CN112341190A - Barium titanate-based powder preparation method, barium titanate-based powder and supercapacitor - Google Patents
Barium titanate-based powder preparation method, barium titanate-based powder and supercapacitor Download PDFInfo
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 175
- 239000000843 powder Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 86
- 239000002243 precursor Substances 0.000 claims abstract description 78
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052788 barium Inorganic materials 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 69
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000975 co-precipitation Methods 0.000 claims description 20
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 19
- 229910001626 barium chloride Inorganic materials 0.000 claims description 19
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- ANBZWDBEKOZNHY-UHFFFAOYSA-N ethanol;oxalic acid Chemical compound CCO.OC(=O)C(O)=O ANBZWDBEKOZNHY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000005750 Copper hydroxide Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 12
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 27
- 238000009826 distribution Methods 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 5
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 description 134
- 239000013078 crystal Substances 0.000 description 27
- 239000000919 ceramic Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 15
- 238000007731 hot pressing Methods 0.000 description 11
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- -1 titanium ions Chemical class 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
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- 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
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
In order to overcome the problems of wide size distribution and poor dielectric property of the existing barium titanate-based powder, the invention provides a preparation method of the barium titanate-based powder, which comprises the following operation steps: preparing barium titanate-based precursor suspension: mixing a barium source, a titanium source and oxalic acid to obtain a barium titanate-based precursor suspension; carbon adsorption: adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material to obtain a carbon-coated barium titanate-based precursor; and (3) calcining: and calcining the carbon-coated barium titanate-based precursor, and thermally decomposing to obtain barium titanate-based powder. Meanwhile, the invention also discloses the barium titanate-based powder prepared by the preparation method and a super capacitor. The preparation method provided by the invention can be used for preparing the tetragonal barium titanate-based powder with excellent crystallization property, small and uniform particle size, and greatly improves the dielectric property of the barium titanate-based powder.
Description
Technical Field
The invention belongs to the technical field of electronic ceramic materials, and particularly relates to a barium titanate-based powder preparation method, barium titanate and a supercapacitor.
Background
Barium titanate is a basic raw material of electronic ceramic materials, and is called a support of electronic ceramic industry. It has high dielectric constant, low dielectric loss, excellent ferroelectric, piezoelectric, voltage withstanding and insulating properties, and is widely used in the manufacture of ceramic sensitive elements, such as multilayer ceramic capacitors (MLCCs), piezoelectric ceramics, crystal ceramic capacitors, electro-optic display panels, memory materials, polymer matrix composites, coatings, etc. The ideal ceramic powder raw material has the characteristics of high purity, fine particles and dispersion state, and the characteristics all guide the direction for developing barium titanate-based powder by people.
The method for preparing barium titanate mainly comprises a solid-phase synthesis method, a coprecipitation method, a sol-gel method, a hydrothermal synthesis method and the like. The solid-phase synthesis method needs ball milling and calcining, and has the advantages of high energy consumption, large grain size and low powder purity. Barium titanate-based powder is generally prepared by a wet process, and compared with a sol-gel method, a hydrothermal synthesis method and the like, an oxalate coprecipitation method in the wet process has the advantages of simple process conditions and suitability for industrial production, and the prepared powder has high purity, good shape and good repeatability, so that the research and application are more, but the traditional method has the defects of nonuniform heating, slow widening of the size distribution of the synthesized powder, serious agglomeration of the powder and difficult dispersion, and the dielectric property of barium titanate can be greatly weakened.
The preparation of Barium Titanate by Oxalate coprecipitation is invented by Clabaugh, e.g. [ "preparation of Barium Titanate oxide for Conversion to Barium Titanate of High Purity", Journal of Research of the National Bureau of Standards, vol.56, No.5, pp.289-291, 1956]The specific process is as follows: chlorination ofBarium and titanium chloride were mixed in a ratio of about 1:1, the mixture was added to oxalic acid to precipitate barium titanyl oxalate, and then the barium titanyl oxalate was washed, filtered, and thermally decomposed at a temperature of about 800 c to obtain barium titanate-based powder. However, hard agglomerates are formed among particles during thermal decomposition, strong grinding is required, the particle size distribution becomes excessively broad during grinding, the resulting fine particles are hardly dispersed during molding, and abnormal growth of crystal grains is observed during sintering, thus adversely affecting the dielectric properties. Yamamura et al further invented a Method of replacing water with an Ethanol Solution to obtain a fine-grained precipitate, such as "Preparation of Bar titanium by oxide Method in Ethanol Solution", Ceramic International, vol.11, No.1, pp.17-22,1985]It is described. Subsequently, [ "Particle Size Control of Bar titanium precursor from Bar titanium oxide", joural of the American Ceramic Society, vol.80, No.6, pp.1599-1604,1997]Cho et al used varying aging times and solvents to obtain fine barium titanate particles. "research on preparation of barium titanate ultrafine powder by improved oxalate coprecipitation method", journal of aviation materials, vol.1, No.28, pp.49-52,2008]In Zhengzhou university Hookeri et al, an improved oxalate coprecipitation method for preparing BaTi0 was proposed3The powder preparation method prepares the tetragonal phase BaTiO with fine and uniform particles and good thermal stability3And (3) powder. Chinese patent application publication No. CN 103796956 a provides a method for producing barium titanate having excellent crystallinity despite its small particle size by the oxalate method. In addition, the chinese patent application publication No. CN 107973600 a, which is directed to preparing tetragonal barium titanate nano powder by microwave-assisted oxalic acid precipitation, directly adopts microwave energy and internal heating by intermolecular action, so as to reduce the reaction activation energy, and accelerate the temperature rise rate of the solution, so that the whole sample quickly reaches the set temperature, and the phenomenon of widening the size distribution of the synthesized powder caused by uneven and slow heating in the prior art is improved.
