CN114436646A - Ceramic capacitor material and preparation method thereof - Google Patents
Ceramic capacitor material and preparation method thereof Download PDFInfo
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000003989 dielectric material Substances 0.000 claims abstract description 38
- 239000011734 sodium Substances 0.000 claims abstract description 27
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 5
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 40
- 239000000843 powder Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 21
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 17
- 229920003023 plastic Polymers 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007858 starting material Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 14
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 8
- 229910002115 bismuth titanate Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 239000003990 capacitor Substances 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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Abstract
The invention designs a ceramic capacitor material, which is characterized in that: the ceramic capacitor material is a lead-free sodium bismuth titanate-based temperature-stable ceramic capacitor material, and the nominal chemical formula of the ceramic capacitor material is as follows: (1-x) (0.94 Na)0.5Bi0.5TiO3‑0.06BaTiO3)‑xCa0.7La0.2TiO3. The invention adopts the traditional solid phase method to prepare the dielectric material, can obtain X8R type and X9R type ceramic materials with excellent performance by sintering at medium temperature, has simple process, low cost and no harm to the environment, can be produced in large scale, meets the requirements of portability and integration of electronic components in the current era, and has good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of ceramic capacitor materials, in particular to a ceramic capacitor material and a preparation method thereof.
Background
With the rapid development of modern electronics and microelectronics technologies, electronic component designs tend to be miniaturized, high-frequency, integrated and applied in wide temperature range. Materials with wide temperature stability and low loss have attracted the attention of researchers. Compared with materials such as polymer chemistry, the dielectric ceramic material has the advantages of high dielectric constant, excellent temperature stability, multiple cycle times and the like, and is an excellent candidate material for a temperature-stable capacitor material.
According to EIA standard of International Electronic Industries Association (EIA), the capacitance value of an X8R type capacitor is taken as a reference, and the capacitance change rate (delta C/C25) is less than or equal to +/-15% within the range of-55-150 ℃. In the fields of automobiles, oil drilling, aerospace, war industry and the like, various related electronic components need to bear higher working temperature. For example, high power phased array radars, armored vehicles, missile/rocket-borne circuits, engine systems for aerospace equipment, and electronic equipment for exploring oil and gas reserves, etc., all require the maximum operating temperature of the ceramic capacitor to extend to 150 ℃. It is clear that the upper limit of the use temperature of the capacitor of the X7R type is 125 ℃, which has not been able to meet the practical requirements. According to the electronics industry association class II media standard, the upper temperature limits of X7R and X8R MLCCs are 125 ℃ and 150 ℃, respectively, and thus can fail in extreme environments. In recent years, high temperature dielectrics have attracted the interest of scientists. However, most high temperature media are relaxor ferroelectrics. The dielectric constant of these materials is significantly reduced at low temperatures. In contrast, the X9R material (the temperature change rate is not more than 15% in the temperature range of-55-200 ℃) has great advantages in the low temperature range of-55 ℃.
For example, a patent with publication number CN113061025A discloses a lead-free bismuth titanate sodium-based X9R type ceramic capacitor material and a preparation method thereof, and a patent with publication number CN110423116A discloses an X7R type ceramic capacitor dielectric material and a preparation method thereof, wherein nominal chemical formulas of the ceramic capacitor dielectric material and the preparation method thereof are respectively 0.7(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.3KTaO3And Ba2Sr2SmFe0.5Nb9.5O30The nominal chemical formula is greatly different from the application which introduces Ca in the components0.7La0.2TiO3Using CaCO3、La2O3The raw materials are used for preparing the dielectric material of the ceramic capacitor, so that the cost is further reduced, and the ceramic capacitor can be produced in a large scale.
It follows that ceramic capacitor materials of the X8R and X9R types should be excellent candidates for temperature stable capacitor materials.
Disclosure of Invention
The present invention is directed to a ceramic capacitor material and a method for preparing the same, which solves the above-mentioned problems.
