CN112479705A - Barium titanate-based X8R dielectric material for multilayer ceramic capacitor and preparation method thereof - Google Patents
Barium titanate-based X8R dielectric material for multilayer ceramic capacitor and preparation method thereof Download PDFInfo
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- CN112479705A CN112479705A CN202011207796.XA CN202011207796A CN112479705A CN 112479705 A CN112479705 A CN 112479705A CN 202011207796 A CN202011207796 A CN 202011207796A CN 112479705 A CN112479705 A CN 112479705A
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 43
- 239000003989 dielectric material Substances 0.000 title claims abstract description 40
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 24
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 71
- 239000000919 ceramic Substances 0.000 claims abstract description 67
- 238000000498 ball milling Methods 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- YGBGWFLNLDFCQL-UHFFFAOYSA-N boron zinc Chemical compound [B].[Zn] YGBGWFLNLDFCQL-UHFFFAOYSA-N 0.000 claims abstract description 20
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 18
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 13
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 101000872083 Danio rerio Delta-like protein C Proteins 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 239000003292 glue Substances 0.000 claims abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 33
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000009413 insulation Methods 0.000 description 16
- 239000010949 copper Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 9
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- 239000013078 crystal Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 239000011363 dried mixture Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LFUSWQZWBZPZCV-UHFFFAOYSA-N [Bi].[Na].[Ti] Chemical compound [Bi].[Na].[Ti] LFUSWQZWBZPZCV-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000010953 base metal Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000003574 free electron Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- BDMHSCBWXVUPAH-UHFFFAOYSA-N cobalt niobium Chemical compound [Co].[Nb] BDMHSCBWXVUPAH-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910010069 TiCo Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- AMVVEDHCBDQBJL-UHFFFAOYSA-N [Ca][Zr] Chemical compound [Ca][Zr] AMVVEDHCBDQBJL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a dielectric material for barium titanate-based X8R type multilayer ceramic capacitor and a preparation method thereof, wherein the chemical formula of the material is BaTiO3‑0.01A‑0.005Nd2O3‑x Bi2O3‑y Ho2O3+0.5 wt% of B, wherein x ═ y ═ 0.75 to 1.5 mol%. The preparation method comprises the following steps: 1) by Nb2O5And Co2O3Preparation of Nb-Co composite oxide dopant powder materialA; 2) with Zn (CH)3COO)2·2H2O and H3BO3Preparing boron-zinc sintering aid powder B as a raw material; 3) mixing the materials according to the chemical formula, putting the raw materials into a ball mill, mixing and ball-milling the raw materials by a wet ball-milling method, and drying the raw materials to obtain ceramic powder; 4) grinding, granulating, sieving and dry-pressing the ceramic powder to obtain a ceramic green body; 5) and (4) removing the glue from the ceramic green body and sintering. The dielectric ceramic material prepared by the invention meets the temperature change rate DeltaC/C within the temperature range of-55-150 DEG C25℃Less than or equal to 15 percent, dielectric constant of over 2400 at room temperature, and dielectric loss of not more than 2.0 percent at room temperature.
Description
Technical Field
The invention relates to a dielectric material for a ceramic capacitor, in particular to a barium titanate-based X8R type dielectric material for a multilayer ceramic capacitor with high-temperature stability and a preparation method thereof; belongs to the technical field of dielectric ceramics.
Background
A multilayer ceramic capacitor (MLCC) is a parallel chip electronic component formed by alternately arranging dielectric ceramic diaphragms and internal electrodes. Compared with other capacitors, the MLCC has the advantages of small volume, low price, small equivalent series resistance, good high-frequency characteristic, multiple product types and the like, is the most mainstream product in the capacitor market at present, and is widely applied to various electronic circuits and electronic equipment. With the expansion of the application range, the application requirement of the temperature-stable high-temperature capacitor device in special fields such as aerospace, automobile engines, national defense and military industry and the like is more and more urgent. Satisfying American Electronic Industries Association (Electronic Industries Association) X7R type (X represents the lowest temperature service temperature of-55 ℃; 7 represents the highest temperature of 125 ℃; R represents the maximum deviation of the allowable capacitance along with the temperature change and the capacitance value at the room temperature of 25 ℃ is not more than 15%, namely delta C/C25The temperature is less than or equal to +/-15 percent). The multilayer ceramic capacitor of the X7R standard has not been able to meet the use requirements. Therefore, multilayer ceramic capacitors of the X8R type (8 stands for a maximum use temperature of 150 ℃) are becoming more and more the focus of research.
The current large-capacity lead-free temperature stable MLCC mainly consists of barium titanate (BaTiO)3) Is typically of perovskite (ABO)3) A structural room temperature ferroelectric material. The dielectric constant of the product is high and can reach 200 at room temperature0 to 3000, the dielectric loss is small, and meanwhile, the environment is not polluted in the production and use processes of the composite material, so that the composite material is particularly suitable for manufacturing high-performance dielectric materials. However, pure barium titanate has a curie temperature of about 120 ℃, a large dielectric constant, and a dielectric constant rapidly decreases after the temperature is higher or lower than the curie temperature, so that the temperature-holding characteristic requirements cannot be met.