All the above methods improve the performance of barium titanate-based powder from one aspect or several aspects, for example, fine particles are obtained by a method of using ethanol to replace water, but the crystallization performance of the barium titanate-based powder obtained by the method is poor, and the agglomeration is serious; while patent CN 103796956 a obtained barium titanate with small particle size and excellent crystallinity, the uneven heating and slow heating resulted in a broadening of the powder size distribution; patent CN 107973600 a improves the problem of widening the size distribution of the synthesized powder caused by uneven and slow heating in the prior art, and obtains tetragonal barium titanate with excellent crystallization performance, but the calcination temperature is high and the particle size is large, so all the above methods have limited improvement on the dielectric properties of barium titanate-based powder, and the dielectric properties of barium titanate-based powder also have a large promotion space.
Disclosure of Invention
The invention provides a preparation method of barium titanate-based powder, the barium titanate-based powder and a supercapacitor, aiming at the problems of wide size distribution and poor dielectric property of the existing barium titanate-based powder.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a method for preparing barium titanate-based powder, which comprises the following operation steps:
preparing barium titanate-based precursor suspension: mixing a barium source, a titanium source and oxalic acid to obtain a barium titanate-based precursor suspension;
carbon adsorption: adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material to obtain a carbon-coated barium titanate-based precursor;
and (3) calcining: and calcining the carbon-coated barium titanate-based precursor, and thermally decomposing to obtain barium titanate-based powder.
Optionally, the titanium source is selected from a trivalent titanium ion solution.
Optionally, the operation of "preparing a barium titanate-based precursor suspension" includes:
and adding the mixed aqueous solution of barium chloride and titanium trichloride into an oxalic acid ethanol solution, and carrying out coprecipitation reaction to obtain a barium titanate-based precursor suspension.
Optionally, the mixed aqueous solution is obtained by mixing a barium chloride aqueous solution and a titanium trichloride aqueous solution, the concentration of the barium chloride aqueous solution is 1-2 mol/L, the concentration of the titanium trichloride aqueous solution is 1-2 mol/L, the molar ratio of barium chloride to titanium trichloride in the mixed aqueous solution is 1-1.2: 1, the concentration of the oxalic acid ethanol solution is 0.1-0.5 mol/L, the volume ratio of the mixed aqueous solution to the oxalic acid ethanol solution is 0.01-0.05: 1, the temperature of the coprecipitation reaction is 60-70 ℃, and the stirring is continuously carried out for 1-2 hours.
Optionally, the aperture of the carbon template is 2-50 nm.
Optionally, the carbon template includes powdered mesoporous carbon and/or three-dimensional graphene.
Optionally, the "carbon adsorption" operation comprises:
adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material, stirring for 1-2 h, standing, aging for 3-4 h, washing the aged precipitate with ethanol or deionized water, filtering, and drying at 100-200 ℃ for 2-4 h to obtain the carbon-coated barium titanate-based precursor.
Optionally, the mass ratio of the carbon template to the barium titanate-based precursor suspension is 0.5-5: 100.
Optionally, the "calcining" operation comprises:
the method comprises the steps of carrying out dry crushing on a carbon-coated barium titanate-based precursor, then carrying out thermal decomposition in an air atmosphere, heating at a rate of 3-6 ℃/min, keeping at 700-900 ℃ for 2-4 h, and cooling at a cooling rate of more than 50 ℃/min after calcination.
Optionally, in the operation of preparing the precursor, one or more of a group iia metal source, a lanthanide metal source, and a transition metal source is added and mixed.
Optionally, in the operation of "carbon adsorption", a carbon template and aluminum chloride and/or copper chloride are added to the barium titanate-based precursor suspension, the carbon template is a porous carbon material, the carbon template is uniformly mixed, then alkali is added until aluminum hydroxide and/or copper hydroxide are completely precipitated, and the barium titanate-based precursor wrapped by carbon, aluminum hydroxide and/or copper hydroxide is obtained through aging.
On the other hand, the barium titanate-based powder is prepared by the preparation method, and comprises a plurality of tetragonal barium titanate crystal grains, wherein the size of the tetragonal barium titanate crystal grains is 10-30 nm.
