CN114573336A - Ceramic dielectric material, ceramic capacitor and preparation method thereof - Google Patents
Ceramic dielectric material, ceramic capacitor and preparation method thereof Download PDFInfo
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- CN114573336A CN114573336A CN202210135996.1A CN202210135996A CN114573336A CN 114573336 A CN114573336 A CN 114573336A CN 202210135996 A CN202210135996 A CN 202210135996A CN 114573336 A CN114573336 A CN 114573336A
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- ceramic
- dielectric material
- ceramic capacitor
- ceramic dielectric
- barium titanate
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- 239000000919 ceramic Substances 0.000 title claims abstract description 82
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 74
- 239000003989 dielectric material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 26
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 24
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 13
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 241001089723 Metaphycus omega Species 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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- C04B2235/663—Oxidative annealing
Abstract
The invention discloses a ceramic dielectric material, a ceramic capacitor and a preparation method thereof, belonging to the technical field of materials; the ceramic dielectric material comprises the following components in percentage by mol mass: 94.0-98.0% of barium titanate, 1.2-2.5% of glass phase, 0.5-1.0% of anti-reducing agent, 0.5-1.5% of alkali metal compound and 0.5-3.0% of rare earth element oxide; the oxide of rare earth element comprises Dy2O3、Y2O3And Tm2O3The obtained ceramic dielectric material has stable capacitance characteristic, high dielectric constant and high temperature stabilityQualitative and easier lamination; the ceramic capacitor is formed by sintering the ceramic dielectric material serving as the raw material, the obtained ceramic capacitor meets the X5R standard, and the influence of severe capacitance change caused by temperature can be well stabilized in a normal temperature section; meanwhile, the ceramic dielectric material and the ceramic capacitor provided by the invention have the advantages of simple preparation method, simple and convenient operation, no toxic or harmful substances, high density, small crystal grains and few defects, and are suitable for practical production and application.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a ceramic dielectric material, a ceramic capacitor and a preparation method thereof.
Background
Barium titanate (BaTiO)3) The ceramic is a base material of a II-type capacitor in a chip multilayer ceramic capacitor (MLCC) and has higher dielectric constant. In recent years, the miniaturization of mobile electronic devices has led to the development of MLCCs that are smaller and have larger capacities. Higher demands are made on various properties of barium titanate-based ceramic materials. The following formula is a calculation method of MLCC capacitance, wherein C is capacitance, N is the number of dielectric layers, epsilon0Is a vacuum dielectric constant of ∈rIs the dielectric constant of the material, S is the electrode area, and d is the dielectric layer thickness.
Since the specific MLCC has a fixed size and the capacitance is generally not increased by changing the electrode area, obtaining a large-capacity barium titanate-based MLCC is generally achieved from the following aspects: 1. increasing the dielectric constant of barium titanate-based ceramic materials, typically by changing the doping system or increasing the grain size; 2. increasing the number of stacked layers, i.e., the number N of dielectric layers, is equivalent to decreasing the thickness d of the dielectric layers.
Due to the limitation of the size of the MLCC with a specific specification, and the requirement of the thickness of at least five grains for each dielectric layer to ensure the stability of a base material, the increase of the grain size and the reduction of the thickness of the dielectric layer are in a contrary way in the manufacturing process of the ultrathin MLCC device. Further, in the case where the thickness of the dielectric layer is constant, increasing the crystal grain size may reduce the number of grain boundaries, possibly resulting in a decrease in reliability, but it is difficult to form a stable core-shell structure by reducing the crystal grain size, and it is difficult to achieve the X5R specification.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a ceramic dielectric material, a ceramic capacitor and a preparation method thereof, wherein the ceramic dielectric material has stable capacitance characteristics and high reliability and is easier to laminate.