The Chinese patent application CN103204677A discloses a high dielectric property X8R type ceramic capacitor dielectric material and a preparation method thereof, and the chemical composition general formula of the ceramic dielectric material satisfies: ba1-xBixTiO3+aNb2O5+bCo2O3+cNd2O3+dMnO2+eZrO2Wherein x is more than 0.010 and less than or equal to 0.045, a is 0.6 to 0.9 wt%, b is 0.1 to 0.2 wt%, c is 0.3 to 0.6 wt%, d is 0.01 to 0.03 wt%, e is 0.5 to 2.0 wt%, and the balance is Ba1-xBixTiO3. The performance of the ceramic dielectric material prepared by the invention reaches the following indexes: the ceramic wafer has sintering temperature of 1100-1200 deg.c, grain size of 0.1-0.5 micron and room temperature dielectric loss<1.0 percent. The technical raw material contains MnO2+ZrO2,MnO2And ZrO2Two main roles are played throughout the doped ceramic system, the first: zr4+Or Mn4+Equivalently substituted Ti4+Formation of BaTi1-x(Zr,Mn)xO3The chemical uniformity of (2) doping the non-ferroelectric phase, and simultaneously slightly expanding the unit cell volume, so that the dielectric peak is widened and the Curie point is slightly raised integrally. Secondly, the method comprises the following steps: zr substituting for Ti site to make redundant TiO2The liquid phase is formed by segregation at the grain boundary. Experiments have shown that excess TiO2Can reduce BaTiO3The starting temperature of the sintering shrinkage of the base ceramic. But Zr4+Or Mn4+Are all equivalent substitutions of Ti4+Are not acceptor doped (low valence doping replaces Ti)4+Is acceptor doped) or the problem of semiconducting of barium titanate ceramics during sintering in reducing atmosphere cannot be completely solved because of barium titanate ceramicsSintering the ceramic material in a reducing atmosphere to obtain Ti4+Is reduced to Ti3 +And meanwhile, weak bound electrons and oxygen vacancies which can move freely are generated, so that n-type semi-conduction occurs in the dielectric material, the insulation resistance is greatly reduced, and the performance is degraded. The acceptor doping is a deep potential well of conductive electrons, and can play a role in binding free electrons, increasing insulation resistance and reducing conductivity. Namely, the doping element replaces Ti position to form acceptor doping, so as to obtain the anti-reduction dielectric material. Meanwhile, with the increasing number of MLCC lamination layers, the dosage of electrode materials is increased continuously, for example, the traditional noble metal electrode material palladium and silver are adopted, so that the preparation cost of the MLCC is higher, and the research and development of BME-MLCC using relatively cheap base metals such as nickel (Ni) and copper (Cu) as inner electrodes are promoted. Since Ni and Cu electrodes are easily oxidized when sintered in air, a green BEM-MLCC using Ni and Cu electrodes needs to be sintered in a reducing atmosphere (usually a nitrogen-hydrogen mixture) to ensure the electrical conductivity of the electrodes. However, sintering of barium titanate ceramic materials in a reducing atmosphere results in Ti4+Is reduced to Ti3+And meanwhile, weak bound electrons and oxygen vacancies which can move freely are generated, so that n-type semi-conduction occurs in the dielectric material, the insulation resistance is greatly reduced, and the performance is degraded. The acceptor doping is a deep potential well of conductive electrons, and can play a role in binding free electrons, increasing insulation resistance and reducing conductivity. Namely, the doping element replaces Ti position to form acceptor doping, so as to obtain the anti-reduction dielectric material. Whereas the CN1032046677A patent application does not add an acceptor doping element. In addition, this technique MnO2Mn during sintering in a reducing atmosphere4+Is also easily reduced to Mn3+Or Mn2+And meanwhile, weakly bound electrons and oxygen vacancies which can move freely are generated, so that the dielectric material is further semiconductive.
Chinese invention patent CN102718477A discloses a high dielectric constant X8R type MLCC dielectric material and a preparation method thereof, wherein 100 parts by weight of barium titanate is taken as a base material, and the following components in parts by weight are added: 1.6-2.5 parts of niobium-cobalt compound; 0.722-1.805 parts of a sodium titanium bismuth compound; 1.25-2.0 parts of zirconium calcium compound; 1-3 parts of glass powder; 0.369-1.2 parts of one or more oxides of Ce, Yb, Dy and Ho; 0.1-0.25 parts of manganese carbonate. The technology is an MLCC system, namely barium titanate and titanium bismuth sodium compound are solid-dissolved. Bi participates in the formation of a titanium bismuth sodium compound, the Curie temperature of the compound is about 320 ℃, and the compound and BaTiO3 are compounded into a solid solution with a perovskite structure by utilizing the high Curie point of the compound, so that the Curie temperature can be improved, and the temperature stability of the dielectric constant at a high temperature end can be realized. However, the sintering temperature of the technology is required to be 1270-1310 ℃, so that the ceramic crystal grains are easy to be overlarge, and the technology is not suitable for preparing the miniaturized, thinned and large-capacity MLCC element.
Disclosure of Invention
The invention aims to solve the technical problem of developing a lead-free environment-friendly novel high-performance dielectric material for a multilayer ceramic capacitor, which meets the requirements of EIAX8R standard on wide working temperature range and high temperature stability, and has the advantages of low sintering temperature, high reduction resistance and suitability for using base metal nickel and copper as internal electrodes.
The purpose of the invention is realized by the following technical scheme:
a dielectric material for a high dielectric constant X8R type multilayer ceramic capacitor: it is prepared from tetragonal submicron barium titanate BaTiO3Nb-Co composite oxide dopant A, Nd2O3、Bi2O3、Ho2O3And boron-zinc sintering aid B with the chemical formula of BaTiO3-0.01A-0.005Nd2O3-xBi2O3-yHo2O3+0.5 wt% B, wherein x ═ y ═ 0.75 to 1.5 mol%; the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor meets the temperature change rate DeltaC/C within the temperature range of-55-150 DEG C25The dielectric constant at room temperature is more than 2400 ℃, and the dielectric loss at room temperature is not more than 2.0 percent;
the Nb-Co composite oxide dopant A is Nb2O5And Co2O3Controlling Nb as raw material2O5And Co2O3The molar ratio is 1.5: 1-2.5: 1, ball milling, drying and pre-treating the raw materialsAnd (4) firing to obtain the product.
