CN114566382A - Ceramic dielectric material and preparation method and application thereof - Google Patents
Ceramic dielectric material and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 53
- 239000003989 dielectric material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 40
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 31
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims abstract description 11
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 11
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- 239000002019 doping agent Substances 0.000 claims abstract description 4
- 230000015556 catabolic process Effects 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 15
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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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
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
-
- 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
-
- 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
- H01G4/30—Stacked capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a ceramic dielectric material and a preparation method and application thereof, wherein the main material of the material is BaTiO3The doping material comprises SiO2、CaO、V2O5、ZrO2And oxides of rare earth elements; the oxide of the rare earth element comprises Sc2O3、Sm2O3、Dy2O3、Ho2O3At least two of; in mole percent, BaTiO3The addition amount of (B) is 93.5-95 mol%; the total addition amount of the doping material is 4.6-7 mol%. The invention uses BaTiO3As a main material, a sintering aid, a metal oxide and a rare earth element are used as composite dopants to modify a barium titanate ceramic matrix, and the sintering aid and the doping material are added to refine particles, so that defects are controlled, the uniformity of the grain size is improved, and fine grains which have high reliability, stable capacitance characteristics and are easier to laminate are preparedCeramics and multilayer ceramic capacitors.
Description
Technical Field
The invention relates to a ceramic dielectric material, in particular to a ceramic dielectric material and a preparation method and application thereof.
Background
The multilayer ceramic capacitor (MLCC) realizes the effect of increasing the capacity of a plurality of capacitors in parallel by utilizing a monolithic structure, and is widely applied to communication basic equipment circuits in the fields of communication equipment, automobile electronics, industrial machines, medical machines and the like due to the characteristics of low cost, high capacity, stability and the like. For example, it can be used as a power supply bypass capacitor such as a liquid crystal module (liquid crystal drive voltage line), an LSI/IC/OP amplifier of a high power supply voltage, or as a smoothing capacitor such as a DC-DC converter (input and output), a switching power supply (secondary side), or the like. In recent years, the miniaturization of mobile electronic devices has led to the development of MLCCs that are smaller and have larger capacities. Wherein, barium titanate (BaTiO)3) The dielectric constant of the base material of the II-type capacitor in the MLCC is high, but the lamination number needs to be increased when a large-capacity barium titanate-based MLCC is required to be obtained, and the reliability of the MLCC is greatly reduced due to the lamination number. In addition, the dielectric material temperature coefficients of the II-type capacitor are X5R, X6R, X7R and the like, and the capacitance change rate of X5R corresponding to the temperature of-55 ℃ to 85 ℃ is between + 15% and-15% relative to 25 ℃ as mentioned in the American Electronic Industries Association (EIA) capacitor specification. The dielectric constant of barium titanate greatly fluctuates at-90 ℃, 0 ℃ and 125 ℃, so that the application range of barium titanate is limited by the characteristics.
In order to overcome the above problems, it is urgently needed to perform modification doping and rare earth doping on a barium titanate material to prepare ultra-pure ultrafine powder with good dispersibility so as to refine crystal grains and improve uniformity of crystal grain size and distribution, thereby significantly improving the pressure resistance and reliability of the MLCC product.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a ceramic dielectric material and a preparation method and application thereof. According to the invention, a sintering aid, a metal oxide and a rare earth element are mainly selected as composite dopants, a barium titanate ceramic matrix is modified, the sintering aid and the doping material refined particles are added, defects are controlled, the uniformity of the grain size is improved, and the fine-grained ceramic and the multilayer ceramic capacitor which have high reliability, stable capacitance characteristics and are easy to laminate are prepared.
In order to achieve the purpose, the invention adopts the technical scheme that:
a ceramic dielectric material is prepared from BaTiO as main material3The doping material comprises SiO2、CaO、V2O5、ZrO2And oxides of rare earth elements; the oxide of the rare earth element comprises Sc2O3、Sm2O3、Dy2O3、Ho2O3At least two of; in mole percent, BaTiO3The addition amount of (B) is 93.5-95 mol%; the total addition amount of the doping material is 4.6-7 mol%.
