CN113753944A - Superfine barium titanate powder and preparation method thereof - Google Patents

Superfine barium titanate powder and preparation method thereof Download PDF

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CN113753944A
CN113753944A CN202111197124.XA CN202111197124A CN113753944A CN 113753944 A CN113753944 A CN 113753944A CN 202111197124 A CN202111197124 A CN 202111197124A CN 113753944 A CN113753944 A CN 113753944A
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barium titanate
colloidal solution
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蔡少韩
戴书云
李甜
刘杰
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Fujian Basic Electronic Materials Co ltd
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Abstract

The invention relates to the technical field of dielectric ceramic raw materials, in particular to ultrafine barium titanate powder and a preparation method thereof. The preparation method of the superfine barium titanate powder provided by the invention comprises the following steps: A) TiCl with a concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution; B) subjecting the TiO to a reaction2Removing impurities from the colloidal solution and concentrating to obtain a colloidal solution with the mass content of 8-28%; C) and (2) adding a barium source into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12, dissolving, mixing with the colloidal solution obtained in the step B), reacting at the temperature of 100-110 ℃, and drying the obtained product to obtain the superfine barium titanate powder. The superfine barium titanate powder prepared by the invention has small particle size, uniform distribution, good crystallinity and spherical shape, and improves the current situation of shortage of products with small particle size in the market.In addition, the superfine barium titanate powder prepared by the invention has high purity.

Description

Superfine barium titanate powder and preparation method thereof
Technical Field
The invention relates to the technical field of dielectric ceramic raw materials, in particular to ultrafine barium titanate powder and a preparation method thereof.
Background
At present, the industrial production method of barium titanate powder can be divided into 3 types: high temperature solid phase method, oxalic acid coprecipitation method, hydrothermal method.
The high-temperature solid phase method adopts barium carbonate and titanium dioxide as raw materials to carry out high-temperature solid phase reaction to produce barium titanate powder. The method has the advantages of simple process, reliable equipment, mature technology, good product crystallinity, easily purchased raw materials, easy industrial production formation, high yield and low production cost; the main defects are large particles, irregular appearance, uneven particle size distribution and high energy consumption, so the method is generally used for preparing medium and low-end products with large particle sizes (more than or equal to 400nm) or low requirements.
The oxalic acid coprecipitation method is that the mixed solution of titanium tetrachloride and barium chloride is added into oxalic acid solution at a proper temperature, surfactant is added, barium titanyl oxalate precipitate is generated after reaction, and barium titanate powder is obtained after filtration, washing, drying and calcination. The method has the advantages of high product purity, good crystallinity, simple method and low material cost; the main defect is that the titanium barium ratio fluctuation between batches is large, and the nano powder with small particle size and good distribution is difficult to obtain.
The hydrothermal method is characterized in that a barium source solution and a titanium source in a certain form are mixed and transferred into a high-pressure synthesis kettle to form barium titanate powder at a certain temperature and pressure, the method is generally used for preparing products with the particle size of 100-400 nm, the products prepared by the method are good in crystallinity and excellent in particle size distribution, but the method is high in technical difficulty, and a high-pressure and high-temperature reaction kettle is adopted, so that equipment investment is large, and production cost is high.
With the miniaturization of electronic products, the sizes of components on a circuit board are required to be synchronously reduced, and the MLCC capacitor, as one of core components, is required to be smaller and smaller along with the development of the market. Barium titanate powder is used as a dielectric material or a material for MLCC capacitors, and the particle size thereof directly affects the size of MLCC capacitors, and thus the reduction of the particle size of barium titanate powder is a trend.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an ultrafine barium titanate powder and a preparation method thereof.
The invention provides a preparation method of superfine barium titanate powder, which comprises the following steps:
A) TiCl with a concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution;
B) subjecting the TiO to a reaction2Removing impurities from the colloidal solution and concentrating to obtain a colloidal solution with the mass content of 8-28%;
C) and (2) adding a barium source into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12, dissolving, mixing with the colloidal solution obtained in the step B), reacting at the temperature of 100-110 ℃, and drying the obtained product to obtain the superfine barium titanate powder.