In order to further achieve the object of the present invention, preferably, the ball milling is to put the raw materials into a ball mill and mix and ball mill the raw materials by a wet ball milling method; the pre-sintering process comprises the steps of heating to 900-950 ℃ at a heating rate of 10 ℃/min at room temperature, preserving heat for 1.5-3 h, and then naturally cooling along with a furnace; and the drying is carried out for 12-24 hours at the temperature of 100-120 ℃.
Preferably, the wet ball milling method is to perform mixed ball milling for 22-26 hours by taking zirconia balls and deionized water as media.
The preparation method of the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor comprises the following steps:
1) preparing Nb-Co composite oxide dopant A powder;
2) with Zn (CH)3COOH)2And H3BO3Controlling Zn (CH) as raw material3COOH)2And H3BO3The molar ratio of 11: 14-13: 14, putting the prepared raw materials into a ball mill, mixing and ball-milling by a wet ball-milling method, drying and presintering to obtain boron-zinc sintering aid B powder;
3) with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step 1) and the boron-zinc sintering aid B obtained in the step 2) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005 Nd2O3-x Bi2O3-yHo2O3+0.5 wt% of B ingredient, putting the prepared raw materials into a ball mill, mixing and ball-milling by a wet ball-milling method, and drying to obtain ceramic powder;
4) grinding, granulating and sieving the ceramic powder obtained in the step 3), and then performing dry pressing to obtain a ceramic green body;
5) and (3) placing the ceramic green body obtained in the step 4) in a high-temperature furnace for sintering after glue discharging to obtain the dielectric material with the high dielectric constant of X8R type for the multilayer ceramic capacitor, wherein the sintering temperature is 1160-1210 ℃, and the sintering time is 2-4 hours.
Preferably, in the step 2) and the step 3), the wet ball milling method is to perform mixing ball milling for 22-26 hours by using zirconia balls and deionized water as media.
Preferably, in the step 2), the pre-sintering is carried out by heating to 550-600 ℃ at a heating rate of 3 ℃/min at room temperature, preserving heat for 1-2 h, and then naturally cooling along with the furnace;
preferably, in the step 5), the rubber discharging is carried out by heating to 600 ℃ at room temperature at a heating rate of 2 ℃/min, then keeping the temperature for 2 hours, and then naturally cooling along with the furnace.
Preferably, the temperature rise mode of the sintering is that the temperature is raised to 1160-1210 ℃ from room temperature at the temperature rise rate of 10 ℃/min.
Preferably, in the step 2) and the step 3), the drying is carried out for 12-24 hours at the temperature of 100-120 ℃.
Preferably, in the step 4), the granulation is carried out after polyvinyl alcohol (PVB) accounting for 5-10% of the mass of the ceramic powder is added; and the sieving is to sieve the mixture by a sieve of 60-100 meshes.
In the invention, BaTiO is mixed with3And Nb-Co composite oxide dopant A, Nd2O3Boron-zinc sintering aid B and Bi2O3And Ho2O3And the raw materials are sintered together to form the ceramic. Bi2O3And Ho2O3Is diffused into BaTiO in the sintering process3The shell part of (1), namely the shell, is doped and modified (comprising doping elements such as Bi, Ho and the like) paraelectric phase BaTiO3The "core" is essentially the pure ferroelectric phase BaTiO3。
Proper amount of Bi in the invention2O3And Ho2O3Mixing the raw materials in a ratio of 1: the ratio of 1 codopants is based on the following mechanism. Bi2O3And Ho2O3(1: 1 may be abbreviated as BiHoO)3) When co-doped, Nb5+、Co3+Ion introduction into BaTiO3Lattice substitution of Ti4+Forming a core-shell structure, which can make the dielectric constant-temperature curve flat, and the concrete process is as follows: nb2O5And Co2O3First rapidly neutralize BaTiO3React to form various intermediate phases, and then Nb and Co are diffused from the intermediate phases to the perovskite latticeScattered, but slowly diffused. Nb and Co are both the sites for Ti substitution, but Nb5+Is donor doped and Co3+It is the acceptor doping. Additive Nb2O5And Co2O3Shows strong Co-solubility, and Co enrichment can be observed in the Nb-enriched area, so that the donor defect NbTiAnd acceptor defect CoTiNot independently present in BaTiO3In the crystal lattice, but tends to be in the form of [2 Nb. ]TiCo″Ti]X such a form of defect association enters the perovskite lattice.