The invention uses BaTiO3As a main material, the co-doped barium titanate ceramic dielectric material with high breakdown strength and high reliability is prepared by optimizing the type, formula and specific gravity of the doped material. Wherein SiO is added2As a sintering aid, the sintering temperature is reduced and widened, and the crystal grain growth of ceramic particles in the sintering process is prevented; adding CaO and a small amount of Sc2O3To refine the crystal grains and promote BaTiO together3The density of the ceramic is improved in the mass transfer process; and SiO2The combination with CaO can generate liquid phase in the ceramic sintering process, the liquid phase uniformly wraps each particle to prevent the particles from excessively growing, in addition, the liquid phase on the surface of the inner electrode can prevent metal elements from diffusing to the dielectric layer, the reliability of the MLCC is enhanced, and the advantages of the invention in the application field of the MLCC are increasedThe opposite sex; to prevent Ti4+The ions are reduced to Ti during sintering in a reducing atmosphere3+Generating oxygen vacancies, adding V2O5The V element which can generate valence change is substituted for the Ti position in the Barium Titanate (BT), thereby inhibiting the generation of oxygen vacancy and improving the residual polarization strength and the high-temperature reliability; proper amount of ZrO2Can also increase the band gap and the enthalpy of reduction of the Ti ion, thereby reducing the concentration of oxygen vacancies. In addition, the invention creatively selects rare earth oxide Dy2O3With a small amount of Sm2O3Or Ho2O3The rare earth element doped with the rare earth element is mixed as a co-doping material to form a core-shell structure in a ceramic crystal grain, so that the defect that the concentration of shell elements is uneven due to the fixed ion mobility of a single rare earth element is overcome, the uniform gradient of the concentration of the doping elements from a crystal grain shell part to a core part is facilitated, the complex defect form caused by poor uniformity is avoided to improve the reliability, and the influence of temperature on the capacitance is stabilized.
As a preferred embodiment of the present invention, the doping material comprises SiO2 1.2-1.5mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O3 0-0.4mol％。
As a preferred embodiment of the present invention, the oxide of a rare earth element includes Dy2O3、Sc2O3And Sm2O3、Ho2O3At least one of (1).
As a preferred embodiment of the present invention, the doping material comprises SiO2 1.2-1.4mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0.3-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O3 0.3～0.4mol％。
As a preferred embodiment of the present invention, the host material BaTiO3The grain size of (A) is 180-240 nm.
The inventor finds that the common solid phase method BaTiO is adopted3The powder material can reduce the process complexity and save the cost. BaTiO 23After the nano particles are sintered into a multilayer ceramic capacitor (MLCC), the grain size is grown by 20 to 35 percent, so that the BaTiO main body is controlled3The particle size of the powder is 180-240nm to obtain the final ceramic crystal grain at 200-320 nm.
The invention also provides a preparation method of the ceramic dielectric material, which is to prepare a main material BaTiO3And carrying out wet ball milling on the doped material according to the formula amount, and drying to obtain the ceramic dielectric material.
As a preferred embodiment of the invention, the wet ball milling is carried out for 24 hours by using zirconia balls as a ball milling medium.
The invention also provides the application of the ceramic dielectric material in electronic components; the electronic component includes a multilayer ceramic capacitor.
As a preferred embodiment of the invention, the ceramic dielectric material is sintered for 3-5h at 1200-1260 ℃ in a reducing atmosphere, and is subjected to cutting and end-capping treatment sequentially after annealing to obtain the multilayer ceramic capacitor.
As a preferred embodiment of the present invention, the grain size of the ceramic dielectric in the multilayer ceramic capacitor is 200-320 nm.
As a preferred embodiment of the present invention, the multilayer ceramic capacitor has a dielectric constant of 5000-.
