CN106673644B - Strontium titanate-based energy storage dielectric material for medium-temperature sintering - Google Patents
Strontium titanate-based energy storage dielectric material for medium-temperature sintering Download PDFInfo
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- 238000005245 sintering Methods 0.000 title claims abstract description 41
- 239000003989 dielectric material Substances 0.000 title claims abstract description 29
- 238000004146 energy storage Methods 0.000 title claims abstract description 21
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 37
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017676 MgTiO3 Inorganic materials 0.000 claims abstract description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 7
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 7
- 229910002971 CaTiO3 Inorganic materials 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000009413 insulation Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000012856 weighed raw material Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical class [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
The invention discloses a strontium titanate-based energy storage dielectric material for medium-temperature sintering, which is prepared from the following raw material components in parts by weight: 100 parts of SrTiO317.80 to 29.60 portions of CaTiO37.30 to 20.30 parts of Bi2O3·3TiO20.18-0.26 parts of MnCO30.06 to 0.17 part of Co2O30.60 to 3.06 portions of MgTiO30 to 0.15 part of Y2O30 to 0.18 part of CeO2The strontium titanate-based energy storage dielectric material can realize medium-temperature sintering (sintering temperature: 1140-1160 ℃), has a high dielectric constant (300-360) and low loss (tan: 3-10 × 10)‑4) High insulation resistivity (rho: 3.4-12.2 × 10)13Omega cm), high breakdown voltage (> 280kv/cm) and stable temperature coefficient (fluctuation range is within +/-500 ppm/DEG C); the MLCC trial production by adopting the energy storage medium material can meet the production process of the MLCC, and the MLCC has excellent comprehensive performance, good practical value and wide market prospect.
Description
Technical Field
The invention relates to the technical field of electronic information materials and components, in particular to a strontium titanate-based energy storage dielectric material for medium-temperature sintering, which can be used for MLCC production of silver-palladium inner electrodes for medium-temperature sintering.
Background
The high-energy-storage-density high-voltage-resistance MLCC is one of common electronic components in electronic equipment, has the advantages of high charging and discharging speed, strong cyclic aging resistance, stable performance in extreme environments such as high temperature and high voltage and the like, and has wide application prospect in the fields of hybrid electric vehicles, pulse power supplies, radars, aerospace and the like.
High energy storage density and miniaturization are the development trends of energy storage ceramic dielectric capacitors, and measures are mainly taken for the development trends: (1) optimizing a capacitor structure, and adopting a multilayer ceramic capacitor structure; (2) the dielectric material properties are improved, such as increased dielectric constant, increased breakdown strength, and reduced loss. At present, due to the limitation of equipment and process level, the multilayer ceramic dielectric capacitor structure is difficult to further improve. The development of a dielectric material with high dielectric constant, high breakdown strength and low loss, which can meet the requirements of the current MLCC production process, is an effective path for realizing high energy storage density and miniaturization.
At present, the dielectric materials commonly used as high voltage ceramic capacitors are: barium titanate series, antiferroelectric dielectric ceramics, titanium dioxide series, and strontium titanate series. The barium titanate ceramic has the advantage of high dielectric constant, but the application of the system in the field of high-voltage capacitors is limited due to the large dielectric loss (1-2%), low breakdown voltage (<100kV/cm) and electrostriction phenomenon; the antiferroelectric dielectric ceramic is mainly a lead zirconate titanate system, has the advantages of high dielectric constant, increased dielectric constant after voltage is applied and the like, but is a lead-containing material, can cause environmental pollution in the production and use processes, and is difficult to be widely applied along with the implementation of the limit or forbidding of related regulations on the lead-containing material; the titanium dioxide has the advantages of high breakdown voltage (about 350kV/cm), low dielectric loss (about 0.05 percent) and the like, but the low dielectric constant (about 110) is difficult to produce a capacitor with high energy storage density; the strontium titanate system has the advantages of relatively high dielectric constant (approximately equal to 250), low high-frequency loss, high breakdown strength and the like, and in addition, the strontium titanate is of a paraelectric structure at normal temperature, and the electric domain rotation cannot be caused by applying a certain external electric field, so that the reliability of the capacitor is improved, and the service life of the capacitor is prolonged.
Disclosure of Invention
Aiming at the defects existing in the problems, the invention provides the strontium titanate-based energy storage dielectric material for medium-temperature sintering, which has the advantages of higher dielectric constant, breakdown strength and insulation resistivity, lower loss and sintering temperature, stable and adjustable temperature coefficient and the like. .
In order to achieve the above object, the present invention provides a strontium titanate-based energy storage dielectric material for medium temperature sintering, which is composed of a main material, an auxiliary material, a modifier and a sintering aid, wherein:
the main material is SrTiO3；
The auxiliary material is CaTiO3And Bi2O3·3TiO2；
The modifier is MnCO3、MgTiO3、Co2O3、CeO2And Y2O3Three or more of (1);
the sintering aid BZS consists of H3BO3ZnO and SiO2And (4) forming.
