CN102568821A - High-voltage ceramic capacitor dielectric with high dielectric constant - Google Patents
High-voltage ceramic capacitor dielectric with high dielectric constant Download PDFInfo
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- CN102568821A CN102568821A CN2012100342781A CN201210034278A CN102568821A CN 102568821 A CN102568821 A CN 102568821A CN 2012100342781 A CN2012100342781 A CN 2012100342781A CN 201210034278 A CN201210034278 A CN 201210034278A CN 102568821 A CN102568821 A CN 102568821A
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Abstract
The invention relates to the technical field of inorganic non-metal material, in particular to a high-voltage ceramic capacitor dielectric with high dielectric constant, wherein the capacitor dielectric comprises following components in percentages by weight: 55-90% of BaTiO3, 2-25% of SrTiO3, 2-15% of MgZrO3, 2-10% of Bi3NbZrO3, 0.1-1.0% of CeO2, 0.5-1.5% of ZnO, 0.2-1.0% of MnCO3; the BaTiO3, SrTiO3, MgZrO3 and Bi3NbZrO3 are synthesized by normal chemical materials through a solid state method. The prepared capacitor ceramic material resists high voltage and more than 10kV/mm of direct-current voltage, has high dielectric constant which can reach more than 10000, small capacitance temperature change rate, meets requirement of Y5U characteristic, has less than 0.5% of dielectric loss, has good stable performance, high safety and no environment pollution during the usage.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, refer in particular to a kind of high dielectric high-voltage ceramic condenser medium; It adopts conventional ceramic capacitor dielectric preparation method, utilizes condenser ceramics general chemistry raw material, prepares height Jie high-voltage ceramic condenser medium unleaded, no cadmium, can also reduce the sintering temperature of condenser ceramics; This medium is suitable for preparing monolithic ceramic capacitor and multiple-layer sheet ceramic capacitor, can reduce the cost of ceramic capacitor greatly, can improve the range of application of proof voltage with the expansion ceramic capacitor simultaneously, and free from environmental pollution in preparation and use.
Background technology
Fields such as colour TV, computer, communication, Aero-Space, guided missile, navigation press for the puncture voltage height, temperature stability is good, reliability is high, miniaturization, jumbo ceramic capacitor; The sintering temperature of general single-chip high voltage ceramic capacitor dielectric is 1300 ~ 1430 ℃; And ceramic capacitor dielectric sintering temperature of the present invention is 1250 ~ 1270 ℃; Can reduce the cost of high voltage ceramic capacitor so greatly; The not leaded and cadmium of while this patent capacitor ceramic dielectric, condenser ceramics is free from environmental pollution in preparation and use; In addition, the dielectric constant of condenser ceramics of the present invention is high, and the capacity and the miniaturization that can improve ceramic capacitor like this meet the development trend of ceramic capacitor, equally also can reduce the cost of ceramic capacitor.
Be generally used for producing in the medium of high voltage ceramic capacitor and contain a certain amount of lead, this not only produce, use and discarded process in human body and environment are worked the mischief, and stability is also had harmful effect.
Chinese periodical " electronic component and material " the 5th phase in 1989 is at " high Jie's high pressure 2B
4Media ceramic " a kind of high-voltage ceramic condenser medium material is disclosed in the literary composition, this dielectric material adopts 97.8wt.%BaTiO
3+ 0.8wt.%Bi
2O
3+ 0.7wt.%Nb
2O
5+ 0.5wt.%CeO
2+ 0.2wt.%MnO
2Prescription, with the prepared sample of routine, its DIELECTRIC CONSTANTS=2500 ~ 2600, tg δ=0.5-1.4%, DC break down voltage intensity is 7KV/mm, though this medium belongs to unleaded dielectric material, it exists resistance to pressure relatively poor, dielectric constant is too little.Prescription is formed and is different from this patent.
Chinese patent " a kind of high-voltage ceramic condenser medium " (patent No. ZL00112050.6) is though disclosed capacitor ceramic dielectric belongs to unleaded dielectric material; But dielectric constant is 1860-3300; Proof voltage can reach 10kV/mm above (direct current); Sintering temperature is 1260-1400 ℃, and is higher than this patent; Dielectric constant is too little, and far below this patent, and the prescription composition is different from this patent.