In another aspect, the invention provides a supercapacitor, which includes a first electrode, a second electrode, and a dielectric, where the dielectric includes the barium titanate-based powder as described above, and the dielectric is located between the first electrode and the second electrode.
According to the preparation method of the barium titanate-based powder provided by the invention, the barium titanate-based precursor suspension is prepared by oxalate coprecipitation, then the carbon template is added into the barium titanate-based precursor suspension, the carbon template is a porous carbon material, the barium titanate-based precursor suspension is adsorbed by the adsorption capacity of the carbon template, so that the precursors generated by a barium source, a titanium source and oxalic acid can be wrapped in the carbon template, the size of the precursors is limited, the precursors form barium titanate-based powder in micropores of the carbon template in the calcining process, the size of crystal grains is controlled by the size of the pores, the carbon template is thermally decomposed and disappears in the calcining process, a large number of crystal boundaries are etched among the crystal grains, the crystal grains are easy to disperse, the combustion and the better heat conductivity of the carbon material are realized, the heat conduction is fast, the inside and the outside of the precursors are uniformly heated in the calcining process, and the temperature required by, is beneficial to obtaining tetragonal barium titanate-based powder with excellent crystallization property, small and uniform particle size, greatly improves the dielectric property of the barium titanate-based powder and obtains the barium titanate-based powder with the dielectric constant as high as 106～107Barium titanate-based powder.
Drawings
FIG. 1 is a flow chart of the preparation of barium titanate-based powder according to the present invention;
FIG. 2 is a schematic diagram of the apparent dielectric properties of barium titanate-based powder according to the present invention;
FIG. 3 is a schematic diagram of the apparent dielectric properties of barium titanate-based powder provided by the present invention;
FIG. 4 is an electron microscope image of the micropore morphology of the three-dimensional graphene provided by the invention;
fig. 5 is a diagram of pore size distribution of three-dimensional graphene provided by the present invention;
FIG. 6 is a chart of process control parameters for the spark plasma hot pressing sintering (SPS) process provided in example 1 of the present invention;
FIG. 7 is a graph of dielectric properties of barium titanate-based powder samples provided in example 4 of the present invention;
FIG. 8 is an electron microscope image of the morphology of crystalline grains of a barium titanate-based powder sample provided in example 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the invention provides a method for preparing barium titanate-based powder, which comprises the following operation steps:
preparing barium titanate-based precursor suspension: mixing a barium source, a titanium source and oxalic acid to obtain a barium titanate-based precursor suspension;
carbon adsorption: adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material to obtain a carbon-coated barium titanate-based precursor;
and (3) calcining: and calcining the carbon-coated barium titanate-based precursor, and thermally decomposing to obtain barium titanate-based powder.
Barium titanate-based powder exhibits an extremely high dielectric constant, and the principle thereof is that an insulating boundary layer is formed at the grain boundary of barium titanate-based powder, which corresponds to series and parallel connection of a plurality of capacitors as a whole, thereby finally obtaining a large apparent dielectric constant, and the principle schematic diagrams are shown in fig. 2 and 3. It can be seen from fig. 2 and 3 that the finer the crystal grain, the better the dispersibility, the more the crystal grain boundary, the higher the apparent dielectric constant of the barium titanate-based powder, the analysis of the invention is developed from the view point of the micro-mechanism, and the multi-aspect factors such as the crystal grain size, the dispersibility, the crystallinity and the heat transfer property are comprehensively considered, the carbon template is a porous carbon material, and the barium titanate-based powder with high dielectric constant is obtained by the oxalate coprecipitation method.
The size of the precursor is limited by micropores of the carbon template, barium titanate is formed in the micropores of the carbon template in the calcining process, the size of crystal grains is controlled by the size of the pores, the carbon template is thermally decomposed and disappears in the calcining process, a large number of crystal boundaries are etched among the crystal grains, the crystal grains are easy to disperse, the combustion and the better heat conduction performance of the carbon material are realized, the heat conduction is quick, the heating inside and outside the precursor is uniform in the calcining process, the temperature required by calcining is reduced, the tetragonal phase barium titanate with excellent crystallization performance, small particle size and uniform particle size is favorably obtained, the dielectric performance of barium titanate-based powder is greatly improved, and the dielectric constant of the obtained barium titanate-based powder is up to 106～107Barium titanate-based powder.
As a further development of the invention, in an embodiment the titanium source is selected from a solution of trivalent titanium ions.
The prior oxalate coprecipitation method for preparing barium titanate generally adopts titanium tetrachloride as a titanium source, wherein titanium ions are tetravalent, however, the inventor finds through a large number of experiments that the method is compared with the method of directly adding Ti4+With Ti3+Is a source of titanium, in the course of the reaction, Ti3+In oxidation to form Ti4+More preferentially to the [ TiO (OH) required to form barium titanate-based precursors2)5]2+A homopolymer of [ TiO (OH)2)5]2+The monomer is of an octahedral structure, can effectively improve the crystallization performance of the barium titanate-based powder, and is beneficial to forming tetragonal crystal grains with narrow particle size distribution, so that the dielectric constant of the barium titanate-based powder is improved.
