CN113285013A - Core-shell structure piezoelectric composite material with high breakdown strength and preparation method and application thereof - Google Patents
Core-shell structure piezoelectric composite material with high breakdown strength and preparation method and application thereof Download PDFInfo
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- 230000015556 catabolic process Effects 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 60
- 239000002105 nanoparticle Substances 0.000 claims abstract description 60
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 238000004146 energy storage Methods 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 230000033444 hydroxylation Effects 0.000 claims abstract description 6
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical group CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- GIKNHHRFLCDOEU-UHFFFAOYSA-N 4-(2-aminopropyl)phenol Chemical group CC(N)CC1=CC=C(O)C=C1 GIKNHHRFLCDOEU-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
The invention relates to the technical field of energy storage, in particular to a high breakdown strength core-shell structure piezoelectric composite material, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) carrying out surface hydroxylation modification on the barium titanate nanoparticles to obtain hydroxylated barium titanate nanoparticles; (2) modifying the hydroxylated barium titanate nanoparticles by using a silane coupling agent to obtain silane coupling agent @ barium titanate nanoparticles; (3) the fluorine-containing aromatic thiourea @ barium titanate nano-particles are prepared by using a silane coupling agent @ barium titanate nano-particles as a core, using p-toluenesulfonic acid as a catalyst and carrying out polycondensation on 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and a thiourea monomer on the surfaces of the silane coupling agent @ barium titanate nano-particles by a microwave polymerization method. The high breakdown strength core-shell structure piezoelectric composite material can realize high dielectric constant and high breakdown strength at the same time, and has wide application prospect in the technical field of dielectric energy storage.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to a core-shell structure piezoelectric composite material with high breakdown strength, and a preparation method and application thereof.
Background
High dielectric constant materials are of interest for their wide application in advanced electronic devices and energy storage systems. It is difficult for a single material to further improve the dielectric constant and breakdown strength of the system. Thus, nano-compounding is a very effective means to increase the energy density of the system.
In recent years, ceramic piezoelectric and ferroelectric materials have been added to vinylidene fluoride-based polymer systems because of their high dielectric constants. However, too much addition results in a significant decrease in the dispersibility and breakdown strength of the system (Nano Energy,2018,44, 364-. Secondly, the low-dielectric carboxyl polystyrene microspheres are also added into a vinylidene fluoride matrix system, so that the system realizes higher breakdown strength. However, the energy density of the system cannot be effectively increased (Journal of Polymer Science Part B: Polymer Physics,2016,54: 1160-.
Disclosure of Invention
The invention provides a preparation method of a core-shell structure piezoelectric composite material with high breakdown strength, aiming at overcoming the problem that the application range is limited because the dielectric constant and the breakdown strength of a system are difficult to further improve by using a single high-dielectric-constant material.
The invention also provides a high breakdown strength core-shell structure piezoelectric composite material prepared by the method, and the piezoelectric composite material can realize high dielectric constant and high breakdown strength at the same time.
The invention also provides application of the high breakdown strength core-shell structure piezoelectric composite material in the technical field of dielectric energy storage.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a core-shell structure piezoelectric composite material with high breakdown strength comprises the following steps:
(1) carrying out surface hydroxylation modification on the barium titanate nanoparticles to obtain hydroxylated barium titanate nanoparticles;
(2) modifying the hydroxylated barium titanate nano-particles obtained in the step (1) by adopting a silane coupling agent to obtain the silane coupling agent @ BaTiO3A nanoparticle;
(3) taking the silane coupling agent @ barium titanate nano-particle obtained in the step (2) as a core, taking p-toluenesulfonic acid as a catalyst, and performing polycondensation on 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and thiourea monomer on the surface of the silane coupling agent @ barium titanate nano-particle by adopting a microwave polymerization method to obtain the fluorine-containing aromatic polythiourea @ barium titanate nano-particle (ArPFTU @ BaTiO)3) And obtaining the high breakdown strength core-shell structure piezoelectric composite material.