Chinese periodical " Jiangsu pottery " the 2nd phase in 1999 is at " BaTiO
3Be the high Jie X7R of easy fired capacitor ceramics " a kind of BaTiO is disclosed in the literary composition
3High Jie of middle easy fired satisfied the capacitor ceramics of X7R characteristic, and the prescription of this dielectric material consists of (mass percent): (BaTiO
3+ Nd
2O
3) 89% ~ 92%+Bi
2O
32TiO
27.5 ~ 10%+ low-melting glass material 0.8%+50%Mn (NO
3)
2(aqueous solution) 0.205%; Wherein, used low-melting glass material is the lead borosilicate low-melting glass, and medium is leaded, and does not relate to proof voltage, and dielectric constant is less than 3500, and much smaller than the dielectric constant of this patent, the prescription of medium is formed and also is different from patent of the present invention.
Chinese periodical " South China Science & Engineering University's journal (natural science edition) " the 3rd phase in 1996 is at " intermediate sintering temperature BaTiO
3Quito mutually ferroelectric porcelain X7R characteristic " inquired into BaTiO in the literary composition
3Base porcelain intermediate sintering temperature mechanism has been analyzed intermediate sintering temperature BaTiO
3The composition of base porcelain and uneven texture distribute to the influence of dielectric constant and temperature characterisitic; Used BaTiO
3Raw material is to adopt the method for chemical coprecipitation to prepare, and can increase the cost of ceramic capacitor like this, and the used BaTiO of this patent
3, SrTiO
3, CaZrO
3Be respectively to adopt conventional chemical raw material synthetic, form and be different from this patent, contain a certain amount of lead in the component, and do not relate to proof voltage with solid phase method.
Other has patent " high Jie's high-performance intermediate sintering temperature chip multilayer ceramic capacitor porcelain ", and (number of patent application: 97117286.2), it is to adopt synthetic equivalence of solid phase method and different valency ion to replace (Sr simultaneously
2+, Zr
4+, Sn
4+, Nb
5+) BaTiO
3Solid solution adds an amount of boron-lead-zinc-copper glass agglutinant, makes porcelain at intermediate sintering temperature, and its performance is: dielectric constant is more than or equal to 16000, and withstand voltage is 700V/mm; Though this patent dielectric constant is high, the material of being reported withstand voltage too poor is merely 700V/mm, and its component contains a certain amount of lead in addition.
Other has patent " manufacturing approach of high-voltage ceramic condenser medium " (patent No. 91101958.8); It adopts unconventional prepared medium; Be the flow casting molding film, laminated medium body then, with the multilayer dielectricity body carry out the even pressure of heating in vacuum, punching, then carry out binder removal, burn till and get; The shortcoming of this patent be preparation technology's method complicated, cause cost of goods manufactured to increase, the dielectric constant of making the high-voltage capacitor pottery of gained by its medium prescription is 1800-7200, dielectric constant is too little, does not have the dielectric constant of this patent high.
(number of patent application: 97117287.0), it adopts unique prescription (percentage by weight) (BaTiO to also have Chinese patent " high-performance intermediate sintering temperature chip multilayer ceramic capacitor porcelain "
393 ~ 96%+Nb
2O
50.8 ~ 1.5%+Bi
2O
31.0 ~ 2.2%+ flux 1.8 ~ 3.5%+ modifier 0.25 ~ 1.0%) obtain the condenser ceramics that satisfies following performance of intermediate sintering temperature: dielectric constant is 3000, and dielectric loss is less than 1.5%, and withstand voltage is 860V/mm; The flux of this patent contains a certain amount of lead, and the proof voltage of this patent is too poor, and dielectric constant is too low simultaneously, much smaller than this patent.
(number of patent application: 200410041863.x), it adopts unique prescription (percentage by weight) (BaTiO to also have Chinese patent " a kind of low temperature sintering high-voltage ceramic condenser medium "
360-90%, SrTiO
31-20% CaZrO
30.1-10%, Nb
2O
50.01-1%, MgO0.01-1%, CeO
20.01-0.8%, ZnO0.01-0.6%, Co
2O
30.03-1%; Bismuth lithium solid solution 0.05-10%) obtain the condenser ceramics that satisfies following performance of intermediate sintering temperature: dielectric constant is 2000 ~ 3000; Proof voltage is more than the 6kV/mm; The additive that reduces sintering temperature is a bismuth lithium solid solution, and the dielectric constant of this patent and proof voltage are high less than this patent, and the prescription of this patent is formed and is different from this patent.
