CN112174658B - High-performance BaTiO with core-shell structure3Base ceramic dielectric material and preparation method thereof - Google Patents
High-performance BaTiO with core-shell structure3Base ceramic dielectric material and preparation method thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 38
- 239000011258 core-shell material Substances 0.000 title claims abstract description 16
- 239000000919 ceramic Substances 0.000 title claims description 30
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 44
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 11
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 34
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 28
- 238000009210 therapy by ultrasound Methods 0.000 claims description 27
- 239000012065 filter cake Substances 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229940078552 o-xylene Drugs 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 14
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005576 amination reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229940102396 methyl bromide Drugs 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QEDNABCLVCJRLV-UHFFFAOYSA-N 4-n,4-n-dimethylpyridine-2,4-diamine Chemical compound CN(C)C1=CC=NC(N)=C1 QEDNABCLVCJRLV-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 125000005997 bromomethyl group Chemical group 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QOGHRLGTXVMRLM-UHFFFAOYSA-N 4-bromo-1,2-dimethylbenzene Chemical group CC1=CC=C(Br)C=C1C QOGHRLGTXVMRLM-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62807—Silica or silicates
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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Abstract
The invention discloses high-performance BaTiO with a core-shell structure3The dielectric material comprises the following raw materials in parts by weight: barium titanate base 10-15 parts of coating material and 5-8 parts of coating material; the barium titanate base material is prepared by condensing carboxyl on the surface of graphene and amino on the surface of an aminated preloading body, the coating of silicon dioxide can alleviate the interface effect between matrixes and can share higher voltage, the voltage resistance of the dielectric material is improved, the coating material takes gamma-aminopropyl triethoxysilane and dimethyl dimethoxysilane as raw materials to react to prepare organic silicon resin, and then the organic silicon resin reacts with an intermediate 5 to prepare the coating material by reacting the amino on the organic silicon resin and bromomethyl on the intermediate 5.
Description
Technical Field
The invention belongs to the technical field of dielectric material preparation, and particularly relates to high-performance BaTiO with a core-shell structure3A base ceramic dielectric material and a preparation method thereof.
Background
With the rapid development of information technology and electronic science technology, higher use requirements are put forward on electronic equipment, such as light weight, chip type and miniaturization, multilayer ceramic capacitors (MLCCs) are produced for these reasons, and multilayer capacitors are a class of important passive electronic components, which are indispensable components in the electronic, communication and information industries and can store charges, block direct current, filter alternating current, provide tuning and oscillation, and the like.
The existing BaTiO 3-based ceramic dielectric material has low dielectric constant and poor temperature stability, and the performance of the material changes along with the change of environmental temperature in the use process, so that the material is difficult to be directly used for high-reliability electric ceramic capacitors.
Disclosure of Invention
The invention aims to provide high-performance BaTiO with a core-shell structure3A base ceramic dielectric material and a preparation method thereof.
The technical problems to be solved by the invention are as follows:
existing BaTiO3The dielectric constant of the base ceramic dielectric material is low, the temperature stability is poor, the performance is changed along with the change of the environmental temperature in the using process, and the base ceramic dielectric material is difficult to be directly used for a high-reliability electric ceramic capacitor.
The purpose of the invention can be realized by the following technical scheme:
high-performance BaTiO with core-shell structure3The ceramic dielectric material comprises the following raw materials in parts by weight: 10-15 parts of barium titanate base material and 5-8 parts of coating material;
the BaTiO 3-based ceramic dielectric material is prepared by the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 20-30min under the condition that the rotation speed is 150-;
step S3: and adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1-1.5h under the condition of the frequency of 3-5MHz, and distilling at the temperature of 120-130 ℃ to prepare the BaTiO 3-based ceramic dielectric material.
Furthermore, the amount of the 4-dimethylaminopyridine in the step S2 is 20-25% of the barium titanate base material.