And Nb5+、Co3+Ion introduction into BaTiO3Lattice substitution of Ti4+Helping to form a "core-shell" structure. While the rare earth element Ho has a partial effect in that it can occupy the Ti sites of the grain shell portion and cause lattice expansion, causing lattice mismatch between the formed "core" and "shell" to cause internal stress. The internal stress plays a role in stabilizing the core tetragonal phase, increasing the curie temperature and raising the curie peak. By reasonably adjusting Nb5+、Co3+、Ho3+The proportion can reasonably construct internal stress between the core and the shell, and the effect of lifting the Curie peak is realized. Ho replaces Ti position to form acceptor doping, and the acceptor is deep potential well of conductive electron, which can play the role of restricting free electron and reducing conductivity, so the anti-reduction performance of the ceramic can be improved. In addition, Ho has an ionic radius of 0.0901nm, shows an amphoteric characteristic, can occupy the A position to replace Ba to play a role in donor doping, can occupy the B position to replace Ti to play a role in acceptor doping, and Ho & ltr & gt generated by donor dopingBaAnd Ho 'produced by acceptor doping'TiAttract each other, and cause defect association [ Ho ]BaHo′Ti]The defect has poor mobility under the action of an electric field and can be an obstacle to oxygen vacancy migration, so that the insulation resistivity, the service life, the reliability and the reduction resistance of the dielectric material can be improved. And the diffusivity of Bi is lower than that of Ho, so that the deep diffusion of Ho to the core part can be inhibited, and the stability of the core-shell structure is ensured. The ionic radius of Bi is smaller than that of Ba, so that the substitution of Bi for Ba can enlarge the adjacent oxygen octahedral voids, thereby increasing the substitution of Ho for TiThe probability, the solid solubility of Ho in barium titanate matrix is improved, the formation of pyrochlore phase is reduced, and the peak shift effect is enhanced. In addition, Bi2O3Because of low melting point, it also has a certain liquid-phase sintering-aid action, and can reduce sintering temp., reduce grain size, raise density of medium ceramic body and reduce loss.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the addition of appropriate niobium-cobalt composite oxide can help to form a core-shell structure, and the structure can play a role in suppressing and widening a dielectric peak and is beneficial to reducing the temperature change rate of the material. With simultaneous addition of Nd2O3The volume ratio of the core to the shell can be effectively changed, the dielectric constant of the low-temperature section of the material is improved, and the dielectric constant of the high-temperature section is depressed. In the sintering process, the added boron-zinc sintering aid forms a liquid phase on a crystal boundary, promotes material transmission, can obviously reduce the sintering temperature, reduces the grain size, improves the density of a dielectric ceramic body and reduces the loss.
(2) The invention is a proper amount of Bi2O3And Ho2O3Mixing the raw materials in a ratio of 1:1, doping Ho alone may cause the metastable "core-shell" structure of barium titanate-based ceramics to be destroyed by excessive diffusion of Ho, losing the temperature stability of dielectric constant. And the diffusivity of Bi is lower than that of Ho, and the introduction of Bi obviously helps to inhibit the diffusion of Ho and maintain the stability of a core-shell structure. In addition, Bi2O3Because of low melting point, it also has a certain liquid-phase sintering-aid action, and can reduce sintering temp., reduce grain size, raise density of medium ceramic body and reduce loss. Therefore, the sintering temperature of the invention is obviously lower than that of the Chinese patent application CN 102718477A.
(3) The ceramic dielectric material prepared by the invention has low sintering temperature of 1160-1210 ℃, meets the EIA X8R standard requirement, has good dielectric property and lower dielectric loss (less than or equal to 2.35%), wherein the room-temperature dielectric constant is more than 2400, and the room-temperature (25 ℃) dielectric loss is only 1.64%. The anti-reduction performance is strong, and the method is suitable for the production and application of the base metal nickel and copper as the inner electrode MLCC, and the cost of the material is obviously reduced.
(4) The dielectric material of the invention does not contain lead and is harmless to the environment. The ceramic preparation process adopts a solid phase method, and the process flow is simple and easy to operate.
Drawings
FIG. 1 is a graph of dielectric constant versus temperature for examples 1-4;
FIG. 2 is a graph of dielectric loss as a function of temperature for examples 1-4;
FIG. 3 is a graph showing the temperature change rate of examples 1 to 4 as a function of temperature;
FIG. 4 is a SEM of crystal grains of a sample obtained in example 1
FIG. 5 is an SEM image of the crystal grains of a sample obtained from the Chinese patent application CN 102718477A.
Detailed Description
For better understanding of the present invention, the present invention is further illustrated by the following figures and examples, but the embodiments of the present invention are not limited to the following examples, and the purity of the raw materials used in the present invention is analytical.
Example 1
By Nb2O5And Co2O3As a raw material, according to Nb2O5And Co2O3The molar ratio is 2: 1, mixing materials, putting the prepared raw materials into a ball mill, and mixing and ball-milling by a wet ball-milling method. The ball milling medium is zirconia balls and deionized water, and the mixture is ball milled for 24 hours. And then drying the mixture at 100 ℃ for 12h, and putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 950 ℃ at the room temperature at the heating rate of 10 ℃/min, the temperature is kept for 2 hours, and the Nb-Co composite oxide dopant A powder is obtained after the mixture is naturally cooled along with the furnace;
with Zn (CH)3COOH)2And H3BO3As starting material, according to Zn (CH)3COOH)2And H3BO3The molar ratio is 13: 14, mixing and ball-milling the prepared raw materials in a ball mill by a wet ball-milling method, wherein ball-milling media are zirconia balls and deionized water, and mixing and ball-milling for 24 hours. And then drying the mixture at 100 ℃ for 12h, and putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 550 ℃ at the temperature raising rate of 3 ℃/min at room temperature, the temperature is preserved for 1h,then naturally cooling along with the furnace to obtain boron-zinc sintering aid B powder;
with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step (3) and the boron-zinc sintering aid B obtained in the step (3) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005 Nd2O3-x Bi2O3-yHo2O3+0.5 wt% of B, wherein x is y is 0.75 mol%, the prepared raw materials are put into a ball mill and mixed and ball-milled by a wet ball milling method, the ball milling media are zirconia balls and absolute ethyl alcohol, the mixture is ball-milled for 24 hours, and then the mixture is dried for 24 hours at 100 ℃. Grinding the dried ceramic powder, adding PVB accounting for 10% of the mass of the ceramic powder, granulating, sieving with a 80-mesh sieve, and dry-pressing into a ceramic green body with the diameter of 10 mm and the thickness of 1.2 mm. Heating the obtained ceramic green body to 600 ℃ at room temperature at the heating rate of 2 ℃/min, then preserving heat for 2 hours, then naturally cooling along with the furnace to carry out binder removal, then sintering in a high-temperature furnace, wherein the sintering process is heating to 1210 ℃ at the heating rate of 10 ℃/min at room temperature, preserving heat for 3 hours, and then naturally cooling along with the furnace to obtain the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor.