Summary of the invention
The purpose of this invention is to provide a kind of high dielectric high-voltage ceramic condenser medium.
The objective of the invention is to realize like this:
Said high dielectric high-voltage ceramic condenser medium formula constituent is counted by weight percentage: BaTiO
355-90%, SrTiO
32-25%, MgZrO
32-15%, Bi
3NbZrO
32-10%, CeO
20.1-1.0%, ZnO 0.5-1.5%,, MnCO
30.2-1.0%; BaTiO wherein
3And SrTiO
3, MgZrO
3, Bi
3NbZrO
3Be respectively to adopt conventional chemical raw material synthetic with solid phase method.
Used MgZrO in the medium of the present invention
3Be to adopt following prepared: with the chemical raw material MgO and the ZrO of routine
2Press the 1:1 molar ratio ingredient, put into alumina crucible in 1200 ℃-1230 ℃ insulations 120 minutes after ground and mixed is even, solid phase reaction is synthesized MgZrO
3, ground 200 mesh sieves after the cooling, subsequent use.
Used Bi in the medium of the present invention
3NbZrO
3Be to adopt following prepared: with the chemical raw material Bi of routine
2O
3, Nb
2O
5And ZrO
2Press the 3/2:1/2:1 molar ratio ingredient, put into alumina crucible in 900 ℃-960 ℃ insulations 120 minutes after ground and mixed is even, solid phase reaction is synthesized Bi
3NbZrO
3, ground 200 mesh sieves after the cooling, subsequent use.
The present invention adopts conventional high-voltage ceramic condenser medium preparation technology, promptly at first adopts conventional chemical raw material with the synthetic respectively BaTiO of solid phase method
3, SrTiO
3, MgZrO
3, Bi
3NbZrO
3, by the prescription batching batch ball mill grinding is mixed then, after drying; Add the adhesive granulation, be pressed into green sheet again, in air, carry out binder removal and sintering then; Behind insulation and natural cooling, obtain ceramic capacitor dielectric, on medium by electrode.
The prescription of above-mentioned ceramic dielectric preferably adopts following three kinds of schemes (percentage by weight):
BaTiO
360-86%,SrTiO
33-22%,MgZrO
33-12%,Bi
3NbZrO
33-8%,CeO
20.2-0.6%,ZnO0.8-1.3%?,?MnCO
30.2-0.8%；
BaTiO
365-83%,SrTiO
33-19%,MgZrO
34-10%,Bi
3NbZrO
33-8%,CeO
20.2-0.6%,ZnO0.9-1.2%,?MnCO
30.4-0.7%；
BaTiO
370-81%,SrTiO
35-15%,MgZrO
33-8%,Bi
3NbZrO
34-7%,CeO
20.2-0.6%,ZnO0.9-1.2%?,?MnCO
30.5-0.7%。
The present invention compared with prior art has following advantage:
1, the medium of this patent is intermediate sintering temperature (1250 ~ 1280 a ℃) barium strontium based capacitor pottery, can reduce the cost of high voltage ceramic capacitor so greatly, not leaded and cadmium in the media components of this patent, environmentally safe.
2, the dielectric constant of this medium is high, is more than 10000; Proof voltage is high, and the direct current proof voltage can reach more than the 10kV/mm; Dielectric loss is little, less than 0.5%; The dielectric constant of this medium is high, can realize the miniaturization and big capacity of ceramic capacitor, can reduce cost equally.
3, the percentage of capacitance variation with temperature of this medium is little, meets the requirement of Y5U characteristic; Dielectric loss is less than 0.5%, and stability is good in the use, and is safe.
4, primary raw material employing ceramic capacitor level is pure can produce ceramic dielectric of the present invention.
5, this medium adopts conventional solid phase method ceramic capacitor dielectric preparation technology to prepare.