In order to achieve the purpose, the invention adopts the technical scheme that: a ceramic dielectric material comprising the following components in mole percent: 94.0-98.0% of barium titanate, 1.2-2.5% of glass phase, 0.5-1.0% of anti-reducing agent, 0.5-1.5% of alkali metal compound and 0.5-3.0% of rare earth element oxide; the oxide of rare earth element comprises Dy2O3、Y2O3And Tm2O3。
According to the ceramic dielectric material provided by the invention, the oxide of the rare earth element is selected as a doping agent, barium titanate is modified, and a glass phase, an anti-reducing agent and an alkali metal compound are added to refine particles, so that the ceramic dielectric material which has stable capacitance characteristics and high reliability and is easier to laminate is prepared; the invention selects the oxide form of Y, Dy and Tm as the doping element of the main material barium titanate, which can reduce the Curie temperature and increase the dielectric constant, and the added oxide of rare earth elements can influence the formation of barium titanate crystal grains to form a core-shell structure, thereby reducing the peak value at the Curie temperature and also obviously reducing the temperature change rate.
As a preferred embodiment of the ceramic dielectric material of the present invention, Dy is defined as Dy based on the total mole of the ceramic dielectric material2O30.3-1.2% of the total weight of the composition, and Y2O30.2-1.0%, the Tm is2O30.2-0.7 percent.
In the periodic table of chemical elements, the ionic radii of Dy, Y and Tm elements are arranged from large to small, wherein Dy3+The ionic radius is 0.0908nm, wherein Y3+Has an ionic radius of 0.0893nm, Tm3+Has an ionic radius of 0.087nm, Ba2+And Ti4+The ionic radii of the rare earth elements are 0.0135nm and 0.068nm respectively, and the substitution mechanisms of the rare earth elements in the barium titanate crystal are basically the same; the larger ionic radius after the Ti site is replaced can increase the lattice parameter of barium titanate, so that larger tetragonality is obtained, the dielectric constant is favorably improved, but the larger tetragonality can increase the capacitance loss rate of the MLCC under the direct current bias; when Dy3+When substituting the Ba site, Ti4+Conversion to Ti3+And form conduction electrons to keep the charge neutral, such additional electrons contributing to an increase in the dielectric constant; y is3+And Tm3+The concentration of the shell part can be increased by the 'core-shell' structure formed by ions, so that the stability of the product at high temperature is improved; and, Tm with a smaller radius3+Ions can be dissolved in two sites of Ba and Ti sites, so that the tetragonality can be controlled and cannot be greatly increased, and the loss rate under direct current bias is controlled; in addition, the solid solubility of the rare earth ions with small radius is reduced, the thickness of a shell layer is conveniently controlled in a sintering system to obtain a larger core volume ratio, so that the dielectric temperature curve in a high-temperature section is raised, and the dielectric constant is further improved after peak pressing; by integrating the action mechanisms of the three rare earth elements Dy, Y and Tm, the oxides of the three rare earth elements are selected within the range, so that the excessive increase of the tetragon can be avoided while the tetragon is increased, and the synthesis of the ceramic dielectric material with high dielectric constant and high temperature stability is ensured.
As a preferred embodiment of the ceramic dielectric material of the present invention, the glass phase comprises BaSiO3。
The invention selects BaSiO3As a sintering aid, the Ba source is supplemented, and simultaneously, a liquid phase is generated in the preparation process, so that each particle can be uniformly coated, the sintering temperature is reduced and widened, excessive particle growth can be prevented, and BaTiO is promoted3The density of the product is improved by the mass transfer process; in addition, the liquid phase on the surface of the inner electrode can prevent the metal element from diffusing to the dielectric layer, so that the reliability of subsequent products is enhanced, and the superiority of the invention in the application field of MLCC is increased.
As a preferred embodiment of the ceramic dielectric material of the present invention, the anti-reducing agent includes V2O5。
Ti during reduction sintering when ceramic dielectric materials are used for subsequent ceramic capacitor preparation4+The ions are reduced to Ti during sintering in a reducing atmosphere3+Oxygen vacancies are generated to thereby reduce the remanent polarization, V2O5The addition of (3) allows valence-changeable V to substitute for the Ti site in Barium Titanate (BT), thereby suppressing the generation of oxygen vacancies and improving the remanent polarization.