Ti in solution3+Is completely oxidized to Ti4+The reaction process of (2) continuously generates bubbles, the solution color is changed from brown to yellowish, and the specific reaction process is as follows:
Ti3++6H2O→[Ti(OH2)6]3+，[Ti(OH2)6]3+→[Ti(OH)(OH2)5]2++H+→[TiO(OH2)5]++2H+，4[TiO(OH2)5]++O2+4H+→4[TiO(OH2)5]2++2H2O。
in one embodiment, the "barium titanate-based precursor suspension preparation" operation comprises:
and adding the mixed aqueous solution of barium chloride and titanium trichloride into an oxalic acid ethanol solution, and carrying out coprecipitation reaction to obtain a barium titanate-based precursor suspension.
In this embodiment, the precursor suspension is a suspension of barium titanyl oxalate, and compared with a reaction system of water, ethanol is used to replace part of water, so that the size of precipitated particles of barium titanyl oxalate can be reduced, a fine-grained precipitate is obtained, and reduction of particles of barium titanate-based powder is facilitated.
In some embodiments, the mixed aqueous solution is obtained by mixing a barium chloride aqueous solution and a titanium trichloride aqueous solution, the concentration of the barium chloride aqueous solution is 1-2 mol/L, the concentration of the titanium trichloride aqueous solution is 1-2 mol/L, the molar ratio of barium chloride to titanium trichloride in the mixed aqueous solution is 1-1.2: 1, the concentration of the oxalic acid ethanol solution is 0.1-0.5 mol/L, the volume ratio of the mixed aqueous solution to the oxalic acid ethanol solution is 0.01-0.05: 1, the temperature of the coprecipitation reaction is 60-70 ℃, and the stirring is continuously carried out for 1-2 hours.
In the reaction system, the addition of ethanol is far larger than that of water, so that barium titanyl oxalate with small particle size and uniform distribution is formed.
It should be noted that, in other embodiments, the chloride ion in the barium chloride and the titanium trichloride may be replaced by other anions which do not participate in the reaction, and any modification, equivalent replacement, improvement and the like within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In some embodiments, the carbon template has a pore size of 2 to 50 nm.
As shown in fig. 4 and 5, a microscopic electron microscope image and a pore size distribution image of the carbon template according to an embodiment of the present invention are provided.
The aperture of the carbon template limits the generated particle size of the barium titanate-based precursor, so that the particle size of the finally generated barium titanate-based powder is limited, the particle size of the generated barium titanate-based powder can be effectively controlled to be in a smaller range by controlling the aperture of the carbon template to be 2-50 nm, if the aperture of the carbon template is too small, the adsorption effect on the barium titanate-based precursor is difficult to generate, and the carbon template can have adverse effect on the wrapping of the barium titanate-based precursor; if the pore size of the carbon template is too large, the range of the particle size for molding the barium titanate-based precursor will be affected.
In some embodiments, the carbon template comprises powdered mesoporous carbon and/or three-dimensional graphene.
The powdered carbon template is adopted, so that the adsorption efficiency of the carbon template on the barium titanate-based precursor is improved, and the difficulty of subsequent crushing is reduced.
In some embodiments, the "carbon adsorption" operation comprises:
adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material, stirring for 1-2 h, standing, aging for 3-4 h, washing the aged precipitate with ethanol or deionized water, filtering, and drying at 100-200 ℃ for 2-4 h to obtain the carbon-coated barium titanate-based precursor.
The barium titanyl precursor suspension mainly comprises barium sources, titanium sources and barium titanyl oxalate crystal nucleus suspensions obtained by oxalic acid precipitation, the barium titanyl oxalate crystal nucleus suspensions enter micropores of a carbon template through the adsorption of the carbon template, and then aging treatment is carried out, so that the crystal nucleus of barium titanyl oxalate can grow up, the barium titanyl oxalate crystal nucleus is fully separated out, and meanwhile, the carbon template provides sites for the formation and growth of barium titanyl oxalate crystal nuclei.
In some embodiments, the mass ratio of the carbon template to the barium titanate-based precursor suspension is 0.5-5: 100.
In some embodiments, the "calcining" operation comprises:
the method comprises the steps of carrying out dry crushing on a carbon-coated barium titanate-based precursor, then carrying out thermal decomposition in an air atmosphere, heating at a rate of 3-6 ℃/min, keeping at 700-900 ℃ for 2-4 h, and cooling at a cooling rate of more than 50 ℃/min after calcination.
The dry type crushing comprises grinding, ball milling, jet milling or centrifugal impact, preferably jet milling is adopted, and the average size of the crushed particles is controlled to be 0.5-5 um.