Further, the barium titanate base material is prepared by the following steps:
step A1: adding barium titanate, ethanol and acetic acid into a reaction kettle, stirring for 10-15min under the conditions that the rotating speed is 300-500r/min and the temperature is 35-40 ℃, carrying out ultrasonic treatment for 10-15min under the condition that the frequency is 5-8MHz, adding tetraethyl orthosilicate, uniformly mixing, adding ammonia water until the pH value of reaction liquid is 9-10, continuing ultrasonic treatment for 15-20min, filtering to remove filtrate, and drying a filter cake to obtain a pre-carrier;
step A2: adding the pre-carrier prepared in the step A1 and hydrogen peroxide into a reaction kettle, performing ultrasonic treatment for 10-15min under the condition of frequency of 5-8MHz, performing reflux stirring for 3-5h at the rotation speed of 800-1000r/min and the temperature of 105-110 ℃, filtering to remove filtrate, adding a filter cake and toluene into the reaction kettle, performing ultrasonic treatment for 20-25min under the frequency of 5-8MHz, adding 3-aminopropyltrimethoxysilane and deionized water, introducing nitrogen for protection, performing stirring for 10-15h at the rotation speed of 300-500r/min and the temperature of 70-80 ℃, filtering to remove filtrate, and drying the filter cake to obtain an aminated pre-carrier;
step A3: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 200-300r/min, heating to 70-80 ℃, carrying out reflux stirring for 4-6h, filtering to remove filtrate, dispersing a filter cake into deionized water, adding the amination pre-carrier prepared in the step A2, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, reacting for 1-1.5h under the condition that the temperature is 35-40 ℃, filtering to remove filtrate, and drying the filter cake to obtain the barium titanate base material.
Further, the using amount ratio of the barium titanate, the ethanol and the acetic acid in the step A1 is 20g:50mL:3mL, the using amount of the tetraethyl orthosilicate is 2-3% of the weight of the barium titanate, the using amount ratio of the pre-carrier and the hydrogen peroxide in the step A2 is 2g:10-15mL, the mass fraction of the hydrogen peroxide is 25-30%, the using amount of the 3-aminopropyltrimethoxysilane is 10-15% of the weight of the pre-carrier, the using amount ratio of the graphene and the hydrogen peroxide in the step A3 is 5g:30-50mL, the mass fraction of the hydrogen peroxide is 25-30%, the using amount ratio of the amination pre-carrier and the graphene is 1:1, the using amount of the dicyclohexylcarbodiimide is 10-15% of the weight of the amination pre-carrier, and the using amount of the 4-dimethylamino pyridylamine is 10-15% of the weight of the amination pre-carrier.
Further, the coating material is prepared by the following steps:
step B1: heating 4-bromine-o-xylene at the temperature of 220-230 ℃ for gasifying the 4-bromine-o-xylene, adding the gasified 4-bromine-o-xylene into a tubular fixed bed, taking vanadium pentoxide as a catalyst, and reacting at the feeding airspeed of 2500-3200h-1 and the temperature of 400-420 ℃ to obtain an intermediate 1;
the reaction process is as follows:
step B2: adding the intermediate 1 prepared in the step B1 into tetrahydrofuran, stirring until the intermediate 1 is completely dissolved, adding magnesium powder, stirring for 1-1.5h at the rotation speed of 150-40 ℃ for 2-3h, adding bromomethane, continuing to react for 2-3h to prepare an intermediate 2, adding the intermediate 2 and sodium hydroxide into deionized water, refluxing for 3-5h at the rotation speed of 300-300 r/min and the temperature of 110-120 ℃, and adjusting the pH value of the reaction solution to 2-3 to prepare an intermediate 3;
the reaction process is as follows:
step B3: dissolving the intermediate 3 in dimethylformamide, adding 1-hydroxybenzotriazole under the condition of temperature of 3-5 ℃, stirring for 5-10min, adding aminotriazole, continuing to react for 20-25h under the condition of temperature of 25-30 ℃ to obtain an intermediate 4, dissolving the intermediate 4 in benzene, introducing chlorine, and reacting for 1-1.5h under the condition of illumination to obtain an intermediate 5;
step B4: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-200r/min and the temperature is 60-70 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5-1h, after dropwise adding, heating to the temperature of 75-80 ℃, continuously stirring for 3-5h, adding sodium bicarbonate, continuously stirring to the pH value of 7, and distilling to remove a distillate under the condition that the temperature is 140-150 ℃ to prepare the organic silicon resin;
step B5: and B4, mixing the organic silicon resin prepared in the step B and toluene to prepare an organic silicon resin solution, mixing the intermediate 5 prepared in the step B3 and tetrahydrofuran to prepare an intermediate 5 solution, adding the organic silicon resin solution into a reaction kettle, adding the intermediate 5 solution under the conditions of the rotation speed of 200-50 ℃ and the temperature of 40-50 ℃, stirring for 2-3h, and distilling at the temperature of 115-120 ℃ to prepare the coating material.