In order to solve the above problems, the present invention provides the following technical solutions: a ceramic capacitor material, characterized by: the ceramic capacitor material is a lead-free sodium bismuth titanate-based temperature-stable ceramic capacitor material, and the nominal chemical formula of the ceramic capacitor material is as follows: (1-x) (0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-xCa0.7La0.2TiO3。
Preferably, X is 0.57, and the ceramic capacitor material is an X8R type ceramic capacitor dielectric material. The preparation method of the X8R type ceramic capacitor dielectric material comprises the following steps:
s1: bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.13395: 0.13395: 1: 0.0342: 0.301: after the materials are mixed according to the molar ratio of 0.043, adding an absolute ethyl alcohol ball milling medium, mixing and ball milling for 12 hours, and drying at 80 ℃ for 12 hours; preparing a dried sample;
s2: heating the dried powder prepared in the step S1 to 800-900 ℃ at the speed of 5 ℃/min for presintering for 6 hours to prepare presintered powder;
s3: grinding the pre-sintered powder prepared in the step S2, adding an absolute ethyl alcohol ball milling medium, ball milling for 12 hours, uniformly mixing, drying at 80 ℃ for 12 hours, and grinding into powder;
s4: adding 5 wt% of polyvinyl alcohol aqueous solution into the powder prepared by the S3 as a binder for granulation, then performing tabletting molding in a mold with the diameter of 14mm to obtain a ceramic plastic blank body, and keeping the temperature of the ceramic plastic blank body at 400-600 ℃ for 1-2 hours to discharge colloid;
s5: and calcining the preform obtained in the step S4 at 1100-1200 ℃ for 3 hours, and cooling to room temperature to obtain the X8R type ceramic capacitor dielectric material.
Preferably, X is 0.67, and the ceramic capacitor material is an X9R type ceramic capacitor dielectric material. The preparation method of the X9R type ceramic capacitor dielectric material comprises the following steps:
s1: bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.15745: 0.15745: 1: 0.0372: 0.266: after the materials are mixed according to the molar ratio of 0.038, adding an absolute ethyl alcohol ball milling medium, mixing and ball milling for 12 hours, and drying at 80 ℃ for 12 hours; preparing a dried sample;
s2: heating the dried powder prepared in the step S1 to 800-900 ℃ at the speed of 5 ℃/min for presintering for 6 hours to prepare presintered powder;
s3: grinding the pre-sintered powder prepared in the step S2, adding an absolute ethyl alcohol ball milling medium, ball milling for 12 hours, uniformly mixing, drying at 80 ℃ for 12 hours, and grinding into powder;
s4: adding 5 wt% of polyvinyl alcohol aqueous solution into the powder prepared by the S3 as a binder for granulation, then performing tabletting molding in a mold with the diameter of 14mm to obtain a ceramic plastic blank body, and keeping the temperature of the ceramic plastic blank body at 400-600 ℃ for 1-2 hours to discharge colloid;
s5: and calcining the preform obtained in the step S4 at 1100-1200 ℃ for 3 hours, and cooling to room temperature to obtain the X9R type ceramic capacitor dielectric material.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the traditional solid phase method to prepare the dielectric material, and the X8R type and X9R type ceramic materials with excellent performance can be obtained by sintering at the middle temperature, the process is simple, the cost is low, and the ceramic material is harmless to the environment, for example, the temperature stability of the prepared X8R type ceramic capacitor dielectric material is good, the dielectric constant is more than 500, the temperature of (delta C/C25) is less than or equal to +/-15% in the temperature range of-55-150 ℃, the EIA X8R standard is met, and the X9R material (the temperature change rate of the material is less than or equal to 15% in the temperature range of-55-200 ℃) has great advantages in the temperature range of-55 ℃. The ceramic capacitor dielectric material and the preparation method thereof provided by the invention can be produced in large scale, meet the requirements of portability and integration of electronic components in the current times, and have good industrialization prospect.
Drawings
FIG. 1 shows 0.57(0.94 Na) prepared by the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3X-ray pattern of X8R type ceramic capacitor material.
FIG. 2 shows 0.57(0.94 Na) prepared by the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3Surface micrographs of X8R type ceramic capacitor material.
FIG. 3 shows 0.57(0.94 Na) prepared by the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3The dielectric constant of the X8R type ceramic capacitor material is a regular graph along with the change of temperature.