As a preferred embodiment of the ceramic dielectric material of the present invention, the alkali metal compound includes MgO.
The addition of MgO can refine crystal grains and prevent the crystal grains from excessively growing in the sintering process when the ceramic dielectric material is subsequently utilized to prepare the ceramic capacitor.
As a preferred embodiment of the ceramic dielectric material of the present invention, the particle size of the barium titanate is 180-200 nm.
The barium titanate is used as a main material of the ceramic dielectric material, the process complexity can be reduced, the cost is saved, and meanwhile, in order to obtain the ultrathin-layer ceramic capacitor, the particle size of the barium titanate is preferably 180-200nm in the raw material stage, so that the particle size of the obtained ceramic dielectric material is controlled to be 190-220nm, the particle size of ceramic grains sintered in the subsequent preparation of the ceramic capacitor can be ensured to be 200-250nm, and the thickness of a dielectric layer of the prepared ceramic capacitor is further enabled to be below 1 mu m.
As a preferred embodiment of the ceramic dielectric material, the ceramic dielectric material comprises the following components in percentage by mol: 94.0-98.0% of barium titanate, 1.2-2.0% of glass phase, 0.8-1.0% of anti-reducing agent, 0.5-1.0% of alkali metal compound and Dy2O30.4-0.8％、Y2O30.4-0.8％、Tm2O30.3-0.6％。
When the mole percentage content of the components is in the range, the prepared ceramic dielectric material is ultra-pure and ultrafine powder with good dispersibility, and has more proper grain size and core-shell ratio, so that the ceramic capacitor prepared by further taking the ceramic dielectric material as a raw material has high temperature stability and high dielectric constant, and can reach the X5R standard, namely the capacitance change rate is between + 15% and-15% at the temperature of (-55) -85 ℃.
As a preferred embodiment of the ceramic dielectric material, the ceramic dielectric material comprises the following components in percentage by mol: 95% of barium titanate, 1.5% of glass phase, 1.0% of anti-reducing agent, 0.8% of alkali metal compound and Dy2O30.6％、Y2O30.6％、Tm2O30.5％。
When the mole percentage of the components is the above value, the ceramic capacitor prepared by using the prepared ceramic dielectric material as a raw material has the optimal capacitance characteristics and the lowest dielectric loss.
In addition, the invention also provides a preparation method of the ceramic dielectric material, which comprises the following steps: and mixing, wet grinding and drying the barium titanate and the components to obtain the ceramic dielectric material.
As a preferred embodiment of the preparation method, the wet grinding takes zirconia balls as a ball milling medium, and the time for wet grinding is 18-22 h.
In addition, the invention also provides a ceramic capacitor, which is formed by sintering the ceramic dielectric material.
As a preferred embodiment of the ceramic capacitor of the present invention, the ceramic crystal grain size in the ceramic capacitor is 200-250 nm.
As a preferred embodiment of the ceramic capacitor of the present invention, the ceramic capacitor has a multi-dielectric-layer structure, the number of the dielectric layers is 80 to 100, and the thickness of the dielectric layers is 0.7 to 1 μm.
As a preferred embodiment of the ceramic capacitor of the present invention, the ceramic capacitor has a dielectric constant of 3200-3500 at 25 ℃, a resistivity of 39-41 M.OMEGA.m, a capacitance of 0.093-0.097. mu.F, and a capacitance change rate of + 15% to-15% at a temperature of-55 ℃ to 85 ℃.
In addition, the invention also provides a preparation method of the ceramic capacitor, which comprises the following steps: preparing a ceramic dielectric material into slurry, then casting the slurry into a film with the thickness of 0.85-0.95 mu m, and then forming a green body through electrode printing, laminating, pressing and cutting; then sintering the green body in a reducing atmosphere at 1150-1250 ℃ for 2-4h, then cooling to 950-1100 ℃ for continuous oxidation for 2-4h, and cooling to room temperature after the oxidation is finished; and obtaining a ceramic body, sintering the two ends of the ceramic body to form copper electrodes, and sequentially plating a nickel layer and a tin layer to obtain the ceramic capacitor.