Preferably, in the step A), the hydrolysis temperature is 90-105 ℃, and the hydrolysis is carried out under normal pressure.
Preferably, in step A), the TiO is2The specific surface area of the colloidal particles in the colloidal solution is 50-200 m2(ii)/g, the primary particle size is 8-30 nm;
the TiO is2The crystal form distribution of the colloidal particles in the colloidal solution comprises:
more than or equal to 50 wt% of brookite, less than or equal to 10 wt% of rutile and the balance of anatase.
Preferably, in the step B), the chloride ion concentration of the colloid solution after impurity removal is 100-10000 ppm.
Preferably, in the step B), the pH value of the colloid solution after impurity removal is 1.5-4.5.
Preferably, in the step C), the molar ratio of barium in the barium source to titanium in the colloidal solution obtained in the step B) is 0.9 to 1.1: 1.
preferably, in step C), the alkaline solution comprises a sodium hydroxide solution, a lithium hydroxide solution, a potassium hydroxide solution, a quaternary ammonium base solution or a choline base solution.
Preferably, in the step C), the reaction time is more than or equal to 60 min.
Preferably, step C) further comprises, after the reaction:
standing for precipitation, pouring out supernatant, washing with alcohol solution or other organic solvent, and filtering;
the drying temperature is 150-300 ℃.
The invention also provides the superfine barium titanate powder prepared by the preparation method.
The invention provides a preparation method of superfine barium titanate powder, which comprises the following steps: A) TiCl with a concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution; B) subjecting the TiO to a reaction2Removing impurities from the colloidal solution and concentrating to obtain a colloidal solution with the mass content of 8-28%; C) and (2) adding a barium source into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12, dissolving, mixing with the colloidal solution obtained in the step B), reacting at the temperature of 100-110 ℃, and drying the obtained product to obtain the superfine barium titanate powder. The superfine barium titanate powder prepared by the invention has small particle size, uniform distribution, good crystallinity and spherical shape, and improves the current situation of shortage of products with small particle size in the market. In addition, the superfine barium titanate powder prepared by the invention has high purity.
Drawings
FIG. 1 is an SEM photograph of an ultrafine barium titanate powder of example 1 of the present invention;
FIG. 2 is a particle size distribution diagram of an ultrafine barium titanate powder according to example 1 of the present invention;
FIG. 3 is an XRD pattern of the ultrafine barium titanate powder of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of superfine barium titanate powder, which comprises the following steps:
A) TiCl with a concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution;
B) subjecting the TiO to a reaction2Removing impurities from the colloidal solution and concentrating to obtain a colloidal solution with the mass content of 8-28%;
C) and (2) adding a barium source into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12, dissolving, mixing with the colloidal solution obtained in the step B), reacting at the temperature of 100-110 ℃, and drying the obtained product to obtain the superfine barium titanate powder.
Firstly, TiCl with the concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution.
Specifically, the method comprises the following steps:
TiCl with a concentration of 0.1-1.0 mol/L4Heating the solution to hydrolysis temperature for hydrolysis to obtain TiO2A colloidal solution.
In certain embodiments of the invention, the TiCl is4The concentration of the solution is 0.1mol/L, 0.25mol/L, 0.4mol/L, 0.5mol/L, 0.75mol/L or 1.0 mol/L. In certain embodiments of the invention, the TiCl is4The solvent of the solution is water.
In certain embodiments of the invention, the rate of temperature increase is greater than or equal to 2 deg.C/min. In certain embodiments, the rate of temperature increase is 2 ℃/min.
In some embodiments of the invention, the temperature of the hydrolysis is 90-105 ℃, and the hydrolysis is carried out under normal pressure. In certain embodiments, the temperature of the hydrolysis is 104 ℃. In some embodiments of the present invention, the hydrolysis time is 60 to 240 min. In certain embodiments, the time for hydrolysis is 60 min.