FIG. 4 shows 0.57(0.94 Na) prepared by the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3The change rate of the capacitance of the X8R type ceramic capacitor material is a regular graph along with the change of the temperature.
FIG. 5 shows 0.67(0.94 Na) produced by an example of the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3X-ray pattern of X9R type ceramic capacitor material.
FIG. 6 shows 0.67(0.94 Na) prepared by the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3Micrographs of X9R type ceramic capacitor material.
FIG. 7 shows 0.67(0.94 Na) produced by an example of the present invention0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3The dielectric constant of the X9R type ceramic capacitor material is plotted with the temperature.
FIG. 8 shows an embodiment of the present inventionObtained 0.67(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3A temperature characteristic of an X9R type ceramic capacitor material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Other embodiments, which can be derived by those skilled in the art from the embodiments given herein without inventive faculty, are within the scope of the invention.
The lead-free bismuth sodium titanate-based X8R and X9R temperature-stable ceramic capacitor dielectric material is prepared by a traditional solid phase method, and silver firing treatment is carried out on the surface of ceramic, so that an excellent temperature-stable capacitor element can be obtained.
The present invention will be specifically described below with reference to examples. The following examples are illustrative and not intended to be limiting, and are not intended to limit the scope of the invention.
Example 1
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.13395: 0.13395: 1: 0.0342: 0.301: after the materials are mixed according to the molar ratio of 0.043, an agate ball and a nylon can are selected; using absolute ethyl alcohol as a ball milling medium, mixing and ball milling for 12 hours at the rotating speed of 300 r/min, and drying the obtained product in an oven at the temperature of 80 ℃ for 12 hours; raising the temperature to 850 ℃ at the heating rate of 5 ℃/min for pre-sintering for 3 hours; taking out the pre-sintered powder, grinding, ball milling for 12 hours by taking absolute ethyl alcohol as a ball milling medium, uniformly mixing, drying at 80 ℃ for 12 hours, grinding into powder, granulating by taking a polyvinyl alcohol aqueous solution with the mass percentage concentration of 5% as a binder, and pressing under the pressure of 60MPa to obtain the powder with the diameter ofHeating a disc-shaped plastic blank body with the thickness of 1mm and the temperature of 14mm to 600 ℃ at the heating rate of 1 ℃/min, preserving heat for 2 hours, discharging colloid, heating to 1150 ℃ at the heating rate of 5 ℃/min, preserving heat for 3 hours in the air atmosphere of a high-temperature furnace, sintering, and naturally cooling to room temperature along with the furnace to obtain the X8R type ceramic capacitor dielectric material 0.57(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3。
Example 2
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.13395: 0.13395: 1: 0.0342: 0.301: after the materials are mixed according to the molar ratio of 0.043, an agate ball and a nylon can are selected; using absolute ethyl alcohol as a ball milling medium, mixing and ball milling for 12 hours at the rotating speed of 270 r/min, and drying the obtained product in an oven at the temperature of 70 ℃ for 12 hours; raising the temperature to 800 ℃ at the temperature rise rate of 5 ℃/min for pre-sintering for 3 hours; taking out the presintered powder, grinding, ball-milling with anhydrous ethanol as a ball-milling medium for 12 hours, uniformly mixing, drying at 70 ℃ for 12 hours, grinding into powder, granulating with 5% by mass of polyvinyl alcohol aqueous solution as a binder, pressing under 60MPa pressure into a wafer-shaped plastic blank with the diameter of 14mm and the thickness of 1mm, heating to 400 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2 hours, discharging colloid, heating to 1100 ℃ at the heating rate of 5 ℃/min, keeping the temperature in a high-temperature furnace for 3 hours, sintering, and naturally cooling to room temperature along with the furnace to obtain the X8R type ceramic capacitor dielectric material 0.57(0.94 Na) which is a dielectric material for the ceramic capacitor 0.57(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3。
Example 3