Further, the molar ratio of the used amount of the intermediate 1, the magnesium powder and the methyl bromide in the step B2 is 1:1:1, the molar ratio of the used amount of the intermediate 2 to the used amount of the sodium hydroxide is 1:2, the molar ratio of the used amount of the intermediate 3 to the used amount of the aminotriazole in the step B3 is 1:1, the used amount of the 1-hydroxybenzotriazole is 50-60% of the mass of the intermediate 3, the used amount of the gamma-aminopropyltriethoxysilane and the dimethyldimethoxysilane in the step B4 is 1:1, the used amount of the hydrochloric acid aqueous solution is 1-2 times of the mass sum of the gamma-aminopropyltriethoxysilane and the dimethyldimethoxysilane, the mass fraction of the hydrochloric acid aqueous solution is 10-15%, and the used amount of the organic silicon resin and the intermediate 5 in the step B5 is 2: 1.
A preparation method of a high-performance core-shell structure BaTiO 3-based ceramic dielectric material specifically comprises the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 20-30min under the condition that the rotation speed is 150-;
step S3: and adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1-1.5h under the condition of the frequency of 3-5MHz, and distilling at the temperature of 120-130 ℃ to prepare the BaTiO 3-based ceramic dielectric material.
The invention has the beneficial effects that: the invention prepares a barium titanate base material in the process of preparing a high-performance core-shell structure BaTiO 3-based ceramic dielectric material, the barium titanate base material takes barium titanate as a raw material, tetraethyl orthosilicate is used for coating a layer of silicon dioxide on the surface of the barium titanate to prepare a pre-carrier, hydrogen peroxide is used for oxidizing the pre-carrier and the carrier to ensure that the surface of the pre-carrier contains a large amount of active hydroxyl, 3-aminopropyltrimethoxysilane is used for reaction to ensure that the surface of the pre-carrier contains amino to prepare an aminated pre-carrier, graphene is oxidized by hydrogen peroxide to ensure that the active hydroxyl on the surface of the graphene is converted into carboxyl, the aminated pre-carrier prepared in the step A2 is added to ensure that the carboxyl on the surface of the graphene and the amino on the surface of the aminated pre-carrier are condensed to prepare the barium titanate base material, and the coating of the silicon dioxide can alleviate the interface effect between, the coating material is prepared by taking 4-bromo-o-xylene as a raw material, reacting under the action of a vanadium pentoxide catalyst to prepare an intermediate 1, reacting the intermediate 1 with magnesium powder to prepare a Grignard reagent, further reacting with methyl bromide to prepare an intermediate 2, hydrolyzing the intermediate 2 to prepare an intermediate 3, reacting the intermediate 3 with aminotriazole to prepare an intermediate 4, reacting the intermediate 4 with chlorine to prepare an intermediate 5, reacting by taking gamma-aminopropyltriethoxysilane and dimethyldimethoxysilane as raw materials to prepare organic silicon resin, wherein a side chain of the organic silicon resin contains amino, further reacting the organic silicon resin with the intermediate 5 to react the amino on the organic silicon resin and chloromethyl on the intermediate 5 to prepare the coating material, the cladding material improves the temperature stability of the dielectric material, and prolongs the service life of the dielectric material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
High-performance BaTiO with core-shell structure3The ceramic dielectric material comprises the following raw materials in parts by weight: 10 parts of barium titanate base material and 5 parts of coating material;
the BaTiO 3-based ceramic dielectric material is prepared by the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing a barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 20min at the rotation speed of 150r/min to prepare a dispersion liquid;
step S3: and (3) adding the coating liquid prepared in the step (S1) into the dispersion liquid prepared in the step (S2), carrying out ultrasonic treatment for 1h under the condition of the frequency of 3MHz, and distilling at the temperature of 120 ℃ to prepare the BaTiO 3-based ceramic dielectric material.