According to the invention, the breakdown-resistant insulating polymer is modified on the surface of the barium titanate nano-particles to construct the core-shell structure piezoelectric nano-material, so that a high breakdown-resistant and high-dielectric nano-composite system is successfully realized in a vinylidene fluoride matrix system, and the system realizes higher energy storage density. The shell-core structure piezoelectric composite particle ArPFTU @ BaTiO of the invention3Both a high dielectric constant and a high breakdown strength are achieved.
Preferably, in the step (1), the surface hydroxylation modification method comprises the following steps: and adding the barium titanate nanoparticles into a hydrogen peroxide solution, activating for 12-24 hours at the reflux temperature of 85-90 ℃ under the condition of adding, washing and drying to obtain the hydroxylated barium titanate.
Preferably, the concentration of the hydrogen peroxide solution is 35-50 wt%.
Preferably, in the step (2), the modification method comprises the following steps: adding the hydroxylated barium titanate nanoparticles into a mixed solvent of ethanol and water (volume ratio is 2:1), slowly adding a silane coupling agent, reacting at 75-85 ℃ for 12-24 h, washing, and drying to obtain the silane coupling agent @ barium titanate nanoparticles.
Preferably, the silane coupling agent is 3-ureidopropyltrimethoxysilane (KH-1524, gamma-UPS).
Preferably, in the step (3), the microwave polymerization method comprises the steps of:
(a) adding a silane coupling agent @ barium titanate nano particle into N, N-dimethylacetamide for ultrasonic dispersion, and dissolving 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, a thiourea monomer and p-toluenesulfonic acid in the solution to obtain a mixed solution;
(b) carrying out microwave polymerization on the mixed solution in a microwave reactor; controlling the power to be 250-350W and the frequency of the microwave to be 18-25 Hz in the microwave polymerization reaction process; and centrifugally washing the obtained product with N, N-dimethylacetamide, and drying to obtain the fluorine-containing aromatic thiourea @ barium titanate nano-particles.
Preferably, the amount of the substances of 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, thiourea monomer and p-toluenesulfonic acid is 1:1: 1.
The high breakdown strength core-shell structure piezoelectric composite material prepared by the preparation method.
Preferably, the shell layer thickness of the high breakdown strength core-shell structure piezoelectric composite material is 5-20 nm.
An application of a high breakdown strength core-shell structure piezoelectric composite material in the technical field of dielectric energy storage.
Therefore, the invention has the following beneficial effects:
(1) according to the invention, the breakdown-resistant insulating polymer is modified on the surface of the barium titanate nano-particles to construct the core-shell structure piezoelectric nano-material, a high breakdown-resistant and high-dielectric nano-composite system is successfully realized in a vinylidene fluoride matrix system, the system realizes higher energy storage density, and the preparation method has simple and efficient path and is easy to industrialize;
(2) the high breakdown strength core-shell structure piezoelectric composite material can realize high dielectric constant and high breakdown strength at the same time, and has wide application prospect in the technical field of dielectric energy storage.
Drawings
Fig. 1 is a flowchart of a method for producing a high breakdown strength core-shell structure piezoelectric composite material of example 1.
FIG. 2 shows ArPFTU @ BaTiO prepared in example 1(A), example 2(B) and example 3(C)3TEM images of nanoparticles.
FIG. 3 is a hydroxylated BaTiO of example 13、γ-UPS@BaTiO3And ArPFTU @ BaTiO3Nanoparticle infrared spectra.
FIG. 4 is a schematic representation of the γ -UPS @ BaTiO prepared in examples 1-33And ArPFTU @ BaTiO3XRD spectrum of nanoparticles.
FIG. 5 is the hydroxylated BaTiO obtained in example 13(A) And ArPFTU @ BaTiO3(B) Contact angle test pattern of nanoparticles.
FIG. 6 shows ArPFTU @ BaTiO prepared in examples 1-33Impedance of the nanoparticles is plotted against time.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The following examples of the present invention all prepare the high breakdown strength core-shell structure piezoelectric composite material according to the flow chart shown in fig. 1.
