CN115924963B - Preparation method for synthesizing tetragonal phase nano barium titanate by hydrothermal method, tetragonal phase nano barium titanate and application thereof - Google Patents
Preparation method for synthesizing tetragonal phase nano barium titanate by hydrothermal method, tetragonal phase nano barium titanate and application thereof Download PDFInfo
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 102
- 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 title claims abstract description 37
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract 18
- 239000000243 solution Substances 0.000 claims abstract description 53
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052788 barium Inorganic materials 0.000 claims abstract description 22
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 9
- 159000000009 barium salts Chemical class 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 5
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 claims description 5
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 abstract description 40
- 239000002245 particle Substances 0.000 abstract description 36
- 238000009826 distribution Methods 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 description 85
- 239000012071 phase Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Capacitors (AREA)
Abstract
The invention provides a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, the tetragonal phase nano barium titanate and application thereof, and belongs to the technical field of ceramic powder preparation. The preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method comprises the following steps: preparing a barium salt solution by using a barium source, adding titanium dioxide into the barium salt solution, adding a chloride solution, and adding a mineralizer solution to adjust the pH value of the solution to obtain a barium titanate precursor suspension; transferring the barium titanate precursor suspension to a hydrothermal reaction kettle for hydrothermal reaction; washing the barium titanate suspension synthesized by hydrothermal method with acetic acid and deionized water, and filtering; and then grinding after drying in an oven. The preparation method provided by the invention is simple to operate, low in cost, suitable for mass preparation, high in tetragonality, good in crystallinity, few in impurities, small in particle size, uniform in distribution, about 150nm in average particle size and excellent in performance, and can be applied to multilayer ceramic capacitors.
Description
Technical Field
The invention belongs to the technical field of ceramic powder preparation, and relates to a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, the tetragonal phase nano barium titanate and application thereof.
Background
Barium titanate is widely used in the field of electronic industry with excellent dielectric, ferroelectric and piezoelectric properties, and in particular in the field of ceramic capacitors, multilayer ceramic capacitors (MLCCs) using barium titanate as a material have a major market share. With the continuous development of miniaturization, integration, intellectualization and the like of electronic devices, the multilayer ceramic capacitor is also developed towards a direction of five high and one small. Therefore, the particle size of the raw material barium titanate determines the thickness of the dielectric layer, and simultaneously, higher requirements are also put on the particle size, purity, tetragonal phase and dispersibility of the barium titanate powder.
The conventional methods for industrially preparing barium titanate powder include a solid phase method, a liquid phase method and an oxalate method. The barium titanate powder prepared by the solid phase method has large particle size and low purity, and is difficult to meet the requirements of electronic components, and the powder synthesized by the oxalate method has serious agglomeration and difficult control of the barium-titanium ratio. The hydrothermal method can synthesize nano particles with uniform particle size, controllable particle size and good morphology, and is widely used for commercialized development. Due to the rapid development of miniaturized and reliable electronic components, research and development of barium titanate powder with high tetragonality and small particle size is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, tetragonal phase nano barium titanate and application thereof, and the prepared nano barium titanate powder has high tetragonality, good crystallinity, small particle size, uniform particle size distribution and smooth particle surface; the preparation method is simple and the cost is low.
In order to achieve the above purpose, the invention provides a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, which comprises the following steps:
Preparing a barium salt solution with the concentration of 1-4mol/L by using a barium source;
weighing titanium dioxide according to the proportion that the molar ratio of barium to titanium is more than or equal to 1, and adding the titanium dioxide into a barium salt solution while stirring to obtain a mixed solution 1;
preparing a chloride solution with the concentration of 1-5mol/L, and adding the chloride solution into the mixed solution 1 to obtain a mixed solution 2;
preparing mineralizer solution with molar concentration more than or equal to 1mol/L, adding the mineralizer solution into the mixed solution 2, and regulating the pH value of the solution to be more than or equal to 12 to obtain barium titanate precursor suspension;
Transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the filling degree of a container to be 60% -80%, cooling to room temperature after hydrothermal reaction, and opening the reaction kettle to obtain the barium titanate suspension;
Washing the barium titanate suspension with acetic acid and deionized water for a plurality of times until the filtrate is detected to be free of chloride ions by using a silver nitrate solution;
and drying the washed product in an oven, and grinding the dried product by using a mortar to obtain the tetragonal phase nano barium titanate.
Preferably, the barium source is any one of barium chloride dihydrate, barium hydroxide octahydrate, barium acetate and barium nitrate.
Preferably, the titanium dioxide is in an anatase or rutile phase crystal form and has a particle size of 1-100nm.
Preferably, the chloride is barium chloride or sodium chloride.
Preferably, the mineralizer is any one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the temperature of the hydrothermal reaction is 180-300 ℃, and the time of the hydrothermal reaction is 12-100h.
