CN114477273A - Hydrothermal preparation process of tetragonal phase nano barium titanate powder - Google Patents
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Abstract
The invention discloses a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps: preparing a barium salt solution; weighing a certain amount of titanium tetrachloride, slowly dropwise adding the titanium tetrachloride into deionized water, dropwise adding ammonia water into the solution, uniformly stirring, carrying out solid-liquid separation, and adding an alcohol/water mixed solution into the white precipitate to form an alcohol solution of titanium; transferring the barium sulfate into barium sulfate solution, stirring, and adding ammonia water; then transferring the mixture into a hydrothermal reaction kettle for hydrothermal reaction, cooling the mixture to room temperature, and opening the kettle; washing the hydrothermally synthesized barium titanate suspension with acetic acid and deionized water; the washed product was dried in an oven and ground with a mortar to obtain white barium titanate powder. By adopting the hydrothermal preparation process, the preparation scheme is simple to operate, the cost is low, the hydrothermal preparation process is suitable for macroscopic preparation, the tetragonality is high, the crystallinity is good, the particle morphology is spherical or approximately spherical, the particle size is small, the distribution is uniform, and the average particle size is about 80 nm.
Description
Technical Field
The invention relates to the technical field of barium titanate powder preparation, in particular to a hydrothermal preparation process of tetragonal phase nano barium titanate powder.
Background
Tetragonal barium titanate is widely used in a multilayer ceramic capacitor (MLCC) due to its excellent ferroelectric and dielectric properties. Advances in microelectronic packaging and communication technology currently require MLCCs with thinner dielectric layers, which greatly increases the demand for smaller size, uniform morphology barium titanate powders. The high tetragonality (c/a) of nano barium titanate is crucial for obtaining high capacity MLCCs, but barium titanate nanoparticles have a size effect, and as the particle size decreases, the tetragonality decreases. Therefore, the synthesis of highly tetragonal nano barium titanate powders remains challenging.
The barium titanate has a plurality of synthesis methods, wherein the hydrothermal method can synthesize nanoparticles with small particle size, narrow distribution and good morphology, has the advantages of low synthesis temperature, energy conservation and the like, and is widely researched and used for commercial development. However, most of the synthesized particles by the hydrothermal method are cubic phases or tetragonal phases with less tetragonality, and the cubic phases are converted into the tetragonal phases or the tetragonality of the tetragonal phases is increased by high-temperature heat treatment at 800-1000 ℃, but the high-temperature heat treatment causes the growth or the agglomeration of the particles. Therefore, the hydrothermal synthesis of nano barium titanate with uniform size distribution and high tetragonality is still an extremely important and challenging task.
Disclosure of Invention
The invention aims to provide a hydrothermal preparation process of tetragonal nano barium titanate powder, which has the advantages of simple preparation scheme operation, low cost, suitability for macroscopic preparation, high tetragonality, good crystallinity, spherical or approximately spherical particle appearance, small particle size, uniform distribution and average particle size of about 80 nm.
In order to achieve the purpose, the invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps:
(1) preparing a barium precursor: preparing 2-4mol/L barium salt solution by using a barium source;
(2) preparing a titanium precursor: weighing a certain amount of titanium tetrachloride according to the molar ratio of barium to titanium of more than 1.3, slowly dropwise adding the titanium tetrachloride into deionized water, dropwise adding ammonia water into the solution, uniformly stirring, carrying out solid-liquid separation, and removing ammonium chloride to obtain a white precipitate; adding an alcohol/water mixed solution with the alcohol content of 50% -100% into the white precipitate, and shaking up to form an alcohol solution of titanium;
(3) mixing: transferring the titanium alcohol solution into a barium salt solution, uniformly stirring, adding a certain amount of ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension;
(4) synthesizing: transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the solution filling degree to be 70% -80%, carrying out hydrothermal reaction for 24-48h at the temperature of 220-350 ℃, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: washing the hydrothermally synthesized barium titanate suspension for multiple times by using acetic acid and deionized water;
(6) and (3) drying: the washed product was dried in an oven and then ground with a mortar to obtain white barium titanate powder.
Preferably, the preparation of the barium precursor in the step (1) is specifically to mix a barium source and deionized water, heat and stir for dissolution, and obtain a barium salt solution.
Preferably, in the step (1), the barium source is one of barium hydroxide, barium chloride, barium acetate and barium nitrate.
Preferably, the alcohol in the step (2) is one of ethanol, isopropanol and n-butanol.
Preferably, the molar ratio of the deionized water to the titanium tetrachloride in the step (2) is more than 4, and the molar ratio of the ammonia water to the titanium is more than 4.