As a preferred embodiment of the present invention, the multilayer ceramic capacitor has a capacitance change rate of + -15% at-55 to 85 ℃.
As a preferred embodiment of the present invention, the multilayer ceramic capacitor has an average breakdown strength of 100-125 kV/mm.
As a preferred embodiment of the present invention, the accelerated aging life test result is 2.3 to 2.7 hours.
The multilayer ceramic capacitor MLCC prepared by sintering the co-doped barium titanate ceramic dielectric material in a reducing atmosphere has the breakdown strength of more than 100kV/mm, delays the insulation resistance deterioration at high temperature, reaches the accelerated aging life test for more than 2.3h, has the dielectric constant of 5000-5600, and can meet the requirement of X5R temperature characteristic, namely the capacitance change rate is between + 15% and-15% at the temperature of-55-85 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the breakdown strength of a multilayer ceramic capacitor prepared by sintering the co-doped barium titanate ceramic dielectric material in a reducing atmosphere is above 100kV/mm, the accelerated aging life test is over 2.3h, and the change of the dielectric constant can meet the requirement of X5R.
(2) The co-doped barium titanate ceramic dielectric material provided by the invention uses oxides as sintering aids, has the advantages of multiple types, less dosage and lower cost, and does not contain harmful elements such as lead, mercury and the like.
(3) The multilayer ceramic capacitor prepared by the invention has fine and evenly distributed crystal grains, the ceramic layer is well matched with the base metal inner electrode and the outer electrode, and the electrode has few holes and no stress cracks.
Drawings
Fig. 1 is a FESEM view of a ceramic dielectric material of example 1 of the present invention.
Fig. 2 is a FESEM view of the ceramic dielectric material of example 2 of the present invention.
Fig. 3 is a FESEM view of the ceramic dielectric material of example 3 of the present invention.
Fig. 4 is a FESEM view of the ceramic dielectric material of example 4 of the present invention.
FIG. 5 is a graph of the grain size distribution of the ceramic of example 1, as counted from the FESEM image of FIG. 1.
FIG. 6 is a graph of the grain size distribution of the ceramic of example 2, as counted from the FESEM image of FIG. 2.
FIG. 7 is a graph of the grain size distribution of the ceramic of example 3, as counted from the FESEM image of FIG. 3.
FIG. 8 is a graph of the grain size distribution of the ceramic of example 4, as counted from the FESEM image of FIG. 4.
FIG. 9 is a graph showing the relationship between the rate of change of dielectric constant and temperature of MLCC samples prepared in example 1 of the invention.
FIG. 10 is a graph showing the relationship between the rate of change of dielectric constant and temperature of MLCC samples prepared in example 2 of the invention.
FIG. 11 is a graph showing the relationship between the rate of change of the capacitance constant and the temperature of the MLCC sample prepared in example 3 of the invention.
FIG. 12 is a graph showing the relationship between the rate of change of the capacitance constant and the temperature of the MLCC sample obtained in example 4 of the invention.
FIG. 13 is a graph showing the results of the Weibull distribution of the breakdown strength of the MLCC samples prepared in example 1 of the present invention.
FIG. 14 is a graph showing the results of the Weibull distribution of the breakdown strength of the MLCC samples prepared in example 2 of the present invention.
FIG. 15 is a graph showing the results of the Weibull distribution of the breakdown strength of the MLCC samples prepared in example 3 of the present invention.
FIG. 16 is a graph showing the results of the Weibull distribution of the breakdown strength of the MLCC samples prepared in example 4 of the present invention.
FIG. 17 is a graph showing the results of the accelerated weathering test in example 1 of the present invention.
FIG. 18 is a graph showing the results of the accelerated weathering test in example 2 of the present invention.
FIG. 19 is a graph showing the results of the accelerated weathering test in example 3 of the present invention.
FIG. 20 is a graph showing the results of the accelerated weathering test in example 4 of the present invention.