In certain embodiments of the present invention, after the hydrolysis is completed, the method further comprises: and (6) cooling. In certain embodiments of the invention, the rate of cooling is ≧ 2 ℃/min. In certain embodiments, the rate of cooling is 2 ℃/min. In certain embodiments, the cooled temperature is room temperature.
In certain embodiments of the invention, the TiO is2Of colloidal particles in a colloidal solutionThe specific surface area is 50-200 m2(ii)/g, the primary particle diameter is 8 to 30 nm.
In certain embodiments of the invention, the TiO is2The crystal form distribution of the colloidal particles in the colloidal solution comprises:
more than or equal to 50 wt% of brookite, less than or equal to 10 wt% of rutile and the balance of anatase.
In certain embodiments, the TiO2The crystal form distribution of the colloidal particles in the colloidal solution comprises:
63.62 wt% brookite, 4.21 wt% rutile and 32.71 wt% anatase;
or 72.30 wt% brookite, 0.43 wt% rutile and 27.27 wt% anatase;
or 68.60 wt% brookite, 3.20 wt% rutile, and 68.60 wt% anatase;
or 61.20 wt% brookite, 4.50 wt% rutile and 34.30 wt% anatase;
or 55.60 wt% brookite, 7.80 wt% rutile and 36.60 wt% anatase;
or 52.30 wt% brookite, 9.70 wt% rutile and 38.00 wt% anatase.
The invention passes through low-concentration TiCl4The method of forced hydrolysis can obtain superfine TiO with good dispersity and excellent grain size distribution2A colloidal solution.
To obtain TiO2After colloidal solution, the TiO is added2And removing impurities from the colloidal solution and concentrating to obtain the colloidal solution with the mass content of 8-28%. The obtained superfine TiO2The colloidal solution is stable and does not precipitate even after being placed for a long time.
The invention does not particularly limit the sequence of the impurity removal and concentration.
In certain embodiments of the invention, the TiO is paired with an anionic resin2Removing impurities from the colloidal solution.
In certain embodiments of the invention, the anionic resin comprises a PA316 anionic resin.
In certain embodiments of the invention, the anion treeA lipid and said TiO2The dosage ratio of the colloidal solution is 349-3487 g: 1L of the compound. In certain embodiments, the anionic resin and the TiO are2The dosage ratio of the colloidal solution is 1395 g: 1L, 349 g: 1L, 872 g: 1L, 1744 g: 1L, 2615 g: 1L or 3487 g: 1L of the compound.
In some embodiments of the invention, the concentration of chloride ions in the decontaminated colloidal solution is 100 to 10000 ppm. In certain embodiments, the decontaminated colloidal solution has a chloride ion concentration of 315ppm, 265ppm, 303ppm, 247ppm, 334ppm, or 298 ppm.
In some embodiments of the invention, the pH of the colloid solution after impurity removal is 1.5-4.5. In some embodiments, the pH value of the colloid solution after impurity removal is 3.9-4.2. In certain embodiments, the pH of the decontaminated colloidal solution is 4.02, 4.13, 3.94, 4.17, 3.87, or 4.05.
In some embodiments of the present invention, the concentration is a membrane concentration, and the concentration membrane used in the membrane concentration may be selected from membrane modules such as tubular membrane, plate membrane or roll membrane. In certain embodiments, the concentration membrane used for the concentration is a hollow fiber membrane.
In some embodiments of the invention, the mass content of the concentrated colloidal solution is 13% to 17%. In certain embodiments of the invention, the mass content of the concentrated colloidal solution is 13.5%, 16.3%, 14.6%, 15.4%, 15.7%, or 15.1%.
After a colloidal solution with the mass content of 8-28% is obtained, a barium source is put into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12 to be dissolved, the barium source is mixed with the colloidal solution obtained in the step B), the mixture reacts at the temperature of 100-110 ℃, and the obtained product is dried to obtain the superfine barium titanate powder.
In certain embodiments of the invention, the dissolution is stirred dissolution.
In certain embodiments of the invention, the temperature of the alkaline solution at pH ≧ 12 is ≧ 90 ℃. In some embodiments of the present invention, the temperature of the alkaline solution with pH value of more than or equal to 12 is 80-110 ℃, 90-110 ℃ or 90 ℃.
