polyether sulfone/boron nitride/polyoxyethylene amine composite film; coating a layer of polyether sulfone solution on the surface of the polyether sulfone/boron nitride/polyoxyethylene amine composite film, and drying for 10 hours at the temperature of 50 ℃ to obtain a polyether sulfone-based double-layer film; coating a layer of polyether sulfone/boron nitride/polyoxyethylene amine solution on the surface of the polyether sulfone-based double-layer film, and drying for 10 hours at the temperature of 50 ℃ to obtain the polyether sulfone-based three-layer film.
Comparative example 6 the upper and lower layers were not added with benzoic acid as compared to example 3.
Performance testing
The films of the above examples and comparative examples were subjected to vacuum evaporation to prepare metal circular electrodes, and the properties thereof were tested.
(1) Dielectric properties: the test was carried out using an impedance analyzer (Keysight E4990A).
(2) And (3) electric hysteresis loop test: a ferroelectric tester (PK-CPE 1701) is used for testing, and the energy storage density and the charge and discharge efficiency are obtained by calculating a ferroelectric hysteresis loop.
The dielectric properties including dielectric constant and dielectric loss were measured for the examples and comparative examples, respectively, and the polarization curve and the energy storage density were measured at a frequency of 10Hz, and the results of the related property measurements are shown in table 1 below.
TABLE 1 results of dielectric property test of examples and comparative examples
As can be seen from table 1, example 1 has excellent dielectric properties and high-temperature energy storage properties.
Compared with the pure polyether sulfone film of the comparative example 1, the dielectric constant is improved by 21%, and the high-temperature energy storage performance is improved by 158%;
the addition of the titanium dioxide nano-fiber with high dielectric constant can improve the dielectric constant of the polyether sulfone matrix; the addition of the boron nitride nanosheets with high forbidden band widths can effectively reduce the high-temperature leakage loss of the polyether sulfone matrix;
and trace benzoic acid and polyoxyethyleneamine can be adsorbed on the surface of the nanosheet, so that the dispersibility of the boron nitride nanosheet in the polyether sulfone matrix is improved, the movement of current carriers is effectively hindered, the leakage loss is further reduced, and the high-temperature energy storage performance is improved. If benzoic acid or polyoxyethyleneamine is added separately, the dispersibility of the boron nitride nanosheet is poor, and the improvement on the high-temperature energy storage performance of the film is limited.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method of a three-layer structured polyethersulfone-based high-temperature dielectric composite film is characterized by comprising the following steps: the preparation method of the polyether sulfone three-layer film by adopting a coating process comprises the following steps:
s1, preparation of boron nitride nanosheet and dioxide nanofiber
1) Adding h-BN into N-methylpyrrolidone, and grinding by a sand mill and ultrasonic vibration to obtain boron nitride nanosheets;
2) Adding isopropyl titanate, glacial acetic acid and polyvinyl acetate into N-methyl pyrrolidone to form a titanium dioxide precursor spinning solution, performing electrostatic spinning to obtain a titanium dioxide non-woven fabric, and sintering the obtained non-woven fabric in a high-temperature sintering furnace to obtain titanium dioxide nano fibers;
s2, preparation of mixed solution
1) The preparation of the mixed solution comprises the preparation of a polyether sulfone/boron nitride/additive mixed solution and the preparation of a polyether sulfone/titanium dioxide mixed solution;
2) Preparation of polyethersulfone/boron nitride/additive mixed solution: weighing boron nitride nanosheets and additives with fixed mass; mixing polyether sulfone with an organic solvent, and magnetically stirring under a water bath condition to obtain a transparent mixed solution A, wherein the water bath temperature is 50-70 ℃, and the water bath time is 3-5 hours; adding the boron nitride nanosheet and the additive into the mixed solution A, and uniformly stirring by ultrasonic to obtain a polyether sulfone/boron nitride/additive mixed solution;
3) Preparation of polyether sulfone/titanium dioxide mixed solution: weighing titanium dioxide nanofibers with fixed mass; mixing polyether sulfone with an organic solvent, and magnetically stirring in a water bath condition to obtain a transparent mixed solution B, wherein the water bath temperature is 50-70 ℃, and the water bath time is 3-5 hours; adding the titanium dioxide nano-fibers into the mixed solution B, and uniformly stirring by ultrasonic to obtain a polyether sulfone/titanium dioxide mixed solution;
s3, preparation of polyether sulfone three-layer film
Uniformly coating the polyether sulfone/boron nitride/additive mixed solution on a substrate, and drying for 1-10h at 40-100 ℃ to obtain a polyether sulfone/boron nitride/additive composite film; coating a layer of polyether sulfone/titanium dioxide mixed solution on the surface of the polyether sulfone/boron nitride/additive composite film, and drying for 1-10h at the temperature of 40-100 ℃ to obtain a polyether sulfone-based double-layer film; and coating the polyether sulfone/boron nitride/additive mixed solution on the polyether sulfone-based double-layer film, and drying for 1-10h at the temperature of 40-100 ℃ to obtain the polyether sulfone-based three-layer film.