Embodiment
Combine embodiment that the present invention is done further description now.Table 1 provides the embodiments of the invention prescription of totally 9 samples.
The embodiments of the invention primary raw material of the prescription of totally 9 samples adopt the ceramic capacitor level pure, at first adopt conventional chemical raw material with the synthetic respectively BaTiO of solid phase method in the preparation
3, SrTiO
3, MgZrO
3, Bi
3NbZrO
3, by above-mentioned prescription batching, the material for preparing is adopted the planetary ball mill ball mill mixing with distilled water or deionized water, material: ball: the mass ratio=1:3 of water: (0.6 ~ 1.0) then; Behind the ball milling 4 ~ 8 hours, dry dry mash, in dry mash, add the concentration account for its weight 8 ~ 10% and be 10% poly-vinyl alcohol solution, carry out granulation; 40 mesh sieves are crossed in the mixed back of grinding, and under 20 ~ 30Mpa pressure, carry out dry-pressing again and become green sheet, and binder removal and sintering were carried out in insulation in 1 ~ 4 hour under temperature is 1250 ~ 1270 ℃ then; Be incubated 15 minutes down at 780 ~ 870 ℃ again and carry out silver ink firing, form silver electrode, solder taul again; Seal, promptly get ceramic capacitor, test its dielectric property; Above-mentioned dielectric property of respectively filling a prescription sample are listed in table 2, can find out that from table 2 prepared condenser ceramics proof voltage is high, can reach 10kV/mm (direct voltage, DC) more than; Dielectric constant is more than 10000; Dielectric loss is less than 0.5%; Percentage of capacitance variation with temperature is little, meets the requirement of Y5U characteristic.
Table 1 embodiments of the invention are the prescription of totally 9 samples
Respectively the fill a prescription dielectric property of sample of table 2
Claims (5)
1. one kind high dielectric high-voltage ceramic condenser medium is characterized in that: the component of said condenser dielectric is counted by weight percentage and is BaTiO
355-90%, SrTiO
32-25%, MgZrO
32-15%, Bi
3NbZrO
32-10%, CeO
20.1-1.0%, ZnO 0.5-1.5%,, MnCO
30.2-1.0%; BaTiO wherein
3, SrTiO
3, MgZrO
3And Bi
3NbZrO
3Be respectively to adopt conventional chemical raw material synthetic with solid phase method.
2. a kind of high dielectric high-voltage ceramic condenser medium as claimed in claim 1 is characterized in that: BaTiO
360-86%, SrTiO
33-22%, MgZrO
33-12%, Bi
3NbZrO
33-8%, CeO
20.2-0.6%, ZnO0.8-1.3%, MnCO
30.2-0.8%.
3. a kind of high dielectric high-voltage ceramic condenser medium as claimed in claim 1 is characterized in that: BaTiO
365-83%, SrTiO
33-19%, MgZrO
34-10%, Bi
3NbZrO
33-8%, CeO
20.2-0.6%, ZnO0.9-1.2%, MnCO
30.4-0.7%;
A kind of high dielectric high-voltage ceramic condenser medium as claimed in claim 1 is characterized in that: BaTiO
370-81%, SrTiO
35-15%, MgZrO
33-8%, Bi
3NbZrO
34-7%, CeO
20.2-0.6%, ZnO0.9-1.2%, MnCO
30.5-0.7%.
4. a kind of high dielectric high-voltage ceramic condenser medium as claimed in claim 1 is characterized in that: said MgZrO
3Be to adopt following prepared: with the chemical raw material MgO and the ZrO of routine
2Press the 1:1 molar ratio ingredient, put into alumina crucible in 1200 ℃-1230 ℃ insulations 120 minutes after ground and mixed is even, solid phase reaction is synthesized MgZrO
3, ground 200 mesh sieves after the cooling, subsequent use.