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3AsStarting materials, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.13395: 0.13395: 1: 0.0342: 0.301: after the materials are mixed according to the molar ratio of 0.043, an agate ball and a nylon can are selected; using absolute ethyl alcohol as a ball milling medium, mixing and ball milling for 12 hours at the rotating speed of 250 r/min, and drying the obtained product in an oven at the temperature of 90 ℃ for 12 hours; raising the temperature to 900 ℃ at the heating rate of 5 ℃/min for pre-sintering for 3 hours; taking out the presintered powder, grinding, ball-milling with absolute ethyl alcohol as ball-milling medium for 24 hours, uniformly mixing, drying at 90 ℃ for 12 hours, grinding into powder, granulating with 5% polyvinyl alcohol aqueous solution as binder, pressing under 60MPa pressure into a wafer-shaped plastic blank with the diameter of 14mm and the thickness of 1mm, heating to 500 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2 hours, discharging colloid, heating to 1200 ℃ at the heating rate of 5 ℃/min, keeping the temperature in air atmosphere of a high-temperature furnace for 3 hours, sintering, and naturally cooling to room temperature along with the furnace to obtain the X8R type ceramic capacitor dielectric material 0.57(0.94 Na) which is a dielectric material for the ceramic capacitor of the X8 type 0.570.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3。
Analysis of experimental results of examples 1-3:
mixing the obtained 0.57(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3XRD testing of ceramic samples was carried out and it is shown from FIG. 1 that the samples were of a single perovskite structure, illustrating Ca2+And La3+Ions are doped into the NBT-BT ceramic host lattice to form a solid solution.
As shown in fig. 2, fig. 2 presents the surface morphology characteristics of the ceramic, showing a low porosity and a highly dense microstructure, and the relative density of the sample was measured by archimedes method, reaching 96.7%. The dielectric material of the X8R ceramic capacitor prepared by the embodiment is burned with silver electrodes on both sides to prepare a wafer capacitor, then the dielectric constant of the dielectric material is tested and calculated to change with temperature,
as shown in FIG. 3, FIG. 3 shows that the dielectric constant and dielectric loss of the ceramic at different frequencies (100, 1k, 10k, 100kHz) at different temperatures (-55-150 ℃) are both lower than 0.01, and particularly, with the addition of CLT, the dielectric peak at Tm at different frequencies becomes broader and flatter, which further indicates typical relaxation behavior.
As shown in FIG. 4, 0.57(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3The capacitance change rate of the ceramic material is not more than +/-15% in the range of-55-150 ℃, the ceramic material can be used as an X8R type ceramic capacitor dielectric material, and the results show that the capacitance change rate is 0.57(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.43Ca0.7La0.2TiO3Can be used as a ceramic capacitor under the severer working environment.
Example 4
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.15745: 0.15745: 1: 0.0372: 0.266: after the materials are proportioned according to the molar ratio of 0.038, selecting agate balls and nylon tanks; using absolute ethyl alcohol as a ball milling medium, mixing and ball milling for 12 hours at the rotating speed of 300 r/min, and drying the obtained product in an oven at the temperature of 80 ℃ for 12 hours; raising the temperature to 850 ℃ at the heating rate of 5 ℃/min for pre-sintering for 3 hours; taking out the presintered powder, grinding, ball-milling with absolute ethyl alcohol as a ball-milling medium for 12 hours, uniformly mixing, drying at 80 ℃ for 12 hours, grinding into powder, granulating with 5% by mass of polyvinyl alcohol aqueous solution as a binder, pressing under 60MPa pressure into a wafer-shaped plastic blank with the diameter of 14mm and the thickness of 1mm, heating to 600 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2 hours, discharging colloid, heating to 1150 ℃ at the heating rate of 5 ℃/min, keeping the temperature in a high-temperature furnace for 3 hours, sintering, and naturally cooling to room temperature along with the furnace to obtain the X9R type ceramic capacitor dielectric material 0.67(0.94 Na) which is a dielectric material for the ceramic capacitor 0.670.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3。
Example 5