Preferably, the washing mode is suction filtration washing.
Preferably, the temperature of drying in the oven is 70-90 ℃ and the drying time is 12-24 h.
The invention also provides tetragonal phase nano barium titanate which is prepared by adopting the method.
The invention also provides an application of the tetragonal phase nano barium titanate in a multilayer ceramic capacitor.
The invention adopts the technical proposal has the advantages that:
the preparation method for synthesizing the tetragonal phase nano barium titanate by the hydrothermal method has the advantages of simple preparation, easy operation, low raw material cost, suitability for large-scale industrialization and the like. The barium titanate powder prepared by the method has the advantages of high tetragonality, good crystallinity, small particle size, uniform diameter distribution and smooth particle surface, has excellent performance, has the average particle size of about 150nm, and is suitable for application in multilayer ceramic capacitors.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method;
Fig. 2 is an SEM image of the barium titanate powder prepared in example 1;
FIG. 3 is an SEM image of barium titanate powder prepared in example 2;
fig. 4 is an SEM image of the barium titanate powder prepared in example 3;
fig. 5 is an SEM image of the barium titanate powder prepared in comparative example 1;
Fig. 6 is an SEM image of the barium titanate powder prepared in comparative example 2;
FIG. 7 is an SEM image of barium titanate powder prepared in comparative example 3;
Fig. 8 XRD patterns of barium titanate powders prepared in examples and comparative examples.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, the invention provides a preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, which comprises the following steps:
Preparing a barium salt solution with the concentration of 1-4mol/L by using a barium source;
weighing titanium dioxide according to the proportion that the molar ratio of barium to titanium is more than or equal to 1, and adding the titanium dioxide into a barium salt solution while stirring to obtain a mixed solution 1;
preparing a chloride solution with the concentration of 1-5mol/L, and adding the chloride solution into the mixed solution 1 to obtain a mixed solution 2;
preparing mineralizer solution with molar concentration more than or equal to 1mol/L, adding the mineralizer solution into the mixed solution 2, and regulating the pH value of the solution to be more than or equal to 12 to obtain barium titanate precursor suspension;
Transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the filling degree of a container to be 60% -80%, cooling to room temperature after hydrothermal reaction, and opening the reaction kettle to obtain the barium titanate suspension;
Washing the barium titanate suspension with acetic acid and deionized water for a plurality of times until the filtrate is detected to be free of chloride ions by using a silver nitrate solution;
and drying the washed product in an oven, and grinding the dried product by using a mortar to obtain the tetragonal phase nano barium titanate.
In the preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method, the titanium precursor has high specific surface area and high activity in the reaction process, and more barium titanate crystal nuclei are formed in the initial stage of the reaction, so that the reaction rate is accelerated. The addition of the chloride solution accelerates the dissolution of the precursor in the presence of chloride ions, more crystal nuclei can be generated, smaller and more uniform barium titanate crystal nuclei are formed in the early stage of the reaction, and the synthesis of tetragonal phase barium titanate powder is facilitated.
Wherein the barium source is any one or more of barium chloride dihydrate, barium hydroxide octahydrate, barium acetate, barium nitrate and the like. The titanium dioxide is in the crystal form of anatase or rutile phase or a mixture of the anatase and the rutile phase, and the grain size is 1-100nm. The chloride can be selected from any one or more of barium chloride and sodium chloride. The mineralizer is any one or more of sodium hydroxide, potassium hydroxide, ammonia water and the like.
The temperature of the hydrothermal reaction is preferably 180-300 ℃, and the time of the hydrothermal reaction is 12-100h. The washing mode can be selected as suction filtration washing. The drying temperature in the oven is preferably 70-90 ℃ and the drying time is 12-24 h.
The invention also provides tetragonal phase nano barium titanate which is prepared by adopting the method.
The invention also provides an application of the tetragonal phase nano barium titanate in a multilayer ceramic capacitor.
Example 1
A preparation method of tetragonal phase nano barium titanate comprises the following steps:
9.65g of barium hydroxide octahydrate was added to a beaker containing 15ml of deionized water and stirred in a water bath at 85℃with heating until the barium hydroxide octahydrate was completely dissolved in the water.
After the barium solution cooled to room temperature, 1.198g of 5nm anatase titanium dioxide was added to the barium solution with stirring until the titanium dioxide powder was completely dissolved in the barium solution.
4.631G of sodium chloride solution was added to a beaker containing 15ml of deionized water, stirred while heating in a water bath at 85 ℃, and added to the solution after sodium chloride was completely dissolved in water.
And (3) completely transferring the solution with the molar ratio of 2 into a 50ml hydrothermal reaction kettle, adding a certain amount of mineralizer solution, adjusting the pH value of the solution to be more than or equal to 12, carrying out hydrothermal reaction for 48 hours at the temperature of 240 ℃ with the filling rate of the reaction kettle being 70%, cooling to room temperature, and opening the reaction kettle to obtain the barium titanate solution.