In certain embodiments of the present invention, the barium source comprises at least one of barium hydroxide octahydrate, barium hydroxide monohydrate, barium chloride, barium chlorate, barium acetate, barium nitrate, and barium oxide.
In the present invention, the alkaline solution is a catalyst. In certain embodiments of the present invention, the alkaline solution may be an organic alkaline solution or an inorganic alkaline solution. The inorganic alkali solution includes a metal hydroxide solution, and specifically, may be a sodium hydroxide solution, a lithium hydroxide solution, or a potassium hydroxide solution. The organic base solution includes a quaternary ammonium base solution or a choline base solution. In certain embodiments, the quaternary ammonium base solution is a tetramethylammonium hydroxide solution.
In certain embodiments of the invention, the pH of the alkaline solution is ≧ 13. In certain embodiments, the alkaline solution has a pH of 14.
In some embodiments of the present invention, the molar ratio of barium in the barium source to titanium in the colloidal solution obtained in step B) is 0.9 to 1.1: 1. in certain embodiments, the molar ratio of barium in the barium source to titanium in the colloidal solution obtained in step B) is 1.0034: 1. 1.0037: 1. 1.0032: 1. 1.0046: 1. 1.0045: 1 or 1.0035: 1.
in certain embodiments of the invention, the temperature of the reaction is 104 ℃.
In certain embodiments of the invention, the reaction time is 60min or more. In certain embodiments, the reaction time is 1.5 h.
In certain embodiments of the invention, the reaction is carried out under stirring. The stirring method and the rotation speed are not particularly limited in the present invention, and the stirring method and the rotation speed known to those skilled in the art may be used.
In certain embodiments of the present invention, after the reacting, further comprising:
standing for precipitation, pouring out supernatant, washing with alcohol solution or other organic solvent, and filtering.
In some embodiments of the present invention, the cleaning is performed by using an alcohol solution or other organic solvent until the pH value is 7-10. In certain embodiments, the alcohol solution comprises an ethanol solution or a glycol solution. In certain embodiments, the alcohol solution has a mass concentration of 95%.
The invention further uses alcohol solution to clean, and removes alkaline substances, impurities and the like after reaction, thereby obtaining barium titanate powder with higher purity. The purpose of using alcohols is to reduce the influence of washing with water or an acidic solution on the barium titanate crystal and to reduce the damage to the crystal surface.
In some embodiments of the present invention, the temperature of the drying is 150 to 300 ℃. In certain embodiments, the temperature of the drying is 150 ℃. In certain embodiments of the present invention, the method of drying is oven drying.
In certain embodiments of the invention, after drying, further comprising crushing. In some embodiments, after the crushing, further comprising: and (6) sieving. In certain embodiments, the sieve is 120 mesh.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention also provides the superfine barium titanate powder prepared by the preparation method.
The particle size of the superfine barium titanate powder provided by the invention is 10-60 nm. In some embodiments, the particle size of the ultrafine barium titanate powder is 25-30 nm.
In some embodiments of the present invention, the BET of the ultrafine barium titanate powder is 17-68.5 m2(BET) of 14.5 to 58nm and a CV value of 20.3 to 23.2%.
The superfine barium titanate powder provided by the invention has small particle size, uniform distribution, good crystallinity and spherical shape, and improves the current situation of shortage of products with small particle size in the market.
The superfine barium titanate powder prepared by the invention has higher purity. The impurities of the superfine barium titanate powder provided by the invention comprise Fe2O3、Al2O3、SiO2、SrO、Na2O, MgO, CaO and chloride, the content of each impurity is less than 60 mu g/g, the content of each impurity is lower, and the purity of the superfine barium titanate powder is high.