Grinding and polishing two ends of the dielectric material prepared in the embodiment, coating electrodes, drying and burning silver to obtain a dielectric ceramic element, and then testing and calculating the relative dielectric constant epsilon of the dielectric ceramic elementrDielectric loss tan delta and capacity temperature change rate delta C/C25DEG C. FIG. 1, FIG. 2 and FIG. 3 show the dielectric constant ε of example 1rDielectric loss tan delta and capacity temperature change rate DeltaC/C25The temperature is changed along with the temperature. Specific dielectric property parameters are listed in Table 1, and the temperature change rate of the ceramic, | Delta C/C25The temperature of | is not more than 15% in the temperature range of-55-150 ℃, and the EI X8R standard is met. The dielectric constant can reach 2668 at room temperature, the loss is only 1.35%, and the insulation resistivity reaches 2.58 multiplied by 1012Ω·cm。
As can be seen from Table 1, the dielectric ceramic element obtained in the present example had an insulation resistivity of 2 to 3X 1012Omega cm order of magnitude, and the same method tests Chinese hairThe insulation resistivity of the sample obtained in example 1 of the patent application CN1032046677A is only 2-3 x 1010In the order of Ω · cm. The product has the insulation resistivity far larger than CN1032046677A, has strong anti-reduction performance, is suitable for the production and application of the internal electrode MLCC made of base metal nickel and copper, and obviously reduces the cost of materials. The main reason is that the use amount of electrode materials is increasing with the increasing number of MLCC stacked layers, for example, the traditional noble metal electrode material palladium and silver are adopted to make the MLCC preparation cost higher, which promotes the research and development of BME-MLCC using relatively cheap base metals such as nickel (Ni), copper (Cu) and the like as internal electrodes. Since Ni and Cu electrodes are easily oxidized when sintered in air, a green BEM-MLCC using Ni and Cu electrodes needs to be sintered in a reducing atmosphere (usually a nitrogen-hydrogen mixture) to ensure the electrical conductivity of the electrodes. However, sintering of barium titanate ceramic materials in a reducing atmosphere results in Ti4+Is reduced to Ti3+And meanwhile, weak bound electrons and oxygen vacancies which can move freely are generated, so that n-type semi-conduction occurs in the dielectric material, the insulation resistance is greatly reduced, and the performance is degraded. The acceptor doping is a deep potential well of conductive electrons, and can play a role in binding free electrons, increasing insulation resistance and reducing conductivity. Namely, the doping element replaces Ti position to form acceptor doping, so as to obtain the anti-reduction dielectric material. Whereas the CN1032046677A patent does not add an acceptor doping element.
TABLE 1 dielectric Properties of ceramic media of different formulations
The invention is a proper amount of Bi2O3And Ho2O3Mixing the raw materials in a ratio of 1:1 co-doping, Bi2O3Because the melting point is low and the sintering aid has a liquid phase sintering effect, the sintering temperature of the invention is greatly reduced compared with the Chinese patent application CN 102718477A. The sintering temperature is lowered, the preparation cost can be reduced, and the grain size can be reduced (SEM pictures of the crystal grains of the sample obtained in the example 1 of the present example and the Chinese patent application CN1032046677A are shown in FIGS. 4 and 5, under the same magnificationThe crystal grains of the sample of the embodiment are obviously smaller than the Chinese patent application CN1032046677A), and the density of the dielectric ceramic body is improved. The Chinese patent application CN102718477A actually uses another MLCC system, namely barium titanate and titanium bismuth sodium compound solid solution. Bi2O3Firstly, the titanium bismuth sodium compound is formed, the Curie temperature of said compound is about 320 deg.C, and it and BaTiO are mixed by utilizing its high Curie point3The solid solution having perovskite structure is compounded to increase Curie temperature and realize temperature stability of dielectric constant at high temperature, so that Bi is used in the application2O3It cannot play a role of reducing the sintering temperature in the present invention.
Invention H2O3Is an amphoteric rare earth oxide, Ho3+The ionic radius is 0.0901nm and is between Ba2+And Ti4+In place of Ba2+And may be substituted for Ti4+. Incorporation of BaTiO3Ti in place of B4+And the doped silicon nitride is doped with an acceptor, and the acceptor can play a role in binding conductive electrons, increasing insulation resistance and reducing conductivity. When Ho3+Ba substituted for A position2+And then belongs to donor doping. Ho. produced by doping of donorsBaAnd Ho 'produced by acceptor doping'TiAttract each other, and cause defect association [ Ho ]BaHo′Ti]The defect has poor mobility under the action of an electric field and can be used as an obstacle for oxygen vacancy migration, so that the insulation resistivity of the dielectric material can be improved, namely the effect of improving the reduction resistance of the ceramic is achieved.
Invention Ho3+In BaTiO3Low solid solubility in (C), excessive Ho3+Optionally substituted Ti4+Reaction to form Ho2Ti2O7The generated second phase with lower dielectric constant can play a part of the role of broadening dielectric peak and can play a role of pinning to limit BaTiO3The average grain size is kept small at 300 nm. The theory of fine crystals states that: BaTiO with average grain size of 100nm-700nm3Natural has better temperature stability and slightly higher CurieAnd (3) temperature. However, the content of the second phase should not be too large, which may cause BaTiO3Becomes small and even destroys BaTiO3Core-shell structure of (a).