The barium titanate base material is prepared by the following steps:
step A1: adding barium titanate, ethanol and acetic acid into a reaction kettle, stirring for 10min under the conditions that the rotating speed is 300r/min and the temperature is 35 ℃, carrying out ultrasonic treatment for 10min under the condition that the frequency is 5MHz, adding tetraethyl orthosilicate, uniformly mixing, adding ammonia water until the pH value of reaction liquid is 9, continuing ultrasonic treatment for 15min, filtering to remove filtrate, and drying a filter cake to obtain a pre-carrier;
step A2: adding the pre-carrier prepared in the step A1 and hydrogen peroxide into a reaction kettle, performing ultrasonic treatment for 10min under the condition of 5MHz, performing reflux stirring for 3h at the rotation speed of 800r/min and the temperature of 105 ℃, filtering to remove filtrate, adding a filter cake and toluene into the reaction kettle, performing ultrasonic treatment for 20min under the condition of 5MHz, adding 3-aminopropyl trimethoxy silane and deionized water, introducing nitrogen for protection, stirring for 10h at the rotation speed of 300r/min and the temperature of 70 ℃, filtering to remove filtrate, and drying the filter cake to prepare the amination pre-carrier;
step A3: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5min at the rotation speed of 200r/min, heating to 70 ℃, refluxing and stirring for 4h, filtering to remove filtrate, dispersing a filter cake into deionized water, adding the aminated pre-carrier prepared in the step A2, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, reacting for 1h at the temperature of 35 ℃, filtering to remove filtrate, and drying the filter cake to obtain the barium titanate base material.
The coating material is prepared by the following steps:
step B1: heating 4-bromine o-xylene at 220 ℃ to gasify the 4-bromine o-xylene, adding the gasified 4-bromine o-xylene into a tubular fixed bed, and reacting at 400 ℃ at a feeding airspeed of 2500h < -1 > and a feeding airspeed of vanadium pentoxide as a catalyst to obtain an intermediate 1;
step B2: adding the intermediate 1 prepared in the step B1 into tetrahydrofuran, stirring until the intermediate 1 is completely dissolved, adding magnesium powder, stirring for 1h at the rotation speed of 120r/min and the temperature of 35 ℃, adding methyl bromide, continuing to react for 2h to prepare an intermediate 2, adding the intermediate 2 and sodium hydroxide into deionized water, refluxing for 3h at the rotation speed of 200r/min and the temperature of 110 ℃, and adjusting the pH value of a reaction solution to 2 to prepare an intermediate 3;
step B3: dissolving the intermediate 3 in dimethylformamide, adding 1-hydroxybenzotriazole under the condition of the temperature of 3 ℃, stirring for 5min, adding aminotriazole, continuing to react for 20h under the condition of the temperature of 25 ℃ to obtain an intermediate 4, dissolving the intermediate 4 in benzene, introducing chlorine, and reacting for 1h under the illumination condition to obtain an intermediate 5;
step B4: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 60 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5h, after dropwise adding, heating to the temperature of 75 ℃, continuously stirring for 3h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 140 ℃ to remove distillate to obtain the organic silicon resin;
step B5: and B, mixing the organic silicon resin prepared in the step B4 with toluene to prepare an organic silicon resin solution, mixing the intermediate 5 prepared in the step B3 with tetrahydrofuran to prepare an intermediate 5 solution, adding the organic silicon resin solution into a reaction kettle, adding the intermediate 5 solution under the conditions of the rotating speed of 200r/min and the temperature of 40 ℃, stirring for 2 hours, and distilling at the temperature of 115 ℃ to prepare the coating material.