And (3) carrying out suction filtration washing on the solution of the hydrothermally synthesized barium titanate for a plurality of times by using acetic acid and deionized water until the filtrate is detected to be free of chloride ions by using silver nitrate solution.
The washed product was placed in a glass vessel and dried in a forced air oven at 80℃for 12h. Then, the mixture was ground with a mortar to obtain barium titanate powder.
The barium titanate powder obtained in example 1 has a Scanning Electron Microscope (SEM) image and a particle size distribution chart as shown in fig. 2, and the average particle size of the sample is about 157nm, the particle size distribution is uniform, the morphology is smooth, and abnormal large particles are not generated. As shown in fig. 8, the X-ray diffraction (XRD) pattern of the barium titanate powder obtained in example 1 has no other impurity phases, and has distinct splitting peaks at characteristic peaks 2θ=44 to 46 °, which correspond to crystal planes (002) and (200) of tetragonal barium titanate, c/a= 1.0088, respectively.
Example 2
A preparation method of tetragonal phase nano barium titanate comprises the following steps:
9.822g of barium chloride dihydrate was added to a beaker containing 25ml of deionized water and stirred in a water bath at 85 ℃ with heating until the barium chloride dihydrate was completely dissolved in the water.
After the barium solution cooled to room temperature, 1.27792 of anatase titanium dioxide was added to the barium solution with stirring until the titanium dioxide powder was completely dissolved in the barium solution.
And (3) completely transferring the uniformly mixed solution with the molar ratio of barium to titanium being 2 into a 50ml hydrothermal reaction kettle, adding a certain amount of mineralizer solution, adjusting the pH value of the solution to be more than or equal to 12, carrying out hydrothermal reaction for 12 hours at the temperature of 300 ℃, cooling to room temperature, and opening the reaction kettle to obtain the barium titanate solution.
And (3) carrying out suction filtration washing on the solution of the hydrothermally synthesized barium titanate for a plurality of times by using acetic acid and deionized water until the filtrate is detected to be free of chloride ions by using silver nitrate solution.
The washed product was placed in a glass vessel and dried in a forced air oven at 80℃for 12h. Then, the mixture was ground with a mortar to obtain barium titanate powder.
The Scanning Electron Microscope (SEM) image and the particle size distribution chart of the barium titanate powder obtained in example 2 are shown in fig. 3, and the average particle size of the sample is about 165nm, the particle size distribution is uniform, the morphology is smooth, and abnormal large particles are avoided. As shown in fig. 8, the X-ray diffraction (XRD) pattern of the barium titanate powder obtained in example 2 shows that the barium titanate powder has a complete crystal form and no other impurity phase, and has distinct splitting peaks at the characteristic peaks 2θ=44 to 46 °, which correspond to crystal planes (002) and (200) of tetragonal barium titanate, respectively, and c/a= 1.0091.
Example 3
A preparation method of tetragonal phase nano barium titanate comprises the following steps:
7.662g of barium acetate was added to a beaker containing 15ml of deionized water and stirred in a water bath at 85 c with heating until the barium acetate was completely dissolved in the water.
After the barium solution cooled to room temperature, 0.798g of 10nm anatase titanium dioxide was added to the barium solution with stirring until the titanium dioxide powder was completely dissolved in the barium solution.
7.305G of sodium chloride solution was added to a beaker containing 15ml of deionized water, stirred while heating in a water bath at 85 ℃, and added to the solution after sodium chloride was completely dissolved in water.
And (3) completely transferring the solution with the molar ratio of 3 into a 50ml hydrothermal reaction kettle, adding a certain amount of mineralizer solution, adjusting the pH value of the solution to be more than or equal to 12, carrying out hydrothermal reaction for 100 hours at the temperature of 240 ℃ with the filling rate of the reaction kettle being 70%, cooling to room temperature, and opening the reaction kettle to obtain the barium titanate solution.
And (3) carrying out suction filtration washing on the solution of the hydrothermally synthesized barium titanate for a plurality of times by using acetic acid and deionized water until the filtrate is detected to be free of chloride ions by using silver nitrate solution.
The washed product was placed in a glass vessel and dried in a forced air oven at 80℃for 12h. Then, the mixture was ground with a mortar to obtain barium titanate powder.
The barium titanate powder obtained in example 3 has a Scanning Electron Microscope (SEM) image and a particle size distribution chart as shown in fig. 4, and the average particle size of the sample is about 150nm, the particle size distribution is uniform, the morphology is smooth, and abnormal large particles are not generated. The X-ray diffraction (XRD) pattern of barium titanate of example 1 is shown in fig. 8, without other impurity phases, with distinct splitting peaks at characteristic peaks 2θ=44 to 46 °, which correspond to crystal planes (002) and (200) of tetragonal phase barium titanate, c/a= 1.0083, respectively.