When the ceramic capacitor is prepared by the method, the grain size can be well controlled, and the prepared ceramic capacitor has good compactness.
As a preferred embodiment of the preparation method of the present invention, the reducing atmosphere comprises the following components in volume percent: 1% of H2And 99% N2。
As a preferred embodiment of the preparation method of the present invention, the sintering temperature for forming the copper electrode by sintering is 800-950 ℃.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the method comprises the following steps: the ceramic dielectric material provided by the invention takes barium titanate as a main material, is doped in the form of oxides of Dy, Y and Tm, and is added with a glass phase, an antioxidant and an alkali metal compound, so that the prepared ceramic dielectric material has stable capacitance characteristic, high dielectric constant, high temperature stability and high reliability and is easier to laminate;
secondly, the method comprises the following steps: the particle size of the ceramic dielectric material provided by the invention is 190-220nm, and the prepared ceramic capacitor can be ensured to have small crystal grains when the ceramic dielectric material is used as a raw material for preparing the ceramic capacitor, so that the thickness of a dielectric layer after lamination is formed can be below 1 mu m, and the dielectric layer can be conveniently superposed to form a multi-layer ceramic capacitor;
thirdly, the method comprises the following steps: the ceramic capacitor provided by the invention can well stabilize the influence of drastic change of capacitance value caused by temperature in a normal temperature section, namely has high temperature stability; meanwhile, when the temperature of the ceramic capacitor is (-55) -85 ℃, the capacitance change rate is between + 15% and-15%, namely the ceramic capacitor can reach the X5R standard;
fourthly: the ceramic dielectric material and the ceramic capacitor provided by the invention have the advantages of simple preparation method, simple and convenient operation, no toxic or harmful substances, high density, small crystal grains and few defects, and are suitable for practical production and application.
Drawings
FIG. 1 is a scanning electron microscope photograph of an MLCC sample according to example 1 of the present invention;
FIG. 2 is a transmission electron microscope photograph of an MLCC sample according to example 1 of the present invention;
FIG. 3 is a graph of the grain size distribution of an MLCC sample according to example 1 of the present invention;
FIG. 4 is a graph of capacitance versus temperature for MLCC samples in accordance with example 1 of the present invention;
FIG. 5 is a graph of the grain size distribution of a comparative MLCC sample of the invention 1;
FIG. 6 is a graph of capacitance versus temperature for comparative example 1 MLCC samples in accordance with the invention;
FIG. 7 is a transmission electron microscope photograph of a MLCC sample according to comparative example 2 of the invention;
FIG. 8 is a Weibull plot of breakdown strength for MLCC samples according to the invention of example 1 and comparative example 2;
FIG. 9 is a core-shell structure and a second phase diagram of a comparative MLCC sample of the invention 3;
FIG. 10 is a graph showing the oxygen vacancy migration activation energies of MLCC samples according to the invention of example 1 and comparative example 3;
FIG. 11 is a graph of resistance IR aging for MLCC samples according to the invention of example 1 and comparative example 3;
FIG. 12 is a Weibull plot of the puncture strength of MLCC samples according to example 1 of the present invention and commercially available products.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The ceramic capacitor of the embodiment, wherein the ceramic dielectric material comprises the following components in percentage by mole: BaTiO 23 95％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 0.6％、Tm2O30.5％；BaTiO3The particle size of (A) is 180 nm;
the preparation method comprises the following steps:
(1) preparation of ceramic dielectric material: weighing the components according to the mole percentage, mixing, placing zirconia balls as ball milling media in a ball mill, adding an ethanol solvent, performing wet ball milling for 20 hours, and drying after ball milling to obtain the ceramic dielectric material;
(2) preparation of a green body: preparing the ceramic dielectric material in the step (1) into slurry, casting the slurry into a 0.9 mu m membrane, and then forming a green body by electrode printing, laminating, pressing and cutting; wherein, the electrode printing adopts nickel slurry as an inner electrode, and the number of lamination layers is 80-100;
(3) preparing a porcelain body: subjecting the green compact of step (2) to a reducing atmosphere (1% H)2+99％N2) Sintering at 1200 deg.C for 2h, cooling to 950 deg.C for re-oxidation treatment for 2h, and cooling to 25 deg.C for sintering to obtain ceramic body;
(4) preparing a ceramic capacitor: and (4) dipping copper slurry on two ends of the ceramic body obtained in the step (3) in a copper dipping mode, sintering at 900 ℃ to form a copper electrode firmly combined with the ceramic body, and electroplating a nickel layer and a tin layer on the surface of the copper electrode in sequence to obtain the ceramic capacitor.