Example 2
High-performance BaTiO with core-shell structure3The ceramic dielectric material comprises the following raw materials in parts by weight: 13 parts of barium titanate base material and 6 parts of coating material;
the BaTiO 3-based ceramic dielectric material is prepared by the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing a barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 25min at the rotation speed of 180r/min to prepare a dispersion liquid;
step S3: and (4) adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1h under the condition of 4MHz, and distilling at the temperature of 130 ℃ to prepare the BaTiO 3-based ceramic dielectric material.
The barium titanate base material is prepared by the following steps:
step A1: adding barium titanate, ethanol and acetic acid into a reaction kettle, stirring for 10min under the conditions that the rotating speed is 300r/min and the temperature is 40 ℃, carrying out ultrasonic treatment for 10min under the condition that the frequency is 8MHz, adding tetraethyl orthosilicate, uniformly mixing, adding ammonia water until the pH value of reaction liquid is 10, continuing ultrasonic treatment for 15min, filtering to remove filtrate, and drying a filter cake to obtain a pre-carrier;
step A2: adding the pre-carrier prepared in the step A1 and hydrogen peroxide into a reaction kettle, performing ultrasonic treatment for 10min under the condition of the frequency of 8MHz, performing reflux stirring for 5h at the rotation speed of 1000r/min and the temperature of 105 ℃, filtering to remove filtrate, adding a filter cake and toluene into the reaction kettle, performing ultrasonic treatment for 25min under the condition of the frequency of 5MHz, adding 3-aminopropyl trimethoxy silane and deionized water, introducing nitrogen for protection, stirring for 10h at the rotation speed of 300r/min and the temperature of 80 ℃, filtering to remove filtrate, and drying the filter cake to prepare the amination pre-carrier;
step A3: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5min at the rotation speed of 300r/min, heating to 80 ℃, refluxing and stirring for 4h, filtering to remove filtrate, dispersing a filter cake into deionized water, adding the aminated pre-carrier prepared in the step A2, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, reacting for 1h at the temperature of 40 ℃, filtering to remove filtrate, and drying the filter cake to obtain the barium titanate base material.
The coating material is prepared by the following steps:
step B1: heating 4-bromine o-xylene at 220 ℃ to gasify the 4-bromine o-xylene, adding the gasified 4-bromine o-xylene into a tubular fixed bed, and reacting at 400 ℃ at a feeding airspeed of 3200h-1 by using vanadium pentoxide as a catalyst to prepare an intermediate 1;
step B2: adding the intermediate 1 prepared in the step B1 into tetrahydrofuran, stirring until the intermediate 1 is completely dissolved, adding magnesium powder, stirring for 1.5h at the rotation speed of 150r/min and the temperature of 35 ℃, adding methyl bromide, continuing to react for 2h to prepare an intermediate 2, adding the intermediate 2 and sodium hydroxide into deionized water, refluxing for 5h at the rotation speed of 300r/min and the temperature of 110 ℃, and adjusting the pH value of a reaction solution to 2 to prepare an intermediate 3;
step B3: dissolving the intermediate 3 in dimethylformamide, adding 1-hydroxybenzotriazole under the condition of 5 ℃, stirring for 5min, adding aminotriazole, continuing to react for 20h under the condition of 30 ℃ to obtain an intermediate 4, dissolving the intermediate 4 in benzene, introducing chlorine, and reacting for 1.5h under the illumination condition to obtain an intermediate 5;
step B4: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10min at the rotation speed of 150r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid aqueous solution for 1h, heating to the temperature of 75 ℃ after dropwise adding, continuously stirring for 5h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 140 ℃ to remove distillate to obtain the organic silicon resin;
step B5: and B, mixing the organic silicon resin prepared in the step B4 with toluene to prepare an organic silicon resin solution, mixing the intermediate 5 prepared in the step B3 with tetrahydrofuran to prepare an intermediate 5 solution, adding the organic silicon resin solution into a reaction kettle, adding the intermediate 5 solution under the conditions of the rotating speed of 200r/min and the temperature of 50 ℃, stirring for 2 hours, and distilling at the temperature of 120 ℃ to prepare the coating material.