Preferably, the amount of the ammonia water used in the step (3) is such that the pH is not less than 13.
Preferably, the mass percentage of the acetic acid in the step (5) is 36%.
Preferably, the washing mode in the step (5) is suction filtration washing or centrifugal washing.
Preferably, in the step (6), the washed product is dried in an oven at 60-80 ℃ for 12-14 h.
Therefore, the hydrothermal preparation process of the tetragonal nano barium titanate powder has the advantages of simple preparation scheme operation, low cost, suitability for macroscopic preparation, high tetragonality, good crystallinity, spherical or approximately spherical particle shape, small particle size, uniform distribution and average particle size of about 80 nm.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a flow diagram of a manufacturing process of the present invention;
FIG. 2 is an X-ray diffraction (XRD) spectrum of barium titanate powders prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2;
FIG. 3 is a partial enlarged view of XRD spectrums of barium titanate powders prepared in examples 1 to 4 of the present invention and comparative examples 1 to 2;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of barium titanate powder prepared in example 1 of the present invention, wherein a is the SEM photograph at a magnification of 100k, and b is the SEM photograph at a magnification of 20.0 k;
FIG. 5 is a Transmission Electron Micrograph (TEM) of barium titanate powder prepared according to example 1 of the present invention, wherein a is a low magnification TEM image, b is a high magnification TEM image, and c is a selected area electron diffraction pattern;
FIG. 6 is an SEM photograph of barium titanate powder prepared in example 2 of the present invention, wherein a is an SEM photograph at a magnification of 100k and b is an SEM photograph at a magnification of 25.0 k;
FIG. 7 is an SEM photograph of barium titanate powder prepared in example 3 of the present invention, wherein a is the SEM photograph at a magnification of 100k, and b is the SEM photograph at a magnification of 20.0 k;
FIG. 8 is an SEM photograph of barium titanate powder prepared in example 4 of the present invention, wherein a is the SEM photograph at a magnification of 100k, and b is the SEM photograph at a magnification of 20.0 k;
FIG. 9 is an SEM photograph of a barium titanate powder prepared in comparative example 1 of the present invention, wherein a is an SEM photograph at a magnification of 100k, and b is an SEM photograph at a magnification of 20.0 k;
FIG. 10 is an SEM photograph of a barium titanate powder prepared in comparative example 2 of the present invention, wherein a is an SEM photograph at a magnification of 100k and b is an SEM photograph at a magnification of 20.0 k.
Detailed Description
The technical solution of the present invention is further illustrated by the accompanying drawings and examples.
The invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps:
(1) preparing a barium precursor: mixing a barium source and deionized water, heating, stirring and dissolving to prepare a barium salt solution with the concentration of 2-4mol/L, wherein the barium source is one of barium hydroxide, barium chloride, barium acetate and barium nitrate.
(2) Preparing a titanium precursor: weighing a certain amount of titanium tetrachloride according to the molar ratio of barium to titanium of more than 1.3, slowly dripping the titanium tetrachloride into deionized water, wherein the deionized water is excessive, so that the titanium tetrachloride can be fully hydrolyzed; dropwise adding ammonia water into the solution, wherein the molar ratio of the ammonia water to titanium is more than 4, uniformly stirring, carrying out solid-liquid separation, removing ammonium chloride, obtaining white precipitate, adding the ammonia water to fully hydrolyze titanium tetrachloride and remove chloride ions, adding an alcohol/water mixed solution with the alcohol content of 50-100% into the white precipitate, shaking uniformly to form an alcohol solution of titanium, wherein the alcohol is one of ethanol, isopropanol and n-butanol, and the alcohol is mainly used for dispersing. The deionized water is excessive, so that the titanium tetrachloride can be fully hydrolyzed, the whole reaction process is carried out rapidly at high temperature and slowly at low temperature, an intermediate product can be separated out, if the water quantity is insufficient, the hydrolysis process can stay at a certain intermediate stage, if the water quantity is excessive, the hydrolysis process of the titanium tetrachloride is completed, and the orthotitanic acid existing in a colloid form is separated out.
(3) Mixing: and transferring the titanium alcohol solution into a barium salt solution, uniformly stirring, adding ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension.
(4) Synthesizing: transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the solution filling degree to be 70% -80%, carrying out hydrothermal reaction for 24-48h at the temperature of 220-350 ℃, cooling to room temperature, and opening the kettle to obtain the barium titanate suspension.