Example 2
The ceramic capacitor of the embodiment, wherein the ceramic dielectric material comprises the following components in percentage by mole: BaTiO 23 95％、BaSiO3 2.3％、MgO 0.5％、V2O5 1.5％、Dy2O30.3％、Y2O3 0.2％、Tm2O30.2％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Example 3
The ceramic capacitor of the embodiment, wherein the ceramic dielectric material comprises the following components in percentage by mole: BaTiO 23 96％、BaSiO3 1.8％、MgO 0.5％、V2O5 0.5％、Dy2O30.4％、Y2O3 0.2％、Tm2O30.6％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Example 4
The ceramic capacitor of the embodiment, wherein the ceramic dielectric material comprises the following components in percentage by mole: BaTiO 23 95％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 0.6％、Tm2O30.5％；BaTiO3The particle size of (A) is 200 nm; the preparation method is the same as that of example 1.
Comparative example 1
The ceramic capacitor of the comparative example, wherein the ceramic dielectric material comprises the following components in mole percent: BaTiO 23 95％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 0.6％、Tm2O30.5％；BaTiO3The particle size of (D) is 150 nm; the preparation method is the same as that of example 1.
Comparative example 2
A ceramic capacitor of this comparative example, whereinThe ceramic dielectric material comprises the following raw materials in percentage by mole: BaTiO 23 93.5％、BaCO3 1.5％、SiO2 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O30.6％、Tm2O30.5％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Comparative example 3
The ceramic capacitor of the comparative example, wherein the ceramic dielectric material comprises the following components in mole percent: BaTiO 23 94.5％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 1.1％、Tm2O30.5％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Comparative example 4
The ceramic capacitor of the comparative example, wherein the ceramic dielectric material comprises the following components in mole percent: BaTiO 23 95.5％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 0.6％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Comparative example 5
The ceramic capacitor of the comparative example, wherein the ceramic dielectric material comprises the following components in mole percent: BaTiO 23 95.6％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Y2O3 0.6％、Tm2O30.5％；BaTiO3The particle size of (A) is 180 nm; the preparation method is the same as that of example 1.
Comparative example 6
The ceramic capacitor of the comparative example, wherein the ceramic dielectric material comprises the following components in mole percent: BaTiO 23 95％、BaSiO3 1.5％、MgO 0.8％、V2O5 1％、Dy2O30.6％、Y2O3 0.6％、Yb2O30.5％；BaTiO3The particle size of (D) is 150 nm; the preparation method is the same as that of example 1.
Comparative example 7
A ceramic capacitor of this comparative example was different from example 1 only in that the sintering temperature in step (3) was 1280 ℃.
Comparative example 8
A ceramic capacitor of this comparative example is different from that of example 1 only in that the sintering time in step (3) is 1 hour.