Example 3
High-performance BaTiO with core-shell structure3The ceramic dielectric material comprises the following raw materials in parts by weight: 15 parts of barium titanate base material and 8 parts of coating material;
the BaTiO 3-based ceramic dielectric material is prepared by the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing a barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 30min at the rotation speed of 200r/min to prepare a dispersion liquid;
step S3: and (4) adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1.5h under the condition of 5MHz, and distilling at the temperature of 130 ℃ to prepare the BaTiO 3-based ceramic dielectric material.
The barium titanate base material is prepared by the following steps:
step A1: adding barium titanate, ethanol and acetic acid into a reaction kettle, stirring for 15min under the conditions of a rotating speed of 500r/min and a temperature of 40 ℃, carrying out ultrasonic treatment for 15min under the condition of a frequency of 8MHz, adding tetraethyl orthosilicate, uniformly mixing, adding ammonia water until the pH value of a reaction solution is 10, continuing ultrasonic treatment for 20min, filtering to remove filtrate, and drying a filter cake to obtain a pre-carrier;
step A2: adding the pre-carrier prepared in the step A1 and hydrogen peroxide into a reaction kettle, performing ultrasonic treatment for 15min under the condition of 8MHz frequency, performing reflux stirring for 5h at the rotation speed of 1000r/min and the temperature of 110 ℃, filtering to remove filtrate, adding a filter cake and toluene into the reaction kettle, performing ultrasonic treatment for 25min under the condition of 8MHz frequency, adding 3-aminopropyl trimethoxy silane and deionized water, introducing nitrogen for protection, stirring for 15h at the rotation speed of 500r/min and the temperature of 80 ℃, filtering to remove filtrate, and drying the filter cake to prepare the amination pre-carrier;
step A3: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 10min at the rotation speed of 300r/min, heating to 80 ℃, refluxing and stirring for 6h, filtering to remove filtrate, dispersing a filter cake into deionized water, adding the aminated pre-carrier prepared in the step A2, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, reacting for 1.5h at the temperature of 40 ℃, filtering to remove the filtrate, and drying the filter cake to obtain the barium titanate base material.
The coating material is prepared by the following steps:
step B1: heating 4-bromine o-xylene at 230 ℃ to gasify the 4-bromine o-xylene, adding the gasified 4-bromine o-xylene into a tubular fixed bed, and reacting at 420 ℃ with vanadium pentoxide as a catalyst at a feeding airspeed of 3200h-1 to obtain an intermediate 1;
step B2: adding the intermediate 1 prepared in the step B1 into tetrahydrofuran, stirring until the intermediate 1 is completely dissolved, adding magnesium powder, stirring for 1.5h at the rotation speed of 150r/min and the temperature of 40 ℃, adding methyl bromide, continuing to react for 3h to prepare an intermediate 2, adding the intermediate 2 and sodium hydroxide into deionized water, refluxing for 5h at the rotation speed of 300r/min and the temperature of 120 ℃, and adjusting the pH value of a reaction solution to 3 to prepare an intermediate 3;
step B3: dissolving the intermediate 3 in dimethylformamide, adding 1-hydroxybenzotriazole under the condition of 5 ℃, stirring for 10min, adding aminotriazole, continuing to react for 25h under the condition of 30 ℃ to obtain an intermediate 4, dissolving the intermediate 4 in benzene, introducing chlorine, and reacting for 1.5h under the illumination condition to obtain an intermediate 5;
step B4: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 15min at the rotation speed of 200r/min and the temperature of 70 ℃, dropwise adding a hydrochloric acid aqueous solution for 1h, heating to 80 ℃ after dropwise adding, continuously stirring for 5h, adding sodium bicarbonate, continuously stirring until the pH value is 7, and distilling at the temperature of 150 ℃ to remove distillate to obtain the organic silicon resin;
step B5: and B, mixing the organic silicon resin prepared in the step B4 with toluene to prepare an organic silicon resin solution, mixing the intermediate 5 prepared in the step B3 with tetrahydrofuran to prepare an intermediate 5 solution, adding the organic silicon resin solution into a reaction kettle, adding the intermediate 5 solution under the conditions of the rotating speed of 300r/min and the temperature of 50 ℃, stirring for 3 hours, and distilling at the temperature of 120 ℃ to prepare the coating material.
Comparative example
The comparative example is a common dielectric material in the market.