Bi of the invention2O3And Ho2O3(1: 1 may be abbreviated as BiHoO)3) Upon co-doping, a portion of the rare earth element Ho occupies the Ti site of the crystal shell portion and causes lattice expansion, and lattice mismatch of the "core" and "shell" causes internal stress. The internal stress plays a role in stabilizing the core tetragonal phase, increasing the curie temperature and raising the curie peak. Ho doping is the root cause of the Curie temperature increase, and Bi doping alone does not have a peak shift effect. In addition, doping Ho alone can result in the destruction of the metastable "core-shell" structure of the barium titanate-based ceramic due to excessive diffusion of Ho, which can lose the temperature stability of the dielectric constant. And the diffusivity of Bi is lower than that of Ho, and the introduction of Bi obviously helps to inhibit the diffusion of Ho and maintain the stability of a core-shell structure. In fact, when the atomic ratio of Bi/Ho is too small, the barium titanate-based ceramic also undergoes a solid solution phenomenon, and only when the atomic ratio of Bi/Ho is greater than 1:1 has a significant effect of increasing the Curie temperature. Because of Bi3+Has an ionic radius of 0.134nm less than Ba2+Has an ionic radius of 0.161nm, so that Bi3+Substituted Ba2+Then the adjacent oxygen octahedron gaps are enlarged, thereby increasing Ho3+Substituted Ti4+The probability of (c). When Ho2O3Bi with a constant content and high content2O3The doping amount is beneficial to more Ho3+Ground access BaTiO3Lattice, thereby reducing the generation of pyrochlore phases. In conclusion, the ratio of the two is determined as 1: 1. the invention uses 1: molar ratio of 1 Bi2O3,Ho2O3The co-doping of BaTiO3 can not only properly reduce the sintering temperature, but also broaden the dielectric peak, increase the Curie temperature and improve the dielectric temperature characteristic and the anti-reduction performance of the barium titanate ceramic. In addition, Bi2O3Because of low melting point, it also has a certain liquid-phase sintering-aid action, and can reduce sintering temp., reduce grain size, raise density of medium ceramic body and reduce loss.
Example 2
By Nb2O5And Co2O3As a raw material, according to Nb2O5And Co2O3The molar ratio is 1.5: 1, mixing materials, putting the prepared raw materials into a ball mill, and mixing and ball-milling by a wet ball-milling method. The ball milling medium is zirconia balls and deionized water, and the mixture is ball milled for 24 hours. And then drying the mixture at 100 ℃ for 16h, and putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is increased to 900 ℃ at the room temperature at the heating rate of 10 ℃/min, the temperature is kept for 3 hours, and the Nb-Co composite oxide dopant A powder is obtained after the mixture is naturally cooled along with the furnace;
with Zn (CH)3COOH)2And H3BO3As starting material, according to Zn (CH)3COOH)2And H3BO3The molar ratio of 12: 14, mixing and ball-milling the prepared raw materials in a ball mill by a wet ball-milling method, wherein ball-milling media are zirconia balls and deionized water, and mixing and ball-milling for 26 hours. And then drying the mixture at 120 ℃ for 20 hours, and putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 600 ℃ at room temperature at the heating rate of 3 ℃/min, the temperature is kept for 1h, and then the boron-zinc sintering aid B powder is obtained after the boron-zinc sintering aid B powder is naturally cooled along with the furnace;
with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step (3) and the boron-zinc sintering aid B obtained in the step (3) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005 Nd2O3-x Bi2O3-yHo2O3+0.5 wt% of B, wherein x is y is 1.0 mol%, the prepared raw materials are put into a ball mill and mixed and ball-milled by a wet ball milling method, the ball milling media are zirconia balls and absolute ethyl alcohol, the mixture is ball-milled for 26 hours, and then the mixture is dried for 24 hours at 120 ℃. Grinding the dried ceramic powder, adding PVB accounting for 8% of the mass of the ceramic powder, granulating, sieving by a 60-mesh sieve, and dry-pressing into a ceramic green body with the diameter of 10 mm and the thickness of 1.2 mm. Heating the obtained ceramic green body to 600 ℃ at room temperature at a heating rate of 2 ℃/min, then preserving heat for 2 hours, then naturally cooling along with the furnace to discharge glue, and then sintering in a high-temperature furnace, wherein the sintering process is that the temperature is increased to 1180 ℃ at room temperature at a heating rate of 10 ℃/min andkeeping the temperature for 2 hours, and then naturally cooling along with the furnace to obtain the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor.