Effects of the invention
The ceramic capacitors prepared in examples 1 to 4 of the present invention and comparative examples 1 to 8 were subjected to a performance test, and the data obtained by the test are shown in table 1, wherein the model of a commercially available sample was 01005X5R 104-6.3V; meanwhile, the ceramic capacitor prepared in the embodiment 1 and the product prepared in the comparative example are subjected to a breakdown strength Weibull test, an oxygen vacancy migration activation energy test and a resistivity loss rate test, wherein the breakdown strength Weibull test is performed under the condition that a direct current voltage with the boosting rate of 2V/s is applied to two ends of a device, when a passing current value reaches 2mA, a sample is regarded as being broken down, the breakdown voltage at the moment is recorded, and after the process is repeated for multiple times, the breakdown electric field intensity is calculated according to the Weibull breakdown distribution; the conditions of the oxygen vacancy migration activation energy test are that the polarization field strength Ep is 2KV/cm, the polarization temperature is 200 ℃, the polarization time is 10min, and the temperature rise rate is 4 ℃/min; the conditions of the resistivity loss rate test are that the test temperature is 200 ℃, and the direct-current voltage is 9.45V;
table 1: tables for testing the performance of the ceramic capacitors prepared in examples 1 to 4 and comparative examples 1 to 8
As can be seen from Table 1, when the technical scheme of the invention is adopted, the dielectric constant of the prepared ceramic capacitor is 3200-3500 at 25 ℃, the resistivity is 39-41M omega-M, and the capacitance is 0.093-0.097 muF, and the ceramic capacitor provided by the invention has the capacitance change rate of between + 15% and-15% at the temperature of-55 ℃ to 85 ℃, namely, the ceramic capacitor can reach the X5R standard;
the ceramic capacitor prepared in the embodiment 1 is characterized by a scanning electron microscope and a transmission electron microscope, and as can be seen from the characterization results of fig. 1 and fig. 2, the sample prepared in the embodiment 1 of the invention has good density and no obvious holes; then, the size distribution of the ceramic crystal grains is counted according to fig. 2 and is shown in fig. 3, and it can be seen from fig. 3 that the average crystal grain size of the product prepared in the embodiment 1 of the present invention is 210nm according to the rule of the size distribution of the product; next, the relationship between the capacitance and the temperature of the ceramic capacitor prepared in example 1 is tested, and as can be seen from fig. 4, the ceramic capacitor prepared in example 1 of the present invention has a very high capacitance, and can well stabilize the influence of drastic change in capacitance value caused by temperature in a normal temperature range.
As can be seen from the data of example 1 and comparative example 1, when BaTiO is used3When the particle size of (A) is not within 180-200nm but 150nm, the product prepared in the comparative example 1 is subjected to size distribution mapping, as can be seen from FIG. 5, the particle size of the ceramic crystal grain is 188nm, namely the particle size is smaller, and the capacitance of the product in the comparative example 1 is also obviously reduced, and the relationship between the capacitance and the temperature of the product prepared in the comparative example 1 is further tested, as can be seen from FIG. 6, the temperature capacity change rate of the product in the high temperature section of the comparative example 1 exceeds the design range, because the smaller crystal grain size causes the area of the core part of the crystal grain formed by doping to be reduced relative to the shell part, thereby causing the temperature capacity change rate of the high temperature section to be unstable;
when the ceramic capacitor prepared in comparative example 2 was observed by a scanning electron microscope, it was found from FIG. 7 that a large number of pores were present in the internal structure of the product, since BaSiO was not added in comparative example 23Added with BaCO3And SiO2Due to the addition of BaCO3And SiO2In particular BaCO3Can generate large scale in the preparation processAmount of CO2Gas is generated, so that pores are reflected on a scanning electron microscope picture, and the generated pores influence the density of the material, so that the density is reduced, and the breakdown strength is poor; the ceramic capacitors prepared in example 1 and comparative example 2 were subjected to a breakdown test, and the results are shown in fig. 8, and it is apparent from fig. 8 that the breakdown strength of example 1 was 110Kv/mm and the slope of the fitted straight line was 49.39, indicating that the ceramic capacitor of example 1 was excellent in stability and uniformity, while the ceramic capacitor of comparative example 2 had a breakdown strength of only 98Kv/mm and the slope of the fitted straight line was 16.92, indicating that the ceramic capacitor of comparative example 2 was poor in stability and uniformity;