The barium titanate-based precursor forms barium titanate-based powder during thermal decomposition, and the barium titanate-based powder is crystallized to form tetragonal crystal grains and continuously grow up in the calcining process, in the embodiment, the grain size growth of the barium titanate-based powder can be effectively controlled by controlling the heating efficiency to be 3-6 ℃/min and keeping the heating efficiency at 700-900 ℃ for 2-4 h, and more preferably, after the calcining is completed, the temperature is rapidly reduced at a temperature reduction rate of more than 50 ℃/min, so that the grain size of the obtained barium titanate-based powder is relatively close, and the problems of wide grain size distribution range and large grain size caused by continuous growth of barium titanate particles in subsequent temperature reduction are solved.
In some embodiments, one or more of a group IIA metal source, a lanthanide metal source and a transition metal source are also added and mixed during the "precursor preparation" operation.
Specifically, the IIA group metal source, the lanthanide series metal source and the transition metal source can be introduced into a reaction system in the form of metal salt, and combined with a titanium source, a barium source and oxalic acid in a coprecipitation manner to obtain one or more doped barium titanate-based precursors of the IIA group metal, the lanthanide series metal and the transition metal, and then one or more of the IIA group metal, the lanthanide series metal and the transition metal is doped into the finally prepared barium titanate-based powder.
In some embodiments, in the "carbon adsorption" operation, a carbon template and aluminum chloride and/or copper chloride are added to a barium titanate-based precursor suspension, the carbon template is a porous carbon material, after being uniformly mixed, alkali is added until aluminum hydroxide and/or copper hydroxide are completely precipitated, and the mixture is aged to obtain a barium titanate-based precursor wrapped by carbon, aluminum hydroxide and/or copper hydroxide.
And the alkali is selected from ammonia water, and the ammonia water is slowly added until the pH value of the system is 10, so that aluminum hydroxide and/or copper hydroxide precipitate is obtained.
In the subsequent calcination process, carbon in the barium titanate-based precursor can be removed by thermal decomposition, and aluminum hydroxide and/or copper hydroxide are thermally decomposed into aluminum oxide and/or copper oxide, so that aluminum oxide and/or copper oxide-coated barium titanate-based powder is finally obtained.
Another embodiment of the present invention provides a barium titanate-based powder prepared by the above preparation method, wherein the barium titanate-based powder includes a plurality of tetragonal barium titanate crystal grains, and the size of the tetragonal barium titanate crystal grains is 10 to 30 nm.
Another embodiment of the present invention provides a supercapacitor, including a first electrode, a second electrode, and a dielectric, where the dielectric includes the barium titanate-based powder as described above, and the dielectric is located between the first electrode and the second electrode.
The super capacitor adopts barium titanate-based powder with an ultrahigh apparent dielectric constant as a dielectric medium, so that the capacitance of the super capacitor can be effectively improved, the energy storage density is improved, and the electrical property of the super capacitor is improved.
The present invention will be further illustrated by the following examples.
Example 1
This embodiment is used to illustrate a barium titanate-based powder and a method for preparing the same disclosed in the present invention, and the method includes the following steps:
10ml of 1.5mol/L barium chloride dihydrate BaCl2·2H2O aqueous solution and 10ml titanium trichloride TiCl with a concentration of 1.5mol/L3The aqueous solutions are mixed to form a mixed solution of Ba and Ti elements. The mixed solution was added to 500ml of a 0.25mol/L oxalic acid ethanol solution while stirring.
After the mixed solution is added, continuously stirring for 1 hour at the temperature of 70 ℃ to perform coprecipitation precipitation reaction, then adding 3.5g of three-dimensional graphene powder while stirring, continuously stirring for 1 hour, stopping stirring after uniform mixing, and cooling the solution in the air for 4 hours so as to facilitate precipitation and aging of the barium titanate precursor.
And washing, filtering and drying the carbon-coated barium titanate precursor precipitate, then crushing in a jet mill, controlling the average size of particles to be about 0.5-5 um, heating and calcining the crushed powder in an electric heating furnace in an air atmosphere at a heating rate of 10 ℃/min for 4 hours at 850 ℃, rapidly cooling at a cooling rate of more than 50 ℃/min, and finally obtaining the barium titanate powder after cooling.
Taking barium titanate powder, and preparing a round ceramic sample wafer with the diameter of phi 10 multiplied by 1mm by a spark plasma hot pressing sintering (SPS) method, wherein the specific hot pressing process parameters are controlled as shown in figure 6.
Taking out the sintered round ceramic sample and polishing, coating silver paste on two sides of the sample as electrodes, testing capacitance C and dielectric loss D of the round ceramic sample by using an impedance analyzer, measuring thickness D and diameter l of the round ceramic sample by using a micrometer, and then according to a formula C ═ epsilon ∈ epsilon0πl2The dielectric constant epsilon is calculated by the/4D, and the dielectric loss D can be directly obtained from the reading measured by the impedance analyzer. The sample obtained in this example was found to have an apparent dielectric constant ε of 1.12X 10 at a frequency of 4Hz6The dielectric loss D was 0.71.