Grinding and polishing two ends of the dielectric material prepared in the embodiment, coating electrodes, drying and burning silver to obtain a dielectric ceramic element, and then testing and calculating the relative dielectric constant epsilon, the dielectric loss tan delta and the temperature change rate delta C/C of the dielectric ceramic element25DEG C. FIG. 1, FIG. 2 and FIG. 3 show the dielectric constant ε of example 2rDielectric loss tan delta and capacity temperature change rate DeltaC/C25The temperature is changed along with the temperature. Specific dielectric property parameters are listed in Table 1, and the temperature change rate of the ceramic, | Delta C/C25The temperature of | is not more than 15% in the temperature range of-55-150 ℃, and the EI X8R standard is met. The dielectric constant can reach 2567 at room temperature, the loss is only 1.41 percent, and the insulation resistivity reaches 3.46 multiplied by 1012Ω·cm。
Example 3
By Nb2O5And Co2O3As a raw material, according to Nb2O5And Co2O3The molar ratio is 2.5: 1, mixing materials, putting the prepared raw materials into a ball mill, and mixing and ball-milling by a wet ball-milling method. The ball milling medium is zirconia balls and deionized water, and the mixture is ball milled for 26 hours. And then drying the mixture for 24 hours at 100 ℃, and then putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 950 ℃ at the room temperature at the heating rate of 10 ℃/min, the temperature is kept for 3 hours, and the Nb-Co composite oxide dopant A powder is obtained after the mixture is naturally cooled along with the furnace; with Zn (CH)3COOH)2And H3BO3As starting material, according to Zn (CH)3COOH)2And H3BO3The molar ratio of 11: 14, mixing and ball-milling the prepared raw materials in a ball mill by a wet ball-milling method, wherein ball-milling media are zirconia balls and deionized water, and mixing and ball-milling for 22 hours. And then drying the mixture for 24 hours at 100 ℃, and then putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 550 ℃ at the temperature raising rate of 3 ℃/min at room temperature, the temperature is preserved for 2 hours, and then the boron-zinc sintering aid B powder is obtained after the boron-zinc sintering aid B powder is naturally cooled along with the furnace;
with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step (3) and the boron-zinc sintering aid B obtained in the step (3) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005 Nd2O3-x Bi2O3-yHo2O3+0.5 wt% of B, wherein x ═ y ═ 1.25 mol%, the prepared raw materials were put into a ball mill and mixed and ball milled by a wet ball milling method with zirconia balls and absolute ethyl alcohol as the milling media, mixed and ball milled for 22 hours, and then dried by baking at 120 ℃ for 20 hours. Grinding the dried ceramic powder, adding PVB accounting for 5% of the mass of the ceramic powder, granulating, sieving with a 100-mesh sieve, and dry-pressing into a ceramic green body with the diameter of 10 mm and the thickness of 1.2 mm. Heating the obtained ceramic green body to 600 ℃ at room temperature at the heating rate of 2 ℃/min, then preserving heat for 2 hours, then naturally cooling along with the furnace to carry out binder removal, then sintering in a high-temperature furnace, wherein the sintering process is heating to 1200 ℃ at the heating rate of 10 ℃/min at room temperature, preserving heat for 4 hours, and then naturally cooling along with the furnace to obtain the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor.
Grinding and polishing two ends of the dielectric material prepared in the embodiment, coating electrodes, drying and burning silver to obtain a dielectric ceramic element, and then testing and calculating the relative dielectric constant epsilon, the dielectric loss tan delta and the temperature change rate delta C/C of the dielectric ceramic element25DEG C. FIG. 1, FIG. 2 and FIG. 3 show the dielectric constant ε of example 3rDielectric loss tan delta and capacity temperature change rate DeltaC/C25The temperature is changed along with the temperature. Specific dielectric property parameters are listed in Table 1, and the temperature change rate of the ceramic, | Delta C/C25The temperature is not more than 15% in the temperature range of-55-150 ℃. And the standard EI X8R is met. The dielectric constant can reach 2515 at room temperature, the loss is only 1.99%, and the insulation resistivity reaches 2.44 multiplied by 1012Omega cm. Example 4
By Nb2O5And Co2O3As a raw material, according to Nb2O5And Co2O3The molar ratio is 2.5: 1, mixing materials, putting the prepared raw materials into a ball mill, and mixing and ball-milling by a wet ball-milling method. The ball milling medium is zirconia balls and deionized water, and the mixture is ball milled for 23 hours. Then dried for 22h at 120 ℃ and then put intoAnd (4) pre-burning in a high-temperature furnace. The pre-sintering process is that the temperature is increased to 920 ℃ at room temperature at the heating rate of 10 ℃/min, the temperature is kept for 2.5 hours, and the Nb-Co composite oxide dopant A powder is obtained after the mixture is naturally cooled along with the furnace; with Zn (CH)3COOH)2And H3BO3As starting material, according to Zn (CH)3COOH)2And H3BO3The molar ratio of 12: 14, mixing and ball-milling the prepared raw materials in a ball mill by a wet ball-milling method, wherein ball-milling media are zirconia balls and deionized water, and mixing and ball-milling for 25 hours. And then drying the mixture at 100 ℃ for 20 hours, and putting the dried mixture into a high-temperature furnace for presintering. The pre-sintering process is that the temperature is raised to 600 ℃ at room temperature at the heating rate of 3 ℃/min, the temperature is kept for 1h, and then the boron-zinc sintering aid B powder is obtained after the boron-zinc sintering aid B powder is naturally cooled along with the furnace;
with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step (3) and the boron-zinc sintering aid B obtained in the step (3) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005 Nd2O3-x Bi2O3-yHo2O3+0.5 wt% of B, wherein x ═ y ═ 1.5 mol%, the prepared raw materials were put into a ball mill and mixed and ball milled by a wet ball milling method with zirconia balls and absolute ethyl alcohol as the milling media, mixed and ball milled for 24 hours, and then dried by baking at 100 ℃ for 24 hours. Grinding the dried ceramic powder, adding PVB accounting for 5% of the mass of the ceramic powder, granulating, sieving with a 100-mesh sieve, and dry-pressing into a ceramic green body with the diameter of 10 mm and the thickness of 1.2 mm. Heating the obtained ceramic green body to 580 ℃ at room temperature at the heating rate of 2 ℃/min, then preserving heat for 2 hours, naturally cooling along with the furnace to carry out binder removal, then sintering in a high-temperature furnace, wherein the sintering process is heating to 1180 ℃ at room temperature at the heating rate of 10 ℃/min, preserving heat for 3 hours, and naturally cooling along with the furnace to obtain the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor.