In order to further illustrate the present invention, the following will describe the ultrafine barium titanate powder and the method for preparing the same in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) 0.4mol/L TiCl is used4Pouring 5L of the solution into a four-mouth flat-bottom flask, heating to 104 ℃ at a heating rate of 2 ℃/min, hydrolyzing at 104 ℃ for 60min, and cooling to room temperature at a rate of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloidal solution is 1395 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 4.02, concentrating the colloidal solution with a chlorine ion concentration of 315ppm by using an Asahi chemical synthesis hollow fiber membrane to obtain a colloidal solution with a mass content of 13.5%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the sodium hydroxide solution to 90 ℃ by an electric heating sleeve, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium in the barium hydroxide octahydrate powder to titanium in the colloidal solution in the step 2) is (Ba/Ti is 1.0034: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
For the TiO obtained in the step 1)2The specific surface area and the crystal form distribution of the colloidal particles in the colloidal solution were measured, and the results are shown in table 1:
TABLE 1 TiO2Specific surface area and crystal form distribution of colloidal particles in colloidal solution
Figure BDA0003303475660000071
The scanning electron microscope analysis of the ultrafine barium titanate powder obtained in example 1 showed the results shown in fig. 1. FIG. 1 is an SEM photograph of an ultrafine barium titanate powder of example 1 of the present invention. As can be seen from fig. 1, the ultrafine barium titanate powder prepared in this example has a sphere-like shape, complete particles, good dispersibility, and uniform particle distribution.
The specific surface area of the ultrafine barium titanate powder obtained in example 1 was measured, and the specific surface area BET of the ultrafine barium titanate powder prepared in example 1 was 34.5722m2(BET) 28.84 nm. Wherein D (BET) is a primary particle size value converted using a specific surface area-BET measurement value.
In this embodiment, 3 to 5 regions of the same sample are photographed, the photographed SEM picture is subjected to particle size dotting, the sizes of the particles obtained by drawing are analyzed in a summary manner, and finally, a particle size distribution diagram is prepared according to the analysis result, as shown in fig. 2. FIG. 2 is a particle size distribution diagram of the ultrafine barium titanate powder of example 1 of the present invention. As can be seen from fig. 2, the particle size of the ultrafine barium titanate powder prepared in this example is concentrated in the range of 25 to 30nm and is normally distributed, and the analysis shows that the standard deviation σ of the plotted particle size is 5.8758, and the CV value is 21.97%, indicating that the particle size distribution is uniform.
The CV value is obtained by summarizing the particle diameters obtained by plotting each particle in the SEM electron micrograph, and calculating the standard deviation δ of the particle diameter and the average value D of the particle diameter according to the formula CV ═ δ/D × 100%.
The XRD analysis of the ultrafine barium titanate powder obtained in example 1 is shown in fig. 3. FIG. 3 is an XRD pattern of the ultrafine barium titanate powder of example 1 of the present invention. As can be seen from FIG. 3, each peak position of the ultrafine barium titanate powder of example 1 was in accordance with BaTiO No. 75 to 04613The PDF cards are consistent.
The impurities of the ultrafine barium titanate powder obtained in example 1 were detected, and the detection results are shown in table 2:
TABLE 2 detection results of impurity content of ultrafine barium titanate powder of example 1
Figure BDA0003303475660000081
Example 2
1) 0.1mol/L TiCl is used4Pouring 5L of the solution into a four-mouth flat-bottom flask, heating to 104 ℃ at a heating rate of 2 ℃/min, hydrolyzing at 104 ℃ for 60min, and cooling to room temperature at a rate of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloid solution is 349 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 4.13, wherein the chloride ion concentration of the colloidal solution is 265ppm, and concentrating by using an Asahi chemical compound hollow fiber membrane to obtain a colloidal solution with the mass content of 16.3%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the solution to 90 ℃ by an electric heating jacket, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium element in the barium hydroxide octahydrate powder to titanium element in the colloidal solution in the step 2) is (Ba/Ti-1.0037: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
Example 3