Detailed Description
The invention aims to prepare a ceramic dielectric material, wherein the main material of the material is BaTiO3The doping material comprises SiO2、CaO、V2O5、ZrO2And oxides of rare earth elements; the oxide of the rare earth element comprises Sc2O3、Sm2O3、Dy2O3、Ho2O3At least two of; in mole percent, BaTiO3The addition amount of (B) is 93.5-95 mol%; the total addition amount of the doping material is 4.6-7 mol%. Wherein, the main material is BaTiO3The particle size of (a) is 180-240 nm.
In the following examples, the co-doped barium titanate ceramic dielectric material and multilayer ceramic capacitor MLCC were prepared as follows:
(1) selecting high-purity BaTiO with the particle size of 180-240nm3Mixing the powder with various doping materials in proportion, placing zirconia balls as ball milling media in a ball mill, carrying out wet ball milling for 24 hours, and drying after ball milling to obtain ceramic dielectric material powder.
(2) Preparation of MLCC samples: the ceramic dielectric material powder obtained by the method is prepared into slurry, the slurry is cast into a film with the thickness of 1.5 mu m, and a green body with certain shape and size is formed by electrode printing, lamination, pressing and cutting. Wherein, adopt the nickel thick liquid as the internal electrode, the lamination is 300 layers. The green sheet was placed in a reducing atmosphere (1.1% H)2+98.9％N2) Sintering for 35h under the condition of 1260 ℃ at medium temperature 1200 ℃, then reducing the temperature to 1050 ℃ for reoxidation degradation treatment for 1.5h, and then reducing the temperature to 25 ℃ to finish sintering to form the monolithic porcelain body. And then, dipping copper slurry on two ends of the ceramic body in a copper dipping mode, sintering to form a copper electrode firmly combined with the ceramic body, electroplating a nickel layer on the surface of the copper electrode, and electroplating a tin layer for the second time to obtain the MLCC sample.
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
In this example, the host material BaTiO3The particle size of the powder was 180nm, and Table 1 is a formulation table of the components of example 1.
Table 1 formulation table of example 1
Example 2
In this example, the host material BaTiO3The particle size of the powder was 240nm, and Table 2 shows the formulation of each component of example 2.
Table 2 formulation table of example 2
Example 3
In this example, the host material BaTiO3The particle size of the powder was 240nm, and Table 3 shows the formulation of each component in example 3.
Table 3 formulation table of example 3
Example 4
In this example, the host material BaTiO3The particle size of the powder was 180nm and Table 3 is a formulation table for each component of example 3.
Table 4 formulation table of example 4
The results of scanning electron microscope (FESEM) characterization of the preferred embodiments 1, 2 and 3 of the present invention and comparative example 4 are shown in fig. 1, 2, 3 and 4, respectively, and the samples prepared in examples 1, 2 and 3 have good density and no obvious holes.
The sizes of the ceramic grains counted according to the SEM images are shown in fig. 5, 6, 7, and 8 (wherein 157 grains are counted in example 1, 165 grains are counted in example 2, 154 grains are counted in example 3, and 171 grains are counted in example 4): the MLCC prepared by the embodiments 1, 2 and 3 of the invention has more uniform grain size distribution, the average grain size is 240nm, 310nm and 320nm, the average grain size of the embodiment 4 is 200nm, but a few grains grow abnormally, the size is more than 800nm, and the uniformity is poorer.
The results of comparing the change rate of the capacitance constant with the temperature of the MLCC samples obtained in examples 1, 2, 3 and 4 of the invention are shown in FIG. 9, FIG. 10, FIG. 11 and FIG. 12: the capacitance change rate is between + 15% and-15% at the temperature of-55-85 ℃, and the requirement of X5R of EIA is basically met.
The results of the weber distribution of the breakdown strength of the MLCC samples prepared by comparing examples 1, 2, 3, and 4 of the present invention are shown in fig. 13, 14, 15, and 16: the samples prepared by the preferred embodiments 1, 2 and 3 of the invention have improved voltage endurance, the average breakdown strength can reach more than 100kV/mm, while the breakdown strength of the comparative embodiment 4 is lower than 60kV/mm, and the breakdown strength of the preferred embodiment is improved by about 2 times.