(5) Washing: washing the hydrothermally synthesized barium titanate suspension for multiple times by using 36% by mass of acetic acid and deionized water, washing by adopting a suction filtration washing mode when the equivalent is large, washing by adopting a suction filtration washing mode or a centrifugal mode when the equivalent is small to be neutral, and washing away barium carbonate and other soluble impurity ions in the product.
(6) And (3) drying: and (3) drying the washed product in an oven at the temperature of 60-80 ℃ for 12-14h, and then grinding the product by using a mortar to obtain white barium titanate powder.
Example 1
The invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps: (1) preparing a barium precursor: adding 11.83g of barium hydroxide octahydrate into a beaker filled with 15mL of deionized water, and putting the beaker into a water bath kettle at 90 ℃ for water bath heating and dissolution to prepare a barium hydroxide solution;
(2) preparing a titanium precursor: slowly dripping 4.74g of titanium tetrachloride into 5mL of deionized water to obtain a titanium tetrachloride solution, dripping 20mL of ammonia water into the solution, uniformly stirring, centrifuging, pouring out the upper layer solution, removing ammonium chloride to obtain a white precipitate, adding an ethanol/water mixed solvent (20mL of ethanol and 5mL of deionized water) into a centrifuge tube filled with the white precipitate, wherein the alcohol content in the alcohol-water mixed solution is 80%, and shaking uniformly to form an alcohol solution of titanium;
(3) mixing: transferring the titanium alcohol solution into a barium hydroxide solution, stirring uniformly, adding ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension, wherein the barium-titanium molar ratio is 1.5;
(4) synthesizing: adding the barium titanate precursor suspension into a 50mL hydrothermal reaction kettle, controlling the solution filling degree to be 70%, carrying out hydrothermal reaction at the temperature of 240 ℃ for 30h, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: centrifuging the hydrothermally synthesized barium titanate suspension, removing the upper solution, leaving a white precipitate, and centrifuging and washing with 36% acetic acid and deionized water for multiple times;
(6) and (3) drying: and (3) drying the washed product in an oven at 80 ℃ for 12h, and grinding the dried product by using a mortar to obtain white barium titanate powder.
The barium titanate powder obtained in example 1 has an X-ray diffraction (XRD) pattern as shown in fig. 2 and 3, and has distinct splitting peaks at about 2 θ ═ 45 °, corresponding to (002) and (200) crystal planes of tetragonal barium titanate, respectively, c/a ═ 1.0089; scanning Electron Microscope (SEM) photographs of the barium titanate powder obtained in example 1 at different magnifications are shown in FIG. 4, and the sample particle size is 50-150nm and the average particle size is about 85 nm. A Transmission Electron Microscope (TEM) pattern of the barium titanate powder obtained in example 1 is shown in fig. 5, and a in fig. 5 is a low magnification TEM image, indicating that the barium titanate particles have good dispersibility; in fig. 5, b is a high magnification TEM image, clear lattice fringes can be observed, and the adjacent plane pitches d are 0.280nm, 0.398nm and 0.409nm, which correspond to the plane pitches of tetragonal barium titanate (110), (100) and (001) (JCPDS card:81-2201), respectively; c in fig. 5 is a selected area electron diffraction pattern showing the barium titanate nanoparticles in a single crystalline phase.
Example 2
The invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps:
(1) preparing a barium precursor: adding 10.41g of barium chloride into 15mL of deionized water, heating and dissolving in a 90 ℃ water bath kettle, and preparing a barium chloride solution;
(2) preparing a titanium precursor: slowly dripping 4.74g of titanium tetrachloride into 5mL of deionized water to obtain a titanium tetrachloride solution, dripping 20mL of ammonia water into the solution, uniformly stirring, carrying out suction filtration, removing ammonium chloride to obtain a white precipitate, adding an isopropanol/water mixed solvent (20mL of isopropanol and 5mL of deionized water) into the white precipitate, wherein the alcohol content in the alcohol-water mixed solution is 80%, and uniformly shaking to form a titanium alcohol solution;
(3) mixing: transferring the titanium alcohol solution into a barium chloride solution, uniformly stirring the barium solution and the titanium solution with the barium-titanium molar ratio of 2, adding ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension;
(4) synthesizing: adding the barium titanate precursor suspension into a 50mL hydrothermal reaction kettle, controlling the solution filling degree to be 80%, carrying out hydrothermal reaction at the temperature of 300 ℃ for 24h, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: carrying out suction filtration and solid-liquid separation on the hydrothermally synthesized barium titanate suspension, leaving white precipitate, and washing with 36% acetic acid and deionized water for multiple times;
(6) and (3) drying: and (3) drying the washed product in an oven at 60 ℃ for 14h, and grinding the dried product by using a mortar to obtain white barium titanate powder.