Comparative example 1
The barium titanate powder was prepared by a method differing from that of example 1 only in that sodium chloride was not added.
The XRD pattern of the barium titanate powder obtained in comparative example 1 is shown in fig. 8, and the cleavage peak at the characteristic peak 2θ=44 to 46 ° is not obvious, and the synthesized barium titanate powder is mainly in a cubic phase crystal form. As shown in FIG. 5, the SEM image of the barium titanate powder obtained in comparative example 1 shows that barium titanate has significantly large particles, and when no chloride ion exists, titanium is slowly dissolved, and nonuniform large crystal nuclei are easily formed, resulting in nonuniform particle size distribution of barium titanate in the later stage.
Comparative example 2
The preparation method of barium titanate powder differs from that of example 2 only in that the molar ratio of barium to titanium is 1.
The XRD pattern of the barium titanate powder obtained in comparative example 2 is shown in fig. 8, and there is a significant cleavage at the characteristic peak 2θ=44 to 46 °, c/a= 1.0085. As shown in fig. 6, the SEM image of the barium titanate powder obtained in comparative example 2 promoted dissolution of the precursor in the presence of chloride ions, but since barium titanate has few nucleation sites, barium titanate has a significant agglomeration phenomenon, and there are many barium titanate particles having a large particle diameter, and the particle size distribution is quite uneven.
Comparative example 3
The barium titanate powder was prepared by a method differing from that of example 3 only in that sodium chloride was not added.
The XRD pattern of the barium titanate powder obtained in comparative example 3 is shown in fig. 8, and the synthesized barium titanate powder is in a cubic phase crystal form, with no obvious cleavage peak, in the characteristic peak 2θ=44 to 46° as a single peak. The SEM image of the barium titanate powder obtained in comparative example 2 is shown in fig. 7, and the barium titanate obviously has obvious agglomeration phenomenon, incomplete crystal form development and quite uneven particle size distribution.
The invention adopts the technical proposal has the advantages that:
the preparation method for synthesizing the tetragonal phase nano barium titanate by the hydrothermal method has the advantages of simple preparation, easy operation, low raw material cost, suitability for large-scale industrialization and the like. The barium titanate powder prepared by the method has the advantages of high tetragonality, good crystallinity, small particle size, uniform diameter distribution and smooth particle surface, has excellent performance, has the average particle size of about 150nm, and is suitable for application in multilayer ceramic capacitors.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The preparation method for synthesizing tetragonal phase nano barium titanate by a hydrothermal method is characterized by comprising the following steps of:
Preparing a barium salt solution with the concentration of 1-4mol/L by using a barium source;
weighing titanium dioxide according to the proportion that the molar ratio of barium to titanium is more than or equal to 1, and adding the titanium dioxide into a barium salt solution while stirring to obtain a mixed solution 1;
preparing a chloride solution with the concentration of 1-5mol/L, and adding the chloride solution into the mixed solution 1 to obtain a mixed solution 2;
preparing mineralizer solution with molar concentration more than or equal to 1mol/L, adding the mineralizer solution into the mixed solution 2, and regulating the pH value of the solution to be more than or equal to 12 to obtain barium titanate precursor suspension;
Transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the filling degree of a container to be 60% -80%, cooling to room temperature after hydrothermal reaction, and opening the reaction kettle to obtain the barium titanate suspension;
Washing the barium titanate suspension with acetic acid and deionized water for a plurality of times until the filtrate is detected to be free of chloride ions by using a silver nitrate solution;
Drying the washed product in a drying oven, and grinding the dried product in a mortar to obtain the tetragonal phase nano barium titanate;
the barium source is any one of barium chloride dihydrate, barium hydroxide octahydrate, barium acetate and barium nitrate;
the chloride is sodium chloride;
the mineralizer is any one or more of sodium hydroxide, potassium hydroxide and ammonia water;
The temperature of the hydrothermal reaction is 180-300 ℃, and the time of the hydrothermal reaction is 12-100h;
The molar ratio of barium to titanium is 2-3;
the crystal form of the titanium dioxide is rutile phase, and the grain diameter is 1-100nm.
2. The method for preparing tetragonal nano barium titanate synthesized by hydrothermal method according to claim 1, wherein the washing mode is suction filtration washing.
3. The method for preparing tetragonal nano barium titanate synthesized by hydrothermal method according to claim 1, wherein the drying temperature in the oven is 70-90 ℃ and the drying time is 12-24h.
4. A tetragonal phase nano barium titanate prepared by the method of any one of claims 1-3.
5. Use of tetragonal phase nano barium titanate according to claim 4 in a multilayer ceramic capacitor.
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