In order to expand the application field of the present invention, examples 1, 2, 3, and 4 were particularly tested, and the obtained samples were subjected to accelerated aging test at 150 ℃ with an increase in DC voltage of 2kV/mmm per 0.25h from 2kV/mm, and the results are shown in FIG. 17, FIG. 18, FIG. 19, and FIG. 20. The aging test life of the preferred examples 1, 2, 3 was also improved by about 1.5 times as compared to comparative example 4.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on 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. The ceramic dielectric material is characterized in that the main material of the material is BaTiO3The doping material comprises SiO2、CaO、V2O5、ZrO2And oxides of rare earth elements; the oxide of the rare earth element comprises Sc2O3、Sm2O3、Dy2O3、Ho2O3At least two of; in mole percent, BaTiO3The addition amount of (B) is 93.5-95 mol%; the total addition amount of the doping material is 4.6-7 mol%.
2. The ceramic dielectric material of claim 1, wherein the dopant material comprises SiO2 1.2-1.5mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O3 0-0.4mol％。
3. The ceramic dielectric material of claim 1, wherein the oxide of a rare earth element comprises Dy2O3、Sc2O3And Sm2O3、Ho2O3At least one of (1).
4. The ceramic dielectric material of claim 3, wherein the dopant material comprises SiO2 1.2-1.4mol％，CaO 1.6-2.0mol％，Sc2O3 0.4-0.6mol％，V2O5 0.6-0.9mol％，ZrO2 0.3-0.5mol％，Sm2O3 0.3-0.4mol％，Dy2O3 0.5-0.7mol％，Ho2O30.3～0.4mol％。
5. A ceramic dielectric material as claimed in claim 1 wherein the host material is BaTiO3The grain size of (A) is 180-240 nm.
6. A method for preparing a ceramic dielectric material according to any one of claims 1 to 5, wherein a host material BaTiO is used3And carrying out wet ball milling on the doped material according to the formula amount, and drying to obtain the ceramic dielectric material.
7. The ceramic dielectric material as claimed in any one of claims 1 to 5 is applied to electronic components; the electronic component includes a multilayer ceramic capacitor.
8. The use of the ceramic dielectric material as claimed in claim 7 in electronic components, wherein the ceramic dielectric material is sintered for 3-5h at 1200-1260 ℃ in a reducing atmosphere, and is subjected to cutting and end-capping treatment after annealing to obtain a multilayer ceramic capacitor.
9. The use of the ceramic dielectric material as claimed in claim 8 in electronic components, wherein the grain size of the ceramic dielectric in the multilayer ceramic capacitor is 200-320 nm.
10. The ceramic dielectric material as claimed in claim 8, wherein the dielectric constant of the multilayer ceramic capacitor at 25 ℃ is 5000-; the capacitance change rate of the multilayer ceramic capacitor is +/-15% at-55-85 ℃; the average breakdown strength of the multilayer ceramic capacitor is 100-125 kV/mm.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041058A (en) * | 2023-01-09 | 2023-05-02 | 山东国瓷功能材料股份有限公司 | Dielectric material, preparation method thereof and multilayer chip ceramic capacitor |
| CN116425528A (en) * | 2023-04-24 | 2023-07-14 | 广东省先进陶瓷材料科技有限公司 | Dielectric ceramic material and chip type multilayer ceramic capacitor prepared from same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041058A (en) * | 2023-01-09 | 2023-05-02 | 山东国瓷功能材料股份有限公司 | Dielectric material, preparation method thereof and multilayer chip ceramic capacitor |
| CN116425528A (en) * | 2023-04-24 | 2023-07-14 | 广东省先进陶瓷材料科技有限公司 | Dielectric ceramic material and chip type multilayer ceramic capacitor prepared from same |
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