Example 2
This embodiment is used for comparative illustration of a barium titanate-based powder and a method for preparing the same disclosed in the present invention, and the method includes the following steps:
10ml of 1.5mol/L barium chloride dihydrate BaCl2·2H2O aqueous solution and 10ml titanium trichloride TiCl with a concentration of 1.5mol/L3The aqueous solutions are mixed to form a mixed solution of Ba and Ti elements. The mixed solution was added to 500ml of a 0.25mol/L oxalic acid ethanol solution while stirring.
After the mixed solution is added, continuously stirring for 1 hour at the temperature of 70 ℃ for coprecipitation precipitation reaction, then adding 3.5g of three-dimensional graphene powder while stirring, continuously stirring for 1 hour for full mixing, then slowly adding 10ml of copper chloride solution with the concentration of 0.8mol/L, after the mixture is uniformly mixed by a stirrer, continuously adding ammonia water, adjusting the pH value of the system to 10, then stirring for 1 hour, stopping heating and stirring after copper hydroxide is completely precipitated, cooling the solution in the air for 4 hours, and aging to obtain carbon and copper hydroxide coated barium titanate precursor precipitate.
And (2) washing, filtering and drying the barium titanate-based precursor sediment wrapped by the carbon and the copper hydroxide, then crushing in an airflow crusher, controlling the average size of particles to be about 0.5-5 um, heating and calcining the crushed powder in an electric heating furnace in an air atmosphere at a heating rate of 10 ℃/min and keeping at 850 ℃ for 4 hours, thermally decomposing a carbon template into carbon dioxide for volatilization, thermally decomposing the copper hydroxide to form copper oxide, and rapidly cooling at a cooling rate of more than 50 ℃/min to finally obtain the barium titanate powder coated by the double-layer copper oxide.
The barium titanate powder coated with copper oxide is prepared into a round ceramic sample wafer with phi 10 multiplied by 1mm by a spark plasma hot pressing sintering (SPS) method, and the specific hot pressing process parameter control is consistent with that of the embodiment 1.
Taking out the sintered round ceramic sample and polishing, coating silver paste on two sides of the sample as electrodes, testing capacitance C and dielectric loss D of the round ceramic sample by using an impedance analyzer, measuring thickness D and diameter l of the round ceramic sample by using a micrometer, and then according to a formula C ═ epsilon ∈ epsilon0πl2The dielectric constant epsilon is calculated by the/4D, and the dielectric loss D can be directly obtained from the reading measured by the impedance analyzer. The sample obtained in this example was found to have an apparent dielectric constant ε of 4.69X 10 at a frequency of 4Hz5The dielectric loss D was 0.43.
Example 3
This embodiment is used to illustrate a barium titanate-based powder and a method for preparing the same disclosed in the present invention, and the method includes the following steps:
10ml of 1.5mol/L barium chloride dihydrate BaCl2·2H2O aqueous solution and 10ml titanium trichloride TiCl with a concentration of 1.5mol/L3The aqueous solutions were mixed and 2ml of 0.8mol/L (heptahydrate) lanthanum chloride LaCl were added3·7H2And O aqueous solution to form mixed solution of Ba, Ti and La. The mixed solution of the three elements was added to 500ml of an ethanol oxalate solution with a concentration of 0.25mol/L while stirring.
After the mixed solution is added, continuously stirring for 1 hour at the temperature of 70 ℃ for coprecipitation precipitation reaction, then adding 4g of three-dimensional graphene powder while stirring, continuously stirring for 1 hour for full mixing, then slowly adding 10ml of aluminum chloride solution with the concentration of 0.8mol/L, after the mixture is uniformly mixed by a stirrer, continuously adding ammonia water, adjusting the pH value of the system to 10, then stirring for 1 hour, stopping heating and stirring after aluminum hydroxide is completely precipitated, cooling the solution in the air for 4 hours, and aging to obtain carbon and aluminum hydroxide coated lanthanum-doped barium titanate precursor precipitate.
And (2) washing, filtering and drying the barium titanate-based precursor sediment wrapped by the carbon and the aluminum hydroxide, then crushing in an airflow crusher, controlling the average size of particles to be about 0.5-5 um, heating and calcining the crushed powder in an electric heating furnace in an air atmosphere at a heating rate of 10 ℃/min and keeping at 850 ℃ for 4 hours, thermally decomposing a carbon template into carbon dioxide for volatilization, thermally decomposing aluminum hydroxide to form aluminum oxide, and rapidly cooling at a cooling rate of more than 50 ℃/min to finally obtain the lanthanum-doped barium titanate powder wrapped by the double-layer aluminum oxide.
Lanthanum-doped barium titanate powder coated by double layers of alumina is taken and made into a round ceramic sample wafer with phi 10 multiplied by 1mm by a spark plasma hot pressing sintering (SPS) method, and the specific hot pressing process parameter control is consistent with that of the embodiment 1.