Example 1
(1) Hydroxylation modification of barium titanate nanoparticles:
putting 3.22g of Barium Titanate (BT) into 10ml of hydrogen peroxide solution with the concentration of 50 wt%, and refluxing, stirring and activating for 24 hours in a silicon oil bath at the temperature of 85-90 ℃ to enable the surface of the BT to have hydroxyl; repeatedly washing the activated barium titanate for 3 times by using distilled water, and carrying out centrifugal separation;
(2) coupling reaction of barium titanate:
adding hydroxylated barium titanate nanoparticles into a mixed solvent of ethanol and water (volume ratio is 2:1), and adding 5ml of 3-urea propyl trimethoxy silane KH1524 (gamma-UPS); after the reaction of 75-85 ℃ silicon oil bath for 12h, repeatedly washing the product with absolute ethyl alcohol for 3 times, centrifugally separating, and drying in vacuum at 80 ℃ for 24h to prepare the gamma-UPS @ BaTiO3Nanoparticles (denoted as γ -UPS @ BT);
(3) preparation of ArPFTU @ BaTiO by microwave polycondensation3Nanoparticles：
Mixing gamma-UPS @ BaTiO3Dissolving the mixture in 20ml of N, N-dimethylacetamide, carrying out ultrasonic treatment for 15min, adding 1.975g of 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.6g of thiourea and 0.172g of p-toluenesulfonic acid (the mass ratio of the three substances is 1:1: 1), and carrying out microwave polymerization, namely, carrying out microwave polymerization twice for 3min on the mixed solution at 18Hz, carrying out microwave polymerization once for 3min at 21Hz, and finally carrying out microwave polymerization once for 3min at 25 Hz; centrifuging and washing the product by DMA for 3 times, drying at 60 ℃ for 36h, and then drying at 120 ℃ for 12h in vacuum to obtain ArPFTU @ BaTiO3The nano particles are the high breakdown strength core-shell structure piezoelectric composite material, a TEM image of the nano particles is shown in FIG. 2A, and the thickness of the shell layer is about 5 nm.
Separately by infrared spectroscopy on hydroxylated BaTiO3Nanoparticles, gamma-UPS @ BaTiO3Nanoparticles and ArPFTU @ BaTiO3The nanoparticles were characterized and the results are shown in fig. 3: hydroxylated BaTiO3The nanoparticles exhibited a typical peak at 520cm-1One strong peak at which tensile vibration of Ti-O bond is observed at 3000cm-1And 1614cm-1The peaks with low intensity are respectively surface adsorbed OH-And BaTiO3Of crystal lattice OH-A group; after the coupling reaction, the concentration of gamma-UPS @ BT was 1700cm-1、2837cm-1And 2853cm-1Three new peaks were found, which are-C ═ O stretching, -CH stretching in the silane coupling agent, respectively3Symmetrical sum-CH2Symmetrical gamma-UPS @ BaTiO3And (3) nanoparticles. Meanwhile, the thickness is 3000-3400 cm-1The band at (B) was significantly reduced, indicating that the silane coupling agent was successfully grafted to BaTiO3On the surface. ArPFTU @ BaTiO after microwave-initiated polymerization3The nano particles are 3500-3428cm-1、1403cm-1And 1123cm-1Three new peaks appear, due to N-H stretch and bow, C-N stretch and C ═ S stretch, respectively, indicating that at γ -UPS @ BaTiO3An ArPFTU shell layer is formed on the surface of the nano-particles.
FIG. 5 is a view of a hydroxylated BaTiO3(5A) And ArPFTU @ BaTiO3The contact angle of the nanoparticle (5B) was measured and found to be 17.0 ° and 107.9 °, respectively. Due to the presence of barium titanate on the surfaceHydroxyl groups, so that the barium titanate film exhibits hydrophilicity. ArPFTU @ BaTiO with surface modification3The water contact angle of the nanoparticles is increased relative to pure barium titanate nanoparticles, which indicates that the hydrophobic polymer chain is well combined on the surface of barium titanate, and also indicates that the ArPFTU shell layer is successfully grafted.
Example 2
Example 2 differs from example 1 in that the microwave polymerization conditions in step (3) are different and are detailed in Table 1, and the rest of the process is exactly the same, and ArPFTU @ BaTiO is obtained3The TEM image of the nanoparticles is shown in fig. 2B: the shell thickness was about 9 nm.