2. The preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the grinding speed of the prepared boron nitride nanosheets is 3000r/min, the grinding medium used is zirconium beads, the grinding times are 2 times, the first grinding time is 2 hours, the diameter of the zirconium beads is 0.5mm, the second grinding time is 2 hours, and the diameter of the zirconium beads is 0.1mm; the power of ultrasonic vibration is 1000-1400W, the ultrasonic time is 2h, and the temperature is 30 ℃.
3. The preparation method of the three-layer structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the proportion of isopropyl titanate, glacial acetic acid, polyvinyl acetate and N-methyl pyrrolidone which are used as raw materials for preparing the titanium dioxide nano-fibers is 15%, 7%, 8% and 70%.
4. The preparation method of the three-layer structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the sintering temperature for preparing the titanium dioxide nano-fibers is 450 ℃, and the sintering time is 30min; the ultrasonic power for preparing the polyether sulfone/boron nitride/additive mixed solution is 900W-1200W, the ultrasonic time is 15min, and the temperature is 30 ℃.
5. The preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the polyethersulfone accounts for 20-40% of the organic solvent by mass percent.
6. The preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film as claimed in claim 1, wherein the additive is a mixture of a low molecular weight acid with a molecular weight of 100-1000 and a non-electrolytic polymer dispersant.
7. The preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film according to claim 6, wherein the additive is a compound of benzoic acid and polyoxyethylene amine, wherein the proportion of benzoic acid is 50%.
8. The preparation method of the three-layer-structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the doping amount of the additive is 0.1-0.5% of the polyethersulfone/boron nitride/additive composite material, the doping amount of the boron nitride nanosheet is 1-10% of the polyethersulfone/boron nitride/additive composite material, and the doping amount of the titanium dioxide nanofiber is 1-7% of the volume of the polyethersulfone/titanium dioxide composite material.
9. The preparation method of the bilayer structure polyethersulfone based high-temperature dielectric composite film according to claim 5, wherein the thickness of the boron nitride nanosheet is 20-50nm, and the width is 100-300nm; the length-diameter ratio of the titanium dioxide nano-fiber is 8-12.
10. The preparation method of the three-layer structure polyethersulfone-based high-temperature dielectric composite film according to claim 1, wherein the organic solvent is any one or more of N-methylpyrrolidone, dimethylacetamide and dimethylformamide.
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| CN114805892A (en) * | 2022-05-19 | 2022-07-29 | 乌镇实验室 | Preparation method of polyether sulfone-based high-temperature dielectric composite film with double-layer structure |
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| CN109161428A (en) * | 2018-07-31 | 2019-01-08 | 张毅 | A kind of high wearproof lubricant and preparation method thereof |
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| CN114805892A (en) * | 2022-05-19 | 2022-07-29 | 乌镇实验室 | Preparation method of polyether sulfone-based high-temperature dielectric composite film with double-layer structure |
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