Taking out the sintered round ceramic sample and polishing, coating silver paste on two sides of the sample as electrodes, testing capacitance C and dielectric loss D of the round ceramic sample by using an impedance analyzer, measuring thickness D and diameter l of the round ceramic sample by using a micrometer, and then according to a formula C ═ epsilon ∈ epsilon0πl2The dielectric constant epsilon is calculated by the/4D, and the dielectric loss D can be directly obtained from the reading measured by the impedance analyzer. The sample obtained in this example was found to have an apparent dielectric constant ε of 8.86X 10 at a frequency of 4Hz6The dielectric loss D was 0.26.
Example 4
This embodiment is used to illustrate a barium titanate-based powder and a method for preparing the same disclosed in the present invention, and the method includes the following steps:
10ml of the solution with the concentration of 1.5mol/L(dihydrate) barium chloride BaCl2·2H2O aqueous solution and 10ml titanium trichloride TiCl with a concentration of 1.5mol/L3The aqueous solutions were mixed and 2ml of 0.8mol/L (heptahydrate) lanthanum chloride LaCl were added3·7H2And O aqueous solution to form mixed solution of Ba, Ti and La. The mixed solution of the three elements was added to 500ml of an ethanol oxalate solution with a concentration of 0.25mol/L while stirring.
After the mixed solution is added, continuously stirring for 1 hour at the temperature of 70 ℃ to perform coprecipitation precipitation reaction, then adding 4g of three-dimensional graphene powder while stirring, continuously stirring for 1 hour, stopping stirring after uniform mixing, and cooling the solution in the air for 4 hours so as to facilitate precipitation and aging of the barium lanthanum titanate precursor.
And (2) washing, filtering and drying the carbon-coated barium lanthanum titanate precursor precipitate, then crushing in a jet mill, controlling the average size of particles to be about 0.5-5 um, heating and calcining the crushed powder in an electric heating furnace in the air atmosphere at a heating rate of 10 ℃/min for 4 hours at a temperature of 850 ℃, rapidly cooling at a cooling rate of more than 50 ℃/min, and finally obtaining lanthanum-doped barium titanate powder after cooling.
Lanthanum-doped barium titanate powder is taken and made into a round ceramic sample wafer with phi 10 multiplied by 1mm by a spark plasma hot pressing sintering (SPS) method, and the specific hot pressing process parameter control is consistent with that of the embodiment 1.
Taking out the sintered round ceramic sample and polishing, coating silver paste on two sides of the sample as electrodes, testing capacitance C and dielectric loss D of the round ceramic sample by using an impedance analyzer, measuring thickness D and diameter l of the round ceramic sample by using a micrometer, and then according to a formula C ═ epsilon ∈ epsilon0πl2The dielectric constant epsilon is calculated by the/4D, and the dielectric loss D can be directly obtained from the reading measured by the impedance analyzer. The dielectric properties of the sample obtained in this example are shown in FIG. 7, and the apparent dielectric constant ε was 1.7X 10 at a frequency of 4Hz7The dielectric loss D was 0.41.
The crystal grain morphology of the sample section is observed by adopting a German Zeiss Sigma 500/VP type scanning electron microscope, and as shown in figure 8, the crystal grain morphology is excellent, the crystal grains are uniform, and the size is about 20 nm.
Comparative example 1
This embodiment is used for comparative illustration of a barium titanate-based powder and a method for preparing the same disclosed in the present invention, and the method includes the following steps:
10ml of 1.5mol/L barium chloride dihydrate BaCl2·2H2O aqueous solution and 10ml titanium trichloride TiCl with a concentration of 1.5mol/L3The aqueous solutions are mixed to form a mixed solution of Ba and Ti elements. The mixed solution was added to 500ml of a 0.25mol/L oxalic acid ethanol solution while stirring.
And after the mixed solution is added, continuously stirring for 2 hours at the temperature of 70 ℃ to perform coprecipitation precipitation reaction, stopping stirring after uniform mixing, and cooling the solution in the air for 4 hours so as to facilitate precipitation and aging of the barium titanate precursor.
And washing, filtering and drying the barium titanate precursor precipitate, then crushing in a jet mill, controlling the average size of particles to be about 0.5-5 um, heating and calcining the crushed powder in an electric heating furnace in an air atmosphere at a heating rate of 10 ℃/min at 850 ℃ for 4 hours, rapidly cooling at a cooling rate of more than 50 ℃/min, and cooling to finally obtain the barium titanate-based powder.
Barium titanate-based powder is taken and made into a round ceramic sample wafer with the diameter of 10 multiplied by 1mm by a spark plasma hot pressing sintering (SPS) method, and the specific hot pressing process parameter control is consistent with that of the embodiment 1.