The XRD pattern of the barium titanate powder obtained in example 2 is shown in fig. 3, which shows a distinct splitting peak around 2 θ ═ 45 °, the synthesized barium titanate is tetragonal phase, and c/a ═ 1.0068; SEM photographs of barium titanate powder obtained in example 2 at different magnifications are shown in FIG. 6, and the sample particle size is 50-110nm and the average particle size is about 70 nm.
Example 3
The invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps:
(1) preparing a barium precursor: adding 9.58g of barium acetate into 15mL of deionized water, heating and dissolving in a 40 ℃ water bath kettle, and preparing a barium acetate solution;
(2) preparing a titanium precursor: slowly dripping 4.74g of titanium tetrachloride into 5mL of deionized water to obtain a titanium tetrachloride solution; dropwise adding 20mL of ammonia water into the solution, stirring uniformly, centrifuging, pouring out the upper-layer solution, and removing ammonium chloride to obtain a white precipitate; adding 25mL of n-butanol into a centrifuge tube filled with the white precipitate, wherein the alcohol content in the alcohol-water mixed solution is 100%, and shaking up to form an alcohol solution of titanium;
(3) mixing: transferring the titanium alcohol solution into a barium acetate solution, stirring uniformly, adding ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension, wherein the barium-titanium molar ratio is 1.5;
(4) synthesizing: adding the barium titanate precursor suspension into a 50mL hydrothermal reaction kettle, controlling the solution filling degree to be 70%, carrying out hydrothermal reaction at 220 ℃ for 48h, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: centrifuging the hydrothermally synthesized barium titanate suspension, removing the upper solution, leaving a white precipitate, and centrifuging and washing with 36% acetic acid and deionized water for multiple times;
(6) and (3) drying: and (3) drying the washed product in an oven at 80 ℃ for 12h, and grinding the dried product by using a mortar to obtain white barium titanate powder.
The XRD pattern of the barium titanate powder obtained in example 3 is shown in fig. 3, which shows a distinct splitting peak at about 2 θ ═ 45 °, c/a ═ 1.0090; SEM photographs of barium titanate powder obtained in example 3 at different magnifications are shown in FIG. 7, and the sample particle size is 50-110nm and the average particle size is about 75 nm.
Example 4
The invention provides a hydrothermal preparation process of tetragonal nano barium titanate powder, which comprises the following steps:
(1) preparing a barium precursor: adding 9.80g of barium nitrate into 15mL of deionized water, and heating and dissolving in a water bath at 90 ℃ to prepare a barium nitrate solution;
(2) preparing a titanium precursor: slowly dripping 4.74g of titanium tetrachloride into 5mL of deionized water to obtain a titanium tetrachloride solution; dropwise adding 20mL of ammonia water into the solution, uniformly stirring, performing suction filtration, and removing ammonium chloride to obtain a white precipitate; adding an ethanol/water mixed solvent (12.5mL of ethanol and 12.5mL of deionized water) into the white precipitate, wherein the alcohol content in the alcohol-water mixed solvent is 50%, and shaking up to form a titanium alcohol solution;
(3) mixing: transferring the titanium alcohol solution into a barium nitrate solution, uniformly stirring the solution with the barium-titanium molar ratio of 1.5, adding ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension;
(4) synthesizing: adding the barium titanate precursor suspension into a 50mL hydrothermal reaction kettle, controlling the solution filling degree to be 80%, carrying out hydrothermal reaction for 30h at the temperature of 240 ℃, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: carrying out suction filtration and solid-liquid separation on the hydrothermally synthesized barium titanate suspension, leaving white precipitate, and washing with 36% acetic acid and deionized water for multiple times;
(6) and (3) drying: and (3) drying the washed product in an oven at 60 ℃ for 14h, and grinding the dried product by using a mortar to obtain white barium titanate powder.
The XRD pattern of the barium titanate powder obtained in example 4 is shown in fig. 3, in which the characteristic peak tends to be split at about 2 θ ═ 45 °, the synthesized barium titanate is tetragonal, and c/a ═ 1.0085; SEM photographs of barium titanate powder obtained in example 4 at different magnifications are shown in FIG. 8, and the sample particle size is 60-120nm and the average particle size is about 80 nm.