The dielectric materials prepared in examples 1-3 and comparative example were subjected to performance tests, the test results of which are shown in table 1 below;
TABLE 1
From the above table 1, it can be seen that the dielectric materials prepared in examples 1-3 have dielectric constants of 1895-1923 at-55 ℃, 2343-2350 at 20 ℃, 2530-2580 at 150 ℃, 1650 at-55 ℃, 1762 at 20 ℃ and 1630 at 150 ℃, and the invention has very high dielectric constant and very good temperature stability.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (5)
1. High-performance BaTiO with core-shell structure3The ceramic dielectric material is characterized in that: the feed comprises the following raw materials in parts by weight: 10-15 parts of barium titanate base material and 5-8 parts of coating material;
the BaTiO3The base ceramic dielectric material is prepared by the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 20-30min under the condition that the rotation speed is 150-;
step S3: adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1-1.5h under the condition of the frequency of 3-5MHz, and distilling at the temperature of 120-130 ℃ to prepare BaTiO3A base ceramic dielectric material;
the barium titanate base material is prepared by the following steps:
step A1: adding barium titanate, ethanol and acetic acid into a reaction kettle, stirring for 10-15min under the conditions that the rotating speed is 300-500r/min and the temperature is 35-40 ℃, carrying out ultrasonic treatment for 10-15min under the condition that the frequency is 5-8MHz, adding tetraethyl orthosilicate, uniformly mixing, adding ammonia water until the pH value of reaction liquid is 9-10, continuing ultrasonic treatment for 15-20min, filtering to remove filtrate, and drying a filter cake to obtain a pre-carrier;
step A2: adding the pre-carrier prepared in the step A1 and hydrogen peroxide into a reaction kettle, performing ultrasonic treatment for 10-15min under the condition of frequency of 5-8MHz, performing reflux stirring for 3-5h at the rotation speed of 800-1000r/min and the temperature of 105-110 ℃, filtering to remove filtrate, adding a filter cake and toluene into the reaction kettle, performing ultrasonic treatment for 20-25min under the frequency of 5-8MHz, adding 3-aminopropyltrimethoxysilane and deionized water, introducing nitrogen for protection, performing stirring for 10-15h at the rotation speed of 300-500r/min and the temperature of 70-80 ℃, filtering to remove filtrate, and drying the filter cake to obtain an aminated pre-carrier;
step A3: adding graphene and hydrogen peroxide into a reaction kettle, stirring for 5-10min under the condition that the rotation speed is 200-300r/min, heating to 70-80 ℃, carrying out reflux stirring for 4-6h, filtering to remove filtrate, dispersing a filter cake into deionized water, adding the amination pre-carrier prepared in the step A2, dicyclohexylcarbodiimide and 4-dimethylaminopyridine, reacting for 1-1.5h under the condition that the temperature is 35-40 ℃, filtering to remove filtrate, and drying the filter cake to obtain a barium titanate base material;
the coating material is prepared by the following steps:
step B1: heating 4-bromine-o-xylene at the temperature of 220-230 ℃ for gasifying the 4-bromine-o-xylene, adding the gasified 4-bromine-o-xylene into a tubular fixed bed, taking vanadium pentoxide as a catalyst, and reacting at the feeding airspeed of 2500-3200h-1 and the temperature of 400-420 ℃ to obtain an intermediate 1;
step B2: adding the intermediate 1 prepared in the step B1 into tetrahydrofuran, stirring until the intermediate 1 is completely dissolved, adding magnesium powder, stirring for 1-1.5h at the rotation speed of 150-40 ℃ for 2-3h, adding bromomethane, continuing to react for 2-3h to prepare an intermediate 2, adding the intermediate 2 and sodium hydroxide into deionized water, refluxing for 3-5h at the rotation speed of 300-300 r/min and the temperature of 110-120 ℃, and adjusting the pH value of the reaction solution to 2-3 to prepare an intermediate 3;
step B3: dissolving the intermediate 3 in dimethylformamide, adding 1-hydroxybenzotriazole under the condition of temperature of 3-5 ℃, stirring for 5-10min, adding aminotriazole, continuing to react for 20-25h under the condition of temperature of 25-30 ℃ to obtain an intermediate 4, dissolving the intermediate 4 in benzene, introducing chlorine, and reacting for 1-1.5h under the condition of illumination to obtain an intermediate 5;
step B4: adding gamma-aminopropyltriethoxysilane, dimethyldimethoxysilane and xylene into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 150-200r/min and the temperature is 60-70 ℃, dropwise adding a hydrochloric acid aqueous solution for 0.5-1h, after dropwise adding, heating to the temperature of 75-80 ℃, continuously stirring for 3-5h, adding sodium bicarbonate, continuously stirring to the pH value of 7, and distilling to remove a distillate under the condition that the temperature is 140-150 ℃ to prepare the organic silicon resin;
step B5: and B4, mixing the organic silicon resin prepared in the step B and toluene to prepare an organic silicon resin solution, mixing the intermediate 5 prepared in the step B3 and tetrahydrofuran to prepare an intermediate 5 solution, adding the organic silicon resin solution into a reaction kettle, adding the intermediate 5 solution under the conditions of the rotation speed of 200-50 ℃ and the temperature of 40-50 ℃, stirring for 2-3h, and distilling at the temperature of 115-120 ℃ to prepare the coating material.