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.15745: 0.15745: 1: 0.0372: 0.266: after the materials are proportioned according to the molar ratio of 0.038, selecting agate balls and nylon tanks; using absolute ethyl alcohol as a ball milling medium, mixing and ball milling for 12 hours at the rotating speed of 270 r/min, and drying the obtained product in an oven at the temperature of 70 ℃ for 12 hours; raising the temperature to 850 ℃ at the heating rate of 3 ℃/min for pre-sintering for 3 hours; taking out the presintered powder, grinding, ball-milling with anhydrous ethanol as a ball-milling medium for 12 hours, uniformly mixing, drying at 70 ℃ for 12 hours, grinding into powder, granulating with 5% polyvinyl alcohol aqueous solution as a binder, pressing under 60MPa pressure into a wafer-shaped plastic blank with the diameter of 14mm and the thickness of 1mm, heating to 600 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2 hours, discharging colloid, heating to 1100 ℃ at the heating rate of 3 ℃/min, keeping the temperature in a high-temperature furnace for 3 hours, sintering, and naturally cooling to room temperature along with the furnace to obtain the X9R type ceramic capacitor dielectric material 0.67(0.94 Na) which is a dielectric material for the ceramic capacitor of the X9 type 0.67(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3。
Example 6
Bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.15745: 0.15745: 1: 0.0372: 0.266: after the materials are proportioned according to the molar ratio of 0.038, selecting agate balls and nylon tanks; to be provided withAbsolute ethyl alcohol is used as a ball milling medium, the ball milling is carried out for 12 hours in a mixing way, the rotating speed is 250 r/min, and the obtained product is dried for 12 hours in a drying oven at the temperature of 90 ℃; raising the temperature to 850 ℃ at the heating rate of 4 ℃/min for pre-sintering for 3 hours; taking out the presintered powder, grinding, ball-milling with anhydrous ethanol as a ball-milling medium for 12 hours, uniformly mixing, drying at 90 ℃ for 12 hours, grinding into powder, granulating with 5% by mass of polyvinyl alcohol aqueous solution as a binder, pressing under 60MPa pressure into a wafer-shaped plastic blank with the diameter of 14mm and the thickness of 1mm, heating to 500 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2 hours, discharging colloid, heating to 1200 ℃ at the heating rate of 4 ℃/min, keeping the temperature in a high-temperature furnace in the air atmosphere for 3 hours, sintering, and naturally cooling to room temperature along with the furnace to obtain the X9R type ceramic capacitor dielectric material 0.67(0.94 Na) which is a dielectric material of a ceramic capacitor 0.670.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3。
Examples 4-6 analysis of experimental results:
0.67(0.94 Na) from example 1 was added0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3XRD testing of ceramic samples was carried out and it is shown from FIG. 1 that the samples were of a single perovskite structure, illustrating Ca2+And La3+Ions are doped into the NBT-BT ceramic host lattice to form a solid solution.
As shown in fig. 2, fig. 2 presents the surface morphology characteristics of the ceramic, showing a low porosity and a highly dense microstructure, and the relative density of the sample was measured by archimedes method, reaching 97.2%. The dielectric material of the X9R ceramic capacitor prepared in this example was fired with silver electrodes on both sides to prepare a wafer capacitor, and then the dielectric material was tested and the change in dielectric constant with temperature was calculated.
As shown in FIG. 3, FIG. 3 shows that the dielectric constant and dielectric loss of the ceramic at different frequencies (100, 500, 1k Hz) at different temperatures (-100 to 250 ℃) are both lower than 0.03, and particularly, with the addition of CLT, the dielectric peak at Tm becomes broader and flatter, which further indicates the typical relaxation behavior.
As shown in FIG. 4, 0.67(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3The capacitance change rate of the ceramic material is not more than +/-15% in the range of-55-200 ℃, and the ceramic material can be used as an X9R type ceramic capacitor dielectric material, and the results show that the capacitance change rate is 0.67(0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-0.33Ca0.7La0.2TiO3Can be used as a ceramic capacitor under the severer working environment.
Although the invention has been described in terms of the above specific embodiments, the inventive idea of the invention is not limited to this invention, and any modification applying the inventive idea is intended to be included in the scope of protection of the patent claims.
Claims (7)
1. A ceramic capacitor material is characterized in that the ceramic capacitor material is a lead-free bismuth sodium titanate-based temperature stable ceramic capacitor material, and the nominal chemical formula of the ceramic capacitor material is as follows: (1-x) (0.94 Na)0.5Bi0.5TiO3-0.06BaTiO3)-xCa0.7La0.2TiO3。
2. The ceramic capacitor material as claimed in claim 1, wherein X is 0.57, and the ceramic capacitor material is a type X8R ceramic capacitor dielectric material.