The method comprises the following specific steps:
mixing gamma-UPS @ BaTiO3Dissolving the mixture in 20ml of N, N-dimethylacetamide, carrying out ultrasonic treatment for 15min, adding 1.975g of 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.6g of thiourea and 0.172g of p-toluenesulfonic acid (the mass ratio of the three substances is 1:1: 1), and carrying out microwave polymerization, namely, carrying out microwave polymerization twice for 3min at 18Hz on the mixed solution, carrying out microwave polymerization twice for 3min at 21Hz, and finally carrying out microwave polymerization once for 3min at 25 Hz; centrifuging and washing the product by DMA for 3 times, drying at 60 ℃ for 36h, and then drying at 120 ℃ for 12h in vacuum to obtain ArPFTU @ BaTiO with a shell layer of 9nm thickness3And (3) nanoparticles.
Example 3
Example 3 differs from example 1 in that the microwave polymerization conditions in step (3) are different and are detailed in Table 1, and the rest of the process is exactly the same, to obtain ArPFTU @ BaTiO3The TEM image of the nanoparticles is shown in fig. 2C: the shell thickness is about 15 nm.
The method comprises the following specific steps:
mixing gamma-UPS @ BaTiO3Dissolving the mixture in 20ml of N, N-dimethylacetamide, carrying out ultrasonic treatment for 15min, adding 1.975g of 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 0.6g of thiourea and 0.172g of p-toluenesulfonic acid (the mass ratio of the three substances is 1:1: 1), and carrying out microwave polymerization, namely, carrying out microwave polymerization twice for 3min on the mixed solution at 18Hz, carrying out microwave polymerization once for 3min at 21Hz, and finally carrying out microwave polymerization twice for 3min step by step at 25 Hz; centrifuging and washing the product with DMA for 3 times, drying at 60 deg.C for 36h, vacuum drying at 120 deg.C for 12h, and making into final productObtaining ArPFTU @ BaTiO with a shell layer of 15nm thickness3And (3) nanoparticles.
TABLE 1 microwave polymerization Process parameters for examples 1-3
FIG. 4 is a schematic representation of the γ -UPS @ BaTiO prepared in examples 1-33And ArPFTU @ BaTiO3XRD spectrum of nanoparticles. The XRD diffraction intensity gradually decreased with the increase of the shell thickness compared to the coupled barium titanate, which is probably due to the presence of the shell ArPFTU, where a large amount of X-rays are reflected and absorbed by the shell, indirectly demonstrating that the shell is successfully synthesized on the surface of the barium titanate.
FIG. 6 shows BaTiO compounds obtained in examples 1 to 33And ArPFTU @ BaTiO3The impedance of the nanoparticles varies with time. BaTiO 23Has an impedance of 75399ohm, 5nm ArPFTU @ BaTiO in example 13Has an impedance of 272102 ohm; 9nm ArPFTU @ BaTiO in example 23Has an impedance of 888717 ohm; 15nm ArPFTU @ BaTiO in example 33Is 6727653 ohm. The high breakdown strength core-shell structure piezoelectric composite material has high dielectric constant and high breakdown strength.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A preparation method of a core-shell structure piezoelectric composite material with high breakdown strength is characterized by comprising the following steps:
(1) carrying out surface hydroxylation modification on the barium titanate nanoparticles to obtain hydroxylated barium titanate nanoparticles;
(2) modifying the hydroxylated barium titanate nano-particles obtained in the step (1) by using a silane coupling agent to obtain silane coupling agent @ barium titanate nano-particles;
(3) and (3) with the silane coupling agent @ barium titanate nano-particles obtained in the step (2) as a core and p-toluenesulfonic acid as a catalyst, carrying out polycondensation on 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and thiourea monomers on the surface of the silane coupling agent @ barium titanate nano-particles by adopting a microwave polymerization method to obtain fluorine-containing aromatic thiourea @ barium titanate nano-particles, and thus obtaining the high breakdown strength core-shell structure piezoelectric composite material.