As a further improvement of the invention, the dielectric material is based on 100 parts by weight of SrTiO3The base material comprises the following components in percentage by weight:
major material SrTiO3100 parts of the raw materials;
CaTiO as auxiliary material317.80-29.60 parts;
side material Bi2O3·3TiO27.30-20.30 parts;
3.50-4.00 parts of sintering aid BZS;
modifier MnCO30.18 to 0.26 portion;
modifier MgTiO30.60-3.06 parts;
modifier Co2O30 to 0.18 portion;
modifier Y2O30 to 0.15 portion;
modifier CeO20 to 0.18 portion;
weighing the components according to the weight, putting the components into a ball milling tank filled with zirconia balls, adding deionized water, ball milling, drying, grinding and sieving, and bagging for later use.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a strontium titanate-based energy storage dielectric material for medium-temperature sintering, which is prepared by adopting a traditional solid phase method, has higher dielectric constant, breakdown strength and insulation resistivity, lower loss and sintering temperature and stable and adjustable temperature coefficient; the dielectric material can be used for MLCC production of silver-palladium inner electrodes, MLCC process verification is carried out on the material (the thickness of a casting membrane is 30 mu m +/-0.3 mu m), manufacturability such as casting and sintering is good, the comprehensive performance of the produced MLCC is excellent, and the dielectric material has good practical value and market prospect.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The raw materials selected by the invention can be purchased through commercial channels if no special description is provided.
Aiming at the problems in the prior art, the strontium titanate-based ceramic material is prepared by combining the traditional solid phase method with the doping modification technology, has higher dielectric constant, breakdown strength and insulation resistivity, lower loss and sintering temperature and stable and adjustable temperature coefficient, and is an energy storage dielectric ceramic material with very promising prospect.
The invention provides a strontium titanate-based energy storage dielectric material for medium-temperature sintering, which is prepared from a main material SrTiO3CaTiO as a side material3And Bi2O3·3TiO2The modifier MnCO3、MgTiO3、Co2O3、CeO2And Y2O3Three or more than three of the raw materials and a sintering aid BZS, wherein the sintering aid BZS is H3BO3ZnO and SiO2And (4) forming. Wherein: major material SrTiO3The mass fraction of the dielectric material is 64.55 wt% -75.23 wt%, and the dielectric material is prepared by 100 weight parts of SrTiO3The base material comprises the following components in percentage by weight: major material SrTiO3100 portions of auxiliary material CaTiO317.80 to 29.60 portions of Bi as an auxiliary material2O3·3TiO27.30 to 20.30 parts of sintering aid BZS, 3.50 to 4.00 parts of,Modifier MnCO30.18 to 0.26 portion of modifier MgTiO30.60 to 3.06 portions of modifier Co2O30 to 0.18 portion of modifier Y2O30 to 0.15 portion and a modifier CeO20 to 0.18 portion. Wherein, the main material, the auxiliary material and the sintering auxiliary agent are all prepared by analytically pure chemical raw materials. The main material SrTiO3Is paraelectric structure, and is made of CaTiO3And Bi2O3·3TiO2The strontium titanate-based energy storage dielectric material is used for adjusting the temperature coefficient and the dielectric constant of the dielectric material, the modifier is used for optimizing comprehensive electrical properties, the sintering aid is used for reducing the sintering temperature, and finally the strontium titanate-based energy storage dielectric material with a serialized and stable temperature coefficient and excellent comprehensive properties for medium-temperature sintering is obtained.
The invention relates to a preparation method of a strontium titanate-based energy storage dielectric material for medium-temperature sintering, which comprises the following steps:
(1) to analytically pure SrCO3And TiO2Weighing SrCO as raw materials according to the molar ratio of 1:13And TiO2Putting the weighed raw materials into a ball milling tank filled with zirconia balls, mixing and ball milling the raw materials by taking deionized water as a medium, and carrying out ball milling for 7-9 hours; then drying in an oven at the drying temperature of 110-120 ℃ for 6-8 hours; then calcining the mixture for 2.5 hours in a muffle furnace at the temperature of 1100 +/-20 ℃ to obtain the main material SrTiO3And (3) powder.
(2) To analytically pure CaCO3And TiO2Weighing CaCO as raw material according to a molar ratio of 1:13And TiO2Putting the weighed raw materials into a ball milling tank filled with zirconia balls, and performing mixed ball milling for 5-6 hours by taking deionized water as a medium; then drying in an oven at the drying temperature of 110-120 ℃ for 6-8 hours; then calcined for 2.5 hours in a muffle furnace at 1050 +/-20 ℃ to obtain a secondary material CaTiO3And (3) powder.