5. a kind of high dielectric high-voltage ceramic condenser medium as claimed in claim 1 is characterized in that: described Bi
3NbZrO
3Be to adopt following prepared: with the chemical raw material Bi of routine
2O
3, Nb
2O
5And ZrO
2Press the 3/2:1/2:1 molar ratio ingredient, put into alumina crucible in 900 ℃-960 ℃ insulations 120 minutes after ground and mixed is even, solid phase reaction is synthesized Bi
3NbZrO
3, ground 200 mesh sieves after the cooling, subsequent use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210034278.1A CN102568821B (en) | 2012-02-16 | 2012-02-16 | High-voltage ceramic capacitor dielectric with high dielectric constant |
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|---|---|---|---|
| CN201210034278.1A CN102568821B (en) | 2012-02-16 | 2012-02-16 | High-voltage ceramic capacitor dielectric with high dielectric constant |
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| CN102568821A true CN102568821A (en) | 2012-07-11 |
| CN102568821B CN102568821B (en) | 2015-02-04 |
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|---|---|---|---|
| CN201210034278.1A Expired - Fee Related CN102568821B (en) | 2012-02-16 | 2012-02-16 | High-voltage ceramic capacitor dielectric with high dielectric constant |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408301A (en) * | 2013-07-19 | 2013-11-27 | 江苏大学 | Ultrahigh voltage ceramic capacitor medium and preparation method thereof |
| CN104692800A (en) * | 2015-02-04 | 2015-06-10 | 桂林理工大学 | Temperature-stable lead-free giant dielectric constant ceramic material |
| CN106587996A (en) * | 2016-11-14 | 2017-04-26 | 江苏大学 | High-frequency granular-boundary-layer ceramic capacitor dielectric |
| CN106587989A (en) * | 2016-11-15 | 2017-04-26 | 江苏大学 | High-dielectric performance grain boundary layer ceramic capacitor medium |
| CN107369554A (en) * | 2017-08-30 | 2017-11-21 | 苏州惠华电子科技有限公司 | A kind of manufacture method of capacitor |
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| US20070247066A1 (en) * | 2004-04-06 | 2007-10-25 | Idemitsu Kosan Co., Ltd. | Electrode Substrate and Its Manufacturing Method |
| CN102101775A (en) * | 2010-12-08 | 2011-06-22 | 汕头高新区松田实业有限公司 | Low-loss high-voltage ceramic capacitor dielectric |
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2012
- 2012-02-16 CN CN201210034278.1A patent/CN102568821B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070247066A1 (en) * | 2004-04-06 | 2007-10-25 | Idemitsu Kosan Co., Ltd. | Electrode Substrate and Its Manufacturing Method |
| CN102101775A (en) * | 2010-12-08 | 2011-06-22 | 汕头高新区松田实业有限公司 | Low-loss high-voltage ceramic capacitor dielectric |
Non-Patent Citations (1)
| Title |
|---|
| 彭家根等: "高压电容器用铁电陶瓷", 《电子元件与材料》, vol. 25, no. 12, 31 December 2006 (2006-12-31), pages 17 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408301A (en) * | 2013-07-19 | 2013-11-27 | 江苏大学 | Ultrahigh voltage ceramic capacitor medium and preparation method thereof |
| CN103408301B (en) * | 2013-07-19 | 2015-04-22 | 江苏大学 | Ultrahigh voltage ceramic capacitor medium and preparation method thereof |
| CN104692800A (en) * | 2015-02-04 | 2015-06-10 | 桂林理工大学 | Temperature-stable lead-free giant dielectric constant ceramic material |
| CN104692800B (en) * | 2015-02-04 | 2016-08-24 | 桂林理工大学 | A kind of temperature-stable unleaded huge dielectric constant ceramic material |
| CN106587996A (en) * | 2016-11-14 | 2017-04-26 | 江苏大学 | High-frequency granular-boundary-layer ceramic capacitor dielectric |
| CN106587996B (en) * | 2016-11-14 | 2020-03-31 | 江苏大学 | High-frequency grain boundary layer ceramic capacitor medium |
| CN106587989A (en) * | 2016-11-15 | 2017-04-26 | 江苏大学 | High-dielectric performance grain boundary layer ceramic capacitor medium |
| CN106587989B (en) * | 2016-11-15 | 2019-08-02 | 江苏大学 | A kind of high dielectric property grain boundary layer ceramic capacitor medium |
| CN107369554A (en) * | 2017-08-30 | 2017-11-21 | 苏州惠华电子科技有限公司 | A kind of manufacture method of capacitor |
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| CN102568821B (en) | 2015-02-04 |
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