Taking out the sintered round ceramic sample and polishing, coating silver paste on two sides of the sample as electrodes, testing capacitance C and dielectric loss D of the round ceramic sample by using an impedance analyzer, measuring thickness D and diameter l of the round ceramic sample by using a micrometer, and then according to a formula C ═ epsilon ∈ epsilon0πl2The dielectric constant epsilon is calculated by the/4D, and the dielectric loss D can be directly obtained from the reading measured by the impedance analyzer. The sample obtained in this example was found to have an apparent dielectric constant ε of 4.49X 10 at a frequency of 4Hz4The dielectric loss D was 1.16.
As can be seen from the results of comparing examples 1 to 4 and comparative example 1, the barium titanate-based powder obtained by the preparation method of the barium titanate-based powder provided by the invention has the advantages of excellent crystallization property, uniform grain size and higher apparent dielectric constant compared with the existing preparation method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (13)
1. The preparation method of the barium titanate-based powder is characterized by comprising the following operation steps of:
preparing barium titanate-based precursor suspension: mixing a barium source, a titanium source and oxalic acid to obtain a barium titanate-based precursor suspension;
carbon adsorption: adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material to obtain a carbon-coated barium titanate-based precursor;
and (3) calcining: and calcining the carbon-coated barium titanate-based precursor, and thermally decomposing to obtain barium titanate-based powder.
2. The method according to claim 1, wherein the titanium source is selected from a trivalent titanium ion solution.
3. The method for preparing barium titanate-based powder according to claim 1 or 2, wherein the operation of "preparing a barium titanate-based precursor suspension" comprises:
and adding the mixed aqueous solution of barium chloride and titanium trichloride into an oxalic acid ethanol solution, and carrying out coprecipitation reaction to obtain a barium titanate-based precursor suspension.
4. The method for preparing barium titanate-based powder according to claim 3, wherein the mixed aqueous solution is obtained by mixing a barium chloride aqueous solution and a titanium trichloride aqueous solution, the concentration of the barium chloride aqueous solution is 1-2 mol/L, the concentration of the titanium trichloride aqueous solution is 1-2 mol/L, the molar ratio of barium chloride to titanium trichloride in the mixed aqueous solution is 1-1.2: 1, the concentration of the oxalic acid ethanol solution is 0.1-0.5 mol/L, the volume ratio of the mixed aqueous solution to the oxalic acid ethanol solution is 0.01-0.05: 1, the temperature of the coprecipitation reaction is 60-70 ℃, and the stirring is continued for 1-2 hours.
5. The method for preparing barium titanate-based powder according to claim 1, wherein the carbon template has a pore size of 2 to 50 nm.
6. The method according to claim 1 or 5, wherein the carbon template comprises powdered mesoporous carbon and/or three-dimensional graphene.
7. The method of preparing a barium titanate-based powder of claim 1, wherein said "carbon adsorption" operation comprises:
adding a carbon template into the barium titanate-based precursor suspension, wherein the carbon template is a porous carbon material, stirring for 1-2 h, standing, aging for 3-4 h, washing the aged precipitate with ethanol or deionized water, filtering, and drying at 100-200 ℃ for 2-4 h to obtain the carbon-coated barium titanate-based precursor.
8. The method for preparing barium titanate-based powder according to claim 1 or 7, wherein the mass ratio of the carbon template to the barium titanate-based precursor suspension is 0.5-5: 100.
9. The method of preparing a barium titanate-based powder of claim 1, wherein said "calcining" operation comprises:
the method comprises the steps of carrying out dry crushing on a carbon-coated barium titanate-based precursor, then carrying out thermal decomposition in an air atmosphere, heating at a rate of 3-6 ℃/min, keeping at 700-900 ℃ for 2-4 h, and cooling at a cooling rate of more than 50 ℃/min after calcination.
10. The method according to claim 1, wherein one or more of a group IIA metal source, a lanthanide metal source and a transition metal source is/are further added and mixed in the precursor preparation operation.
11. The method for preparing barium titanate-based powder according to claim 1, wherein in the carbon adsorption operation, a carbon template and aluminum chloride and/or copper chloride are added into a barium titanate-based precursor suspension, the carbon template is a porous carbon material, after being uniformly mixed, alkali is added until aluminum hydroxide and/or copper hydroxide are completely precipitated, and the barium titanate-based precursor wrapped by carbon, aluminum hydroxide and/or copper hydroxide is obtained by aging.
12. The barium titanate-based powder prepared by the preparation method according to any one of claims 1 to 11, wherein the barium titanate-based powder comprises a plurality of tetragonal barium titanate grains, and the size of the tetragonal barium titanate grains is 10 to 30 nm.
13. A supercapacitor comprising a first electrode, a second electrode, and a dielectric comprising the barium titanate-based powder of claim 12, the dielectric being between the first electrode and the second electrode.
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| CN116041057A (en) * | 2022-12-26 | 2023-05-02 | 广东微容电子科技有限公司 | Barium titanate powder, preparation method and chip type multilayer ceramic capacitor |
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