3. The preparation method of the ceramic capacitor material as claimed in claim 2, wherein the preparation method of the X8R type ceramic capacitor dielectric material comprises the following steps:
s1: bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.13395: 0.13395: 1: 0.0342: 0.301: after the mixture is prepared according to the molar ratio of 0.043,adding a ball milling medium, mixing and ball milling for 12 hours, and drying at 80 ℃ for 12 hours; preparing a dried sample;
s2: heating the dried powder prepared in the step S1 to 800-900 ℃ at the speed of 5 ℃/min for presintering for 6 hours to prepare presintered powder;
s3: grinding the pre-sintered powder prepared in the step S2, adding a ball milling medium, ball milling for 12 hours, uniformly mixing, drying at 80 ℃ for 12 hours, and grinding into powder;
s4: adding 2-8 wt% of polyvinyl alcohol aqueous solution into the powder prepared in the S3 as a binder for granulation, then performing tabletting molding in a mold with the diameter of 14mm to obtain a ceramic plastic blank body, and keeping the temperature of the ceramic plastic blank body at 400-600 ℃ for 1-2 hours to discharge colloid;
s5: and calcining the preform obtained in the step S4 at 1100-1200 ℃ for 3 hours, and cooling to room temperature to obtain the X8R type ceramic capacitor dielectric material.
4. The ceramic capacitor material as claimed in claim 1, wherein X is 0.67, and the ceramic capacitor material is a type X9R ceramic capacitor dielectric material.
5. The preparation method of the ceramic capacitor material as claimed in claim 4, wherein the preparation method of the X9R type ceramic capacitor dielectric material comprises the following steps:
s1: bi with the purity of more than 99 percent2O3、Na2CO3、TiO2、BaCO3、CaCO3、La2O3As starting material, according to Bi2O3：Na2CO3：TiO2：BaCO3：CaCO3：La2O30.15745: 0.15745: 1: 0.0372: 0.266: after the materials are mixed according to the molar ratio of 0.038, adding a ball milling medium, mixing and ball milling for 12 hours, and drying at 80 ℃ for 12 hours; preparing a dried sample;
s2: heating the dried powder prepared in the step S1 to 800-900 ℃ at the speed of 5 ℃/min for presintering for 6 hours to prepare presintered powder;
s3: grinding the pre-sintered powder prepared in the step S2, adding a ball milling medium, ball milling for 12 hours, uniformly mixing, drying at 80 ℃ for 12 hours, and grinding into powder;
s4: adding 2-8 wt% of polyvinyl alcohol aqueous solution into the powder prepared in the S3 as a binder for granulation, then performing tabletting molding in a mold with the diameter of 14mm to obtain a ceramic plastic blank body, and keeping the temperature of the ceramic plastic blank body at 400-600 ℃ for 1-2 hours to discharge colloid;
s5: and calcining the preform obtained in the step S4 at 1100-1200 ℃ for 3 hours, and cooling to room temperature to obtain the X9R type ceramic capacitor dielectric material.
6. The method for producing a ceramic capacitor material as claimed in claim 3 or 5, wherein: in steps S1 and S3, the ball milling medium is anhydrous ethanol.
7. The method for producing a ceramic capacitor material as claimed in claim 3 or 5, wherein: in step S4, the concentration of the polyvinyl alcohol aqueous solution is 5 wt%.
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| CN113061025A (en) * | 2021-05-21 | 2021-07-02 | 安徽大学 | Lead-free bismuth sodium titanate-based X9R type ceramic capacitor material and preparation method thereof |
| CN113264762A (en) * | 2021-05-21 | 2021-08-17 | 安徽大学 | X8R type ceramic capacitor material and preparation method thereof |
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| CN113061025A (en) * | 2021-05-21 | 2021-07-02 | 安徽大学 | Lead-free bismuth sodium titanate-based X9R type ceramic capacitor material and preparation method thereof |
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