2. The method according to claim 1, wherein in the step (1), the surface is modified by hydroxylation by: adding barium titanate nanoparticles into a hydrogen peroxide solution, and refluxing at 85-90 DEGoAnd (5) activating for 12-24 hours with the addition of the C, washing and drying to obtain the hydroxylated barium titanate.
3. The method according to claim 2, wherein the concentration of the aqueous hydrogen peroxide solution is 35 to 50 wt%.
4. The method according to claim 1, wherein in the step (2), the modification is carried out by: adding hydroxylated barium titanate nanoparticles into a mixed solvent of ethanol and water, slowly adding a silane coupling agent, and adding the silane coupling agent at 75-85 DEG CoAnd C, reacting for 12-24 hours, washing and drying to obtain the silane coupling agent @ barium titanate nano-particles.
5. The method according to claim 1 or 4, wherein the silane coupling agent is 3-ureidopropyltrimethoxysilane.
6. The production method according to claim 1,
in the step (3), the microwave polymerization method comprises the following steps:
(a) adding a silane coupling agent @ barium titanate nano particle into N, N-dimethylacetamide for ultrasonic dispersion, and dissolving 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, a thiourea monomer and p-toluenesulfonic acid in the solution to obtain a mixed solution;
(b) carrying out microwave polymerization on the mixed solution in a microwave reactor; controlling the power to be 250-350W and the frequency of the microwave to be 18-25 Hz in the microwave polymerization reaction process; and centrifugally washing the obtained product with N, N-dimethylacetamide, and drying to obtain the fluorine-containing aromatic thiourea @ barium titanate nano-particles.
7. The method of claim 1, wherein the amount of the 2, 2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, thiourea monomer and p-toluenesulfonic acid is 1:1: 1.
8. The high breakdown strength core-shell structure piezoelectric composite material prepared by the preparation method according to any one of claims 1 to 7.
9. The high breakdown strength core-shell structure piezoelectric composite material according to claim 8, wherein the shell layer thickness is 5 to 20 nm.
10. The application of the high breakdown strength core-shell structure piezoelectric composite material as claimed in claim 8 in the technical field of dielectric energy storage.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113845700A (en) * | 2021-09-28 | 2021-12-28 | 四川大学 | Barium titanate matrix composite material and DIW printing forming method and application thereof |
| CN114058046A (en) * | 2021-10-28 | 2022-02-18 | 杭州电子科技大学 | P(VDF-CTFE)/PAMAM(Gx)@BaTiO3Preparation method of (1) |
| CN114394838A (en) * | 2022-02-09 | 2022-04-26 | 江苏耀鸿电子有限公司 | High-breakdown-strength high-frequency copper-clad substrate and preparation method thereof |
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| CN111564549A (en) * | 2020-02-24 | 2020-08-21 | 宁波工程学院 | SiC/ZnO nano heterojunction pressure sensor and preparation method thereof |
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| CN111564549A (en) * | 2020-02-24 | 2020-08-21 | 宁波工程学院 | SiC/ZnO nano heterojunction pressure sensor and preparation method thereof |
Non-Patent Citations (1)
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| YINGXIN CHEN: "Concurrently Improved Breakdown Strength and Storage Energy Capacitance in the Core−Shell-Structured Aromatic Polythiourea@BaTiO3 Polymer Nanocomposites Induced by the Nature of Interfacial Polarization and Crystallization", 《APPLIED ENERGY MATERIALS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845700A (en) * | 2021-09-28 | 2021-12-28 | 四川大学 | Barium titanate matrix composite material and DIW printing forming method and application thereof |
| CN114058046A (en) * | 2021-10-28 | 2022-02-18 | 杭州电子科技大学 | P(VDF-CTFE)/PAMAM(Gx)@BaTiO3Preparation method of (1) |
| CN114058046B (en) * | 2021-10-28 | 2024-01-16 | 杭州电子科技大学 | P(VDF-CTFE)/PAMAM(G x )@BaTiO 3 Is prepared by the preparation method of (2) |
| CN114394838A (en) * | 2022-02-09 | 2022-04-26 | 江苏耀鸿电子有限公司 | High-breakdown-strength high-frequency copper-clad substrate and preparation method thereof |
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