1) 0.25mol/L TiCl is used4Pouring 5L of the solution into a four-mouth flat-bottom flask, heating to 104 ℃ at a heating rate of 2 ℃/min, hydrolyzing at 104 ℃ for 60min, and cooling to room temperature at a rate of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloid solution is 872 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 3.94, concentrating the colloidal solution with a chlorine ion concentration of 303ppm by using an Asahi chemical compound hollow fiber membrane to obtain a colloidal solution with a mass content of 14.6%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the solution to 90 ℃ by an electric heating jacket, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium element in the barium hydroxide octahydrate powder to titanium element in the colloidal solution in the step 2) is (Ba/Ti-1.0032: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
Example 4
1) 0.5mol/L TiCl is used4Pouring 5L of the solution into a four-mouth flat-bottom flask, heating to 104 ℃ at a heating rate of 2 ℃/min, hydrolyzing at 104 ℃ for 60min, and cooling to room temperature at a rate of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloidal solution is 1744 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 4.17, wherein the chloride ion concentration of the colloidal solution is 247ppm, and concentrating by using an Asahi chemical conversion hollow fiber membrane to obtain a colloidal solution with the mass content of 15.4%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the solution to 90 ℃ by an electric heating jacket, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium element in the barium hydroxide octahydrate powder to titanium element in the colloidal solution in the step 2) is (Ba/Ti-1.0046: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
Example 5
1) 0.75mol/L TiCl is used45L of the solution is poured into a four-mouth flat-bottom flask, the temperature is raised to 104 ℃ at the temperature rise speed of 2 ℃/minHydrolyzing at 104 ℃ for 60min, cooling to room temperature at the speed of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloidal solution is 2615 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 3.87, wherein the chloride ion concentration of the colloidal solution is 334ppm, and concentrating by using an Asahi chemical compound hollow fiber membrane to obtain a colloidal solution with the mass content of 15.7%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the solution to 90 ℃ by an electric heating jacket, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium element in the barium hydroxide octahydrate powder to titanium element in the colloidal solution in the step 2) is (Ba/Ti-1.0045: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
Example 6
1) 1.0mol/L TiCl is used4Pouring 5L of the solution into a four-mouth flat-bottom flask, heating to 104 ℃ at a heating rate of 2 ℃/min, hydrolyzing at 104 ℃ for 60min, and cooling to room temperature at a rate of 2 ℃/min to obtain TiO2A colloidal solution;
2) pairing the TiO with Mitsubishi chemical PA316 anion resin2Removing impurities from the colloidal solution, the anionic resin and the TiO2The dosage ratio of the colloid solution is 3487 g: 1L, stopping dechlorination when the pH value of the colloidal solution is 4.05, wherein the chloride ion concentration of the colloidal solution is 298ppm, and concentrating by using an Asahi chemical compound hollow fiber membrane to obtain a colloidal solution with the mass content of 15.1%;
3) preparing 2mol/L sodium hydroxide solution (pH value is 14)1.5L, heating the solution to 90 ℃ by an electric heating jacket, adding 350g of barium hydroxide octahydrate powder, stirring and dissolving, and then adding the colloidal solution obtained in the step 2), wherein the molar ratio of barium element in the barium hydroxide octahydrate powder to titanium element in the colloidal solution in the step 2) is (Ba/Ti-1.0035: 1) the reaction was stirred at 105 ℃ for 1.5h, and the synthesis was complete. Standing for precipitation, pouring out supernatant, washing by using an ethanol solution with the mass concentration of 95% until the pH value is 7, finishing washing, filtering into powder cakes, drying at 150 ℃, and crushing and sieving by using a 120-mesh sieve to obtain the superfine barium titanate powder.
TiCl in various concentrations4Solution-derived TiO2The specific surface area and crystal form distribution of the colloidal particles in the colloidal solution are shown in table 3.
TABLE 3 TiO of examples 2-62Specific surface area and crystal form distribution of colloidal particles in colloidal solution
Figure BDA0003303475660000111
As can be seen from Table 3, with TiCl4Increased concentration of, produced TiO2Decrease in BET of colloidal particles in colloidal solution, increase in primary particle diameter, TiO2The mass content of rutile in the crystal form is increased. The rutile has stable performance and TiO2The colloid can ensure the ordered synthesis only by controlling the rutile content, and when the rutile content is less than or equal to 10 wt%, the BaTiO can be synthesized according with the process3And (5) the synthesis requirement. The molar ratio (Ba/Ti) of the barium element in the barium hydroxide octahydrate powder used in the preparation of the ultrafine barium titanate powder of examples 2 to 6 and the titanium element in the colloidal solution of step 2) and the BET, D (BET) and CV values of the prepared ultrafine barium titanate powder are shown in table 4.