2. The high-performance core-shell structure BaTiO of claim 13The ceramic dielectric material is characterized in that: the using amount of the 4-dimethylaminopyridine in the step S2 is 20-25% of the mass of the barium titanate base material.
3. The high-performance core-shell structure BaTiO of claim 13The ceramic dielectric material is characterized in that: the dosage ratio of the barium titanate, the ethanol and the acetic acid in the step A1 is 20g:50mL:3mL, the dosage of the tetraethyl orthosilicate is 2-3% of the mass of the barium titanate, the dosage ratio of the pre-carrier and the hydrogen peroxide in the step A2 is 2g:10-15mL, and the mass fraction of the hydrogen peroxide isThe amount of the 3-aminopropyl trimethoxy silane is 25-30%, the amount of the 3-aminopropyl trimethoxy silane is 10-15% of the mass of the pre-carrier, the amount ratio of the graphene to the hydrogen peroxide in the step A3 is 5g:30-50mL, the mass fraction of the hydrogen peroxide is 25-30%, the amount ratio of the amination pre-carrier to the graphene is 1:1, the amount of dicyclohexyl carbodiimide is 10-15% of the mass of the amination pre-carrier, and the amount of the 4-dimethylamino pyridylamine is 10-15% of the mass of the amination pre-carrier.
4. The high-performance core-shell structure BaTiO of claim 13The ceramic dielectric material is characterized in that: the using amount molar ratio of the intermediate 1, the magnesium powder and the methyl bromide in the step B2 is 1:1:1, the using amount molar ratio of the intermediate 2 to the sodium hydroxide is 1:2, the using amount molar ratio of the intermediate 3 to the aminotriazole in the step B3 is 1:1, the using amount of the 1-hydroxybenzotriazole is 50-60% of the intermediate 3 by mass, the using amount mass ratio of the gamma-aminopropyltriethoxysilane to the dimethyldimethoxysilane in the step B4 is 1:1, the using amount of the hydrochloric acid aqueous solution is 1-2 times of the sum of the gamma-aminopropyltriethoxysilane and the dimethyldimethoxysilane by mass, the mass fraction of the hydrochloric acid aqueous solution is 10-15%, and the using amount mass ratio of the organic silicon resin to the intermediate 5 in the step B5 is 2: 1.
5. The high-performance core-shell structure BaTiO of claim 13The preparation method of the base ceramic dielectric material is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: dissolving a coating material in toluene to prepare a coating solution;
step S2: dispersing barium titanate base material in deionized water, adding 4-dimethylaminopyridine, and stirring for 20-30min under the condition that the rotation speed is 150-;
step S3: adding the coating liquid prepared in the step S1 into the dispersion liquid prepared in the step S2, carrying out ultrasonic treatment for 1-1.5h under the condition of the frequency of 3-5MHz, and distilling at the temperature of 120-130 ℃ to prepare BaTiO3A base ceramic dielectric material.
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