Grinding and polishing two ends of the dielectric material prepared in the embodiment, coating electrodes, drying and burning silver to obtain a dielectric ceramic element, and then testing and calculating the relative dielectric constant epsilon, the dielectric loss tan delta and the temperature change rate delta C/C of the dielectric ceramic element25DEG C. FIG. 1, FIG. 2 and FIG. 2FIG. 3 shows the dielectric constants ε of example 4rDielectric loss tan delta and capacity temperature change rate DeltaC/C25The temperature is changed along with the temperature. Specific dielectric property parameters are listed in Table 1, and the temperature change rate of the ceramic, | Delta C/C25The temperature of | is not more than 15% in the temperature range of-55-150 ℃, and the EI X8R standard is met. The dielectric constant can reach 2472 at room temperature, the loss is only 1.82%, and the insulation resistivity reaches 2.78 multiplied by 1012Ω·cm。
It should be noted that the embodiments of the present invention are not limited by the above-mentioned examples, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent substitutions, and are included in the scope of the present invention.
Claims (10)
1. A dielectric material for a high dielectric constant X8R type multilayer ceramic capacitor is characterized in that: it is prepared from tetragonal submicron barium titanate BaTiO3Nb-Co composite oxide dopant A, Nd2O3、Bi2O3、Ho2O3And boron-zinc sintering aid B with the chemical formula of BaTiO3-0.01A-0.005Nd2O3-xBi2O3-yHo2O3+0.5 wt% B, wherein x ═ y ═ 0.75 to 1.5 mol%; the dielectric material for the high-dielectric-constant X8R type multilayer ceramic capacitor meets the temperature change rate DeltaC/C within the temperature range of-55-150 DEG C25℃Less than or equal to 15 percent, dielectric constant of over 2400 at room temperature, and dielectric loss of less than or equal to 2.0 percent at room temperature;
the Nb-Co composite oxide dopant A is Nb2O5And Co2O3Controlling Nb as raw material2O5And Co2O3The molar ratio is 1.5: 1-2.5: 1, ball-milling the raw materials, drying and presintering to obtain the product.
2. The dielectric material for high dielectric constant X8R type multilayer ceramic capacitor as claimed in claim 1, wherein: the ball milling is to put the raw materials into a ball mill and mix and ball mill the raw materials by a wet ball milling method; the pre-sintering process comprises the steps of heating to 900-950 ℃ at a heating rate of 10 ℃/min at room temperature, preserving heat for 1.5-3 h, and then naturally cooling along with a furnace; and the drying is carried out for 12-24 hours at the temperature of 100-120 ℃.
3. The dielectric material for high dielectric constant X8R type multilayer ceramic capacitor as claimed in claim 2, wherein: the wet ball milling method adopts zirconia balls and deionized water as media, and the mixing and ball milling is carried out for 22-26 hours.
4. The method for producing a dielectric material for a high dielectric constant X8R type multilayer ceramic capacitor as claimed in any one of claims 1 to 3, characterized by the steps of:
1) preparing Nb-Co composite oxide dopant A powder;
2) with Zn (CH)3COOH)2And H3BO3Controlling Zn (CH) as raw material3COOH)2And H3BO3The molar ratio of 11: 14-13: 14, putting the prepared raw materials into a ball mill, mixing and ball-milling by a wet ball-milling method, drying and presintering to obtain boron-zinc sintering aid B powder;
3) with BaTiO3、Nd2O3、Bi2O3、Ho2O3The Nb-Co composite oxide dopant A powder obtained in the step 1) and the boron-zinc sintering aid B obtained in the step 2) are used as raw materials according to the chemical formula BaTiO3-0.01A-0.005Nd2O3-x Bi2O3-y Ho2O3+0.5 wt% of B ingredient, putting the prepared raw materials into a ball mill, mixing and ball-milling by a wet ball-milling method, and drying to obtain ceramic powder;
4) grinding, granulating and sieving the ceramic powder obtained in the step 3), and then performing dry pressing to obtain a ceramic green body;
5) and (3) placing the ceramic green body obtained in the step 4) in a high-temperature furnace for sintering after glue discharging to obtain the dielectric material with the high dielectric constant of X8R type for the multilayer ceramic capacitor, wherein the sintering temperature is 1160-1210 ℃, and the sintering time is 2-4 hours.
5. The method of claim 4, wherein: in the step 2) and the step 3), the wet ball milling method is to perform mixed ball milling for 22-26 hours by taking zirconia balls and deionized water as media.
6. The method of claim 4, wherein: in the step 2), the pre-sintering is carried out by heating to 550-600 ℃ at a heating rate of 3 ℃/min at room temperature, preserving heat for 1-2 h, and then naturally cooling along with the furnace.
7. The method of claim 4, wherein: in the step 5), the binder removal is carried out by heating to 600 ℃ at room temperature at a heating rate of 2 ℃/min, then carrying out heat preservation for 2 hours, and then carrying out natural cooling along with the furnace.
8. The method of claim 4, wherein: the temperature rise mode of the sintering is that the temperature is raised to 1160-1210 ℃ from room temperature at the temperature rise rate of 10 ℃/min.
9. The method of claim 4, wherein: in the step 2) and the step 3), the drying is carried out for 12-24 hours at the temperature of 100-120 ℃.
10. The method of claim 4, wherein: in the step 4), the granulation is carried out after polyvinyl alcohol accounting for 5-10% of the mass of the ceramic powder is added; the sieving is to sieve the mixture by a sieve of 60-100 meshes.
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