TABLE 4 BET, D (BET) and CV values of Ba/Ti and ultrafine barium titanate powders in examples 2 to 6
TiCl4Concentration of Ba/Ti BET[m2/g] D(BET)[nm] CV value
Example 2 0.1mol/L 1.0037 68.1 14.6 20.37％
Example 3 0.25mol/L 1.0032 52.3 19.1 21.45％
Example 4 0.5mol/L 1.0046 33.9 29.5 21.73％
Example 5 0.75mol/L 1.0045 25.1 39.7 20.49％
Example 6 1.0mol/L 1.0035 17.2 57.9 23.14％
As can be seen from Table 4, under the similar Ba/Ti conditions, the following TiCl reaction occurs4The concentration is increased, the BET of the superfine barium titanate powder is in a descending trend, and the CV value is in an ascending trend. When TiCl is generated4At a concentration of 1.0mol/L, the CV value increased to 23.14%, which was still low, and the particle size distribution of the product was still good.
The impurities of the ultrafine barium titanate powders obtained in examples 2 to 6 were detected, and the detection results are shown in table 5:
TABLE 5 results of measuring impurity content of ultrafine barium titanate powders of examples 2 to 6
Figure BDA0003303475660000121
As can be seen from tables 2 and 5, the impurities of the ultra-fine barium titanate powder prepared according to the present invention include Fe2O3、Al2O3、SiO2、SrO、Na2O, MgO, CaO and chloride, the content of each impurity is less than 60 mu g/g, the content of each impurity is lower, and the purity of the superfine barium titanate powder is high.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A preparation method of superfine barium titanate powder comprises the following steps:
A) TiCl with a concentration of 0.1-1.0 mol/L4Hydrolyzing the solution to obtain TiO2A colloidal solution;
B) subjecting the TiO to a reaction2Removing impurities from the colloidal solution and concentrating to obtain a colloidal solution with the mass content of 8-28%;
C) and (2) adding a barium source into an alkaline solution with the temperature of more than or equal to 80 ℃ and the pH value of more than or equal to 12, dissolving, mixing with the colloidal solution obtained in the step B), reacting at the temperature of 100-110 ℃, and drying the obtained product to obtain the superfine barium titanate powder.
2. The method according to claim 1, wherein the hydrolysis in step A) is carried out at a temperature of 90 to 105 ℃ under normal pressure.
3. The method according to claim 1, wherein in step A), the TiO is2The specific surface area of the colloidal particles in the colloidal solution is 50-200 m2(ii)/g, the primary particle size is 8-30 nm;
the TiO is2The crystal form distribution of the colloidal particles in the colloidal solution comprises:
more than or equal to 50 wt% of brookite, less than or equal to 10 wt% of rutile and the balance of anatase.
4. The preparation method according to claim 1, wherein in the step B), the concentration of chloride ions in the colloid solution after impurity removal is 100 to 10000 ppm.
5. The preparation method according to claim 1, wherein in the step B), the pH value of the colloid solution after impurity removal is 1.5-4.5.
6. The method according to claim 1, wherein in the step C), the molar ratio of the barium element in the barium source to the titanium element in the colloidal solution obtained in the step B) is 0.9 to 1.1: 1.
7. the method according to claim 1, wherein in step C), the alkaline solution comprises a sodium hydroxide solution, a lithium hydroxide solution, a potassium hydroxide solution, a quaternary ammonium base solution, or a choline base solution.
8. The process according to claim 1, wherein the reaction time in step C) is 60min or more.
9. The method according to claim 1, wherein the step C) further comprises, after the reaction:
standing for precipitation, pouring out supernatant, washing with alcohol solution or other organic solvent, and filtering;
the drying temperature is 150-300 ℃.
10. The ultrafine barium titanate powder prepared by the method according to any one of claims 1 to 9.
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