(3) To analytically pure Bi2O3And TiO2Weighing Bi as raw material according to the molar ratio of 1:32O3And TiO2Putting the weighed raw materials into a ball milling tank filled with zirconia balls, and performing mixed ball milling for 5-6 hours by taking deionized water as a medium;then drying in an oven at the drying temperature of 110-120 ℃ for 6-8 hours; then calcining the mixture for 2 hours at 880 +/-30 ℃ in a muffle furnace to obtain a secondary material Bi2O3·3TiO2And (3) powder.
(4) Please supplement H in the sintering aid BZS3BO3ZnO and SiO2The mixture ratio and the preparation method of the composition are that H is weighed according to the mass ratio of 1:2.3:0.73BO3ZnO and SiO2(ii) a Deionized water is selected as a ball milling medium, and the ball milling time is 5 hours; drying at 85 deg.C for 10 hr, and sieving with 80 mesh sieve; the presintering temperature is 570 ℃, the presintering time is 5 hours, and then the furnace is cooled; and after grinding, sieving the mixture by a 100-mesh sieve to obtain the sintering aid BZS, and packaging and storing the sintering aid BZS by a self-sealing bag for later use.
(5) Weighing the main material, the auxiliary material, the modifier and the sintering aid according to the weight ratio of the raw materials in the table 1 (the unit is gram), ball-milling and mixing for 5 hours by taking deionized water as a medium, drying for 6 hours at 120 ℃, taking out ceramic powder, grinding, sieving by a 40-mesh sieve, and packaging and storing by a self-sealing bag.
TABLE 1 formulation of dielectric materials
The performance of the prepared ceramic material is checked: weighing 2g of ceramic powder, adding 6.5 wt% of PVA (polyvinyl alcohol) aqueous solution for granulation, pressing into a wafer with the phi of 10mm under 200MPa, putting the wafer into a resistance furnace, raising the temperature from room temperature to 500-600 ℃ at 2-3 ℃/min, preserving the heat for 2-3 hours, discharging glue, raising the temperature to 1150 +/-10 ℃ at 4-5 ℃/min, sintering into porcelain, cooling along with the furnace, carrying out sample surface treatment, coating and sintering an electrode. After the wafer capacitor is manufactured, the capacitance value, the loss, the insulation resistance and the breakdown voltage are tested, and the relative dielectric constant, the insulation resistivity and the breakdown field strength are calculated; the temperature characteristics were also tested, and the electrical properties are shown in Table 2.
TABLE 2 dielectric Material wafer Properties tabulation
The MLCC chip (with the average dielectric layer thickness of 20 mu m) with the capacity of 220nF is obtained by adopting the ceramic materials corresponding to the formula 1 and the formula 7 and carrying out batching, tape casting, printing, laminating, uniform pressing, binder removal, sintering (sintering temperature of 1150 ℃), chamfering, end coating, end burning and electroplating. The MLCC electrical properties are shown in Table 3.
TABLE 3 dielectric Material chip Properties
The strontium titanate-based energy storage dielectric material for medium-temperature sintering is prepared by adopting a traditional solid phase method, has high dielectric constant, breakdown strength and insulation resistivity, low loss and sintering temperature and stable and adjustable temperature coefficient. The dielectric material can be used for MLCC production of silver-palladium inner electrodes, MLCC process verification is carried out on the material (the thickness of a casting membrane is 30 mu m +/-0.3 mu m), manufacturability such as casting and sintering is good, the comprehensive performance of the produced MLCC is excellent, and the dielectric material has good practical value and market prospect.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (1)
1. The strontium titanate-based energy storage dielectric material for medium-temperature sintering is characterized by comprising a main material, an auxiliary material, a modifier and a sintering aid, wherein:
the main material is SrTiO3；
The auxiliary material is CaTiO3And Bi2O3·3TiO2；
The modifier is MnCO3、MgTiO3、Co2O3、CeO2And Y2O3Three or more of (1);
the sintering aid BZS consists of H3BO3ZnO and SiO2Composition is carried out;
the dielectric material is prepared by 100 weight parts of SrTiO3The base material comprises the following components in percentage by weight:
major material SrTiO3100 parts of the raw materials;
CaTiO as auxiliary material317.80-29.60 parts;
side material Bi2O3·3TiO27.30-20.30 parts;
3.50-4.00 parts of sintering aid BZS;
modifier MnCO30.18 to 0.26 portion;
modifier MgTiO30.60-3.06 parts;
modifier Co2O30 to 0.18 portion;
modifier Y2O30 to 0.15 portion;
modifier CeO20 to 0.18 portion;
weighing the components according to the weight, putting the components into a ball milling tank filled with zirconia balls, adding deionized water, ball milling, drying, grinding and sieving, and bagging for later use.
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