Comparative example 1
The procedure of example 1 was followed, except that the conditions were not changed, to change the alcohol content in the alcohol-water mixed solution to 0. The XRD pattern of the barium titanate powder obtained in comparative example 1 is shown in fig. 3, which shows a single peak at about 2 θ ═ 45 ° and the synthesized barium titanate is a cubic phase; scanning electron microscope SEM photographs of the barium titanate powder obtained in comparative example 1 at different magnifications are shown in FIG. 9, and the sample particle size is 60nm to 660nm, the average particle size is 130nm, and the particles are unevenly distributed.
Comparative example 2
The preparation of example 2 was followed, with the hydrothermal temperature being changed to 180 ℃ without changing the other conditions.
The XRD pattern of the barium titanate powder obtained in comparative example 2 is shown in fig. 3, which shows a single peak at about 2 θ ═ 45 ° and the synthesized barium titanate is a cubic phase; SEM photographs of barium titanate powder obtained in comparative example 2 at different magnifications are shown in FIG. 10, and the sample particle size is 40-120nm and the average particle size is about 65 nm.
Therefore, the hydrothermal preparation process of the tetragonal nano barium titanate powder has the advantages of simple preparation scheme operation, low cost, suitability for macroscopic preparation, high tetragonality, good crystallinity, spherical or approximately spherical particle shape, small particle size, uniform distribution and average particle size of about 80 nm.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (9)
1. A hydrothermal preparation process of tetragonal nano barium titanate powder is characterized by comprising the following steps:
(1) preparing a barium precursor: preparing 2-4mol/L barium salt solution by using a barium source;
(2) preparing a titanium precursor: weighing a certain amount of titanium tetrachloride according to the molar ratio of barium to titanium of more than 1.3, slowly dropwise adding the titanium tetrachloride into deionized water, dropwise adding ammonia water into the solution, uniformly stirring, carrying out solid-liquid separation, and removing ammonium chloride to obtain a white precipitate; adding an alcohol/water mixed solution with the alcohol content of 50% -100% into the white precipitate, and shaking up to form an alcohol solution of titanium;
(3) mixing: transferring the titanium alcohol solution into a barium salt solution, uniformly stirring, adding a certain amount of ammonia water, and adjusting the pH value of the solution to be more than or equal to 13 to obtain a barium titanate precursor suspension;
(4) synthesizing: transferring the barium titanate precursor suspension into a hydrothermal reaction kettle, controlling the solution filling degree to be 70% -80%, carrying out hydrothermal reaction for 24-48h at the temperature of 220-350 ℃, cooling to room temperature, and opening the kettle to obtain a barium titanate suspension;
(5) washing: washing the hydrothermally synthesized barium titanate suspension for multiple times by using acetic acid and deionized water;
(6) and (3) drying: the washed product was dried in an oven and then ground with a mortar to obtain white barium titanate powder.
2. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: the preparation of the barium precursor in the step (1) is specifically to mix a barium source with deionized water, heat and stir for dissolution, and obtain a barium salt solution.
3. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: the barium source in the step (1) is one of barium hydroxide, barium chloride, barium acetate and barium nitrate.
4. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: and (3) in the step (2), the alcohol is one of ethanol, isopropanol and n-butanol.
5. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: the molar ratio of the deionized water to the titanium tetrachloride in the step (2) is more than 4, and the molar ratio of the ammonia water to the titanium is more than 4.
6. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: the dosage of the ammonia water in the step (3) is that the pH value is more than or equal to 13.
7. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: the mass percentage of the acetic acid in the step (5) is 36%.
8. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: and (5) carrying out suction filtration washing or centrifugal washing.
9. The hydrothermal preparation process of tetragonal nano barium titanate powder as claimed in claim 1, wherein: and (6) drying the washed product in an oven at the temperature of 60-80 ℃ for 12-14 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210144148.7A CN114477273A (en) | 2022-02-17 | 2022-02-17 | Hydrothermal preparation process of tetragonal phase nano barium titanate powder |
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| CN116639972A (en) * | 2023-05-29 | 2023-08-25 | 重庆新申世纪新材料科技有限公司 | Tetragonal phase nano barium titanate powder and preparation method and application thereof |
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| CN117208966B (en) * | 2023-10-13 | 2024-05-17 | 扬州大学 | Preparation method of barium titanate coated cobalt-titanium doped barium ferrite core-shell structure nano-particles |
| CN117509718A (en) * | 2023-12-13 | 2024-02-06 | 湖北展鹏电子材料有限公司 | Spherical-like nano barium titanate and preparation method thereof |
| CN117509718B (en) * | 2023-12-13 | 2024-05-28 | 湖北展鹏电子材料有限公司 | Spherical-like nano barium titanate and preparation method thereof |
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