the ceramic capacitor prepared in comparative example 3 was observed by a scanning electron microscope, and as can be seen from FIG. 9, due to Y added in comparative example 32O3Excessive amount of the second phase is easily generated, resulting in low shell concentration, reduced Schottky barrier of the shell, reduced oxygen vacancy migration activation energy, and consequently poor aging resistance, the ceramic capacitors prepared in example 1 and comparative example 3 were subjected to an oxygen vacancy migration activation energy test, the results of which are shown in FIG. 10, wherein the curve obtained in example 1 is Ea＝1.103±0.009eV，R2Comparative example 3 gave a curve E of 0.996a＝1.218±0.019eV，R20.995; that is, the product of comparative example 3 had an oxygen vacancy migration activation energy of 1.013eV, which is significantly lower than 1.218eV of example 1; then, the ceramic capacitors prepared in example 1 and comparative example 3 were subjected to a resistance loss rate test, and as can be seen from fig. 11, the resistivity loss rate of the product of comparative example 3 was 87.3%, which is much higher than the resistivity loss rate of the product of example 1 by 63.4%;
as can be seen from example 1 and comparative example 4, when Tm is not added to the ceramic dielectric material2O3In the meantime, the ceramic crystal grain size and the capacitance value of the sample of comparative example 4 were both in accordance with the standards, but since the diffusion rate of Dy is much greater than Tm, the Dy is continuously diffused due to lack of Tm restriction, and finally the core area proportion is decreased and the shell area proportion is increased, resulting in a sharp stability of the temperature coefficient of capacitance (Tcc) at the high temperature endDescending;
as can be seen from example 1 and comparative example 5, when Dy is not added to the ceramic dielectric material2O3In the meantime, the ceramic grain size and the capacitance value of the sample of comparative example 5 both meet the standards, but since the diffusion rate of Tm is much smaller than Dy, the shell area ratio is greatly reduced under the same process, resulting in a sharp decrease in the stability of the temperature coefficient of capacitance (Tcc) at the low temperature end;
as can be seen from example 1 and comparative example 6, Ho was used in the ceramic dielectric material2O3Alternative Tm2O3While the ceramic grain size and capacitance values of the sample of comparative example 6 both met the standards, Dy and Ho were located close together in the periodic table of the elements, and the ionic radii of these two elements were almost the same, with Ho having an ionic radius of 0.0894nm and Dy having an ionic radius of 0.0908nm, and the diffusion rates were consistent and relatively fast with respect to Tm during sintering, resulting in an increase in shell area fraction, a decrease in core area fraction, and finally a sharp decrease in Tcc at the high temperature end;
as can be seen from example 1 and comparative example 7, when the sintering temperature is increased, although the Tcc finally tested meets the design standard, the tested capacitance value exceeds the design limit of ± 15%, and the sintering temperature is too high, which causes the crystal grains to grow excessively, and destroys the originally formed core-shell structure, so that the crystal grains in a solid solution state occupy a dominant position, and the dielectric constant is lowered, so that the final capacitance value deviates from the design standard;
as can be seen from example 1 and comparative example 8, when the sintering time is reduced, the ceramic grain size and capacitance in comparative example 8 both meet the standard, but the Tcc at the low temperature end exceeds the design standard, because the grain formation and the diffusion of the doping element require a certain sintering time, and after the sintering time is reduced, the doping element is not fully diffused, the area occupation ratio of the shell part is reduced, and the Tcc at the low temperature end is reduced;
meanwhile, the ceramic capacitor and the commercial product in example 1 of the present invention were subjected to a weibull distribution test of breakdown strength, and the test results are shown in fig. 12, from fig. 12, it can be seen that the average breakdown strength of the commercial product is 97V/μm, and the slope of the fitted straight line is smaller than 20.56, which indicates that the stability and consistency of the commercial product are far inferior to those of the ceramic capacitor prepared by the technical scheme of the present invention.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A ceramic dielectric material is characterized by comprising the following components in percentage by mol: 94.0-98.0% of barium titanate, 1.2-2.5% of glass phase, 0.5-1.0% of anti-reducing agent, 0.5-1.5% of alkali metal compound and 0.5-3.0% of rare earth element oxide;
the oxide of rare earth element comprises Dy2O3、Y2O3And Tm2O3。
2. The ceramic dielectric material of claim 1, wherein Dy is present in an amount corresponding to the total mole of the ceramic dielectric material2O30.3-1.2% of the total weight of the composition, and Y2O30.2-1.0%, the Tm is2O30.2-0.7 percent.
3. The ceramic dielectric material of claim 1, wherein the glass phase comprises BaSiO3Said anti-reducing agent comprises V2O5The alkali metal compound includes MgO.
4. The ceramic dielectric material as claimed in claim 1, wherein the particle size of the barium titanate is 180-200 nm.
5. The ceramic dielectric material of claim 1, wherein the ceramic dielectric isThe material comprises the following components in percentage by mol mass: 94.0-98.0% of barium titanate, 1.2-2.0% of glass phase, 0.8-1.0% of anti-reducing agent, 0.5-1.0% of alkali metal compound and Dy2O30.4-0.8％、Y2O30.4-0.8％、Tm2O30.3-0.6％。
6. The method of preparing a ceramic dielectric material according to any one of claims 1 to 5, comprising in particular the steps of: and mixing, wet grinding and drying the barium titanate and the components to obtain the ceramic dielectric material.
7. A ceramic capacitor obtained by sintering the ceramic dielectric material according to any one of claims 1 to 5.
8. The ceramic capacitor as claimed in claim 7, wherein the ceramic capacitor has a multi-dielectric-layer structure, the number of the dielectric layers is 80-100, and the thickness of the dielectric layers is 0.7-1 μm.
9. The ceramic capacitor as claimed in claim 8, wherein the ceramic capacitor has a dielectric constant of 3200-3500 at 25 ℃, a resistivity of 39-41M Ω -M, a capacitance of 0.093-0.097 μ F, and a capacitance change rate of + 15% to-15% at-55 ℃ to 85 ℃.
10. The method for producing a ceramic capacitor as claimed in any one of claims 7 to 9, comprising the steps of: preparing ceramic dielectric material into slurry, casting the slurry into a film with the thickness of 0.85-0.95 mu m, and then printing, laminating, pressing and cutting an electrode to form a green body; then sintering the green body in a reducing atmosphere at 1150-1250 ℃ for 2-4h, then cooling to 950-1100 ℃ for continuous oxidation for 2-4h, and cooling to room temperature after the oxidation is finished to obtain a porcelain body; and then sintering the two ends of the ceramic body to form copper electrodes, and sequentially plating a nickel layer and a tin layer to obtain the ceramic capacitor.
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|---|---|---|---|---|
| JP2005277393A (en) * | 2004-02-25 | 2005-10-06 | Kyocera Corp | Laminated ceramic capacitor and its manufacturing method |
| JP2007169090A (en) * | 2005-12-20 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Dielectric ceramic composition and laminated ceramic capacitor using the same |
| CN114014649A (en) * | 2021-12-13 | 2022-02-08 | 深圳先进电子材料国际创新研究院 | Co-doped barium titanate ceramic dielectric material, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005277393A (en) * | 2004-02-25 | 2005-10-06 | Kyocera Corp | Laminated ceramic capacitor and its manufacturing method |
| JP2007169090A (en) * | 2005-12-20 | 2007-07-05 | Matsushita Electric Ind Co Ltd | Dielectric ceramic composition and laminated ceramic capacitor using the same |
| CN114014649A (en) * | 2021-12-13 | 2022-02-08 | 深圳先进电子材料国际创新研究院 | Co-doped barium titanate ceramic dielectric material, preparation method and application thereof |
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