CN101567264A - Base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor - Google Patents
Base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor Download PDFInfo
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- CN101567264A CN101567264A CNA2008100942549A CN200810094254A CN101567264A CN 101567264 A CN101567264 A CN 101567264A CN A2008100942549 A CNA2008100942549 A CN A2008100942549A CN 200810094254 A CN200810094254 A CN 200810094254A CN 101567264 A CN101567264 A CN 101567264A
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Abstract
The invention relates to base metal nickel internal electrode slurry of a microwave multiple-layer sheet ceramic capacitor, which comprises 40 to 50 of high-crystallinity nanometer nickel powder, 2 to 10 of yttrium oxide stable zirconia nanometer powder bodies and 40 to 58 of organic carriers according to the weight percentage, wherein the organic carriers comprise 2 percent to 6 percent of cellulosic resin and 38 percent to 52 percent of dihydroterpineol. Aiming at the stress problem of a metal part and a ceramic part of the microwave multiple-layer sheet ceramic capacitor, the invention can reduce the volume change caused by the phase change to reduce the internal stress, microcracks of a dielectric layer are reduced to increase the reliability of the microwave ceramic capacitor, and consequently, the microwave multiple-layer sheet ceramic capacitor can also use a base metal nickel electrode technology to replace the prior silver palladium noble metal technology. The invention saves social resources, greatly reduces the production cost and quickly realizes the industrialization.
Description
Technical field
The present invention relates to a kind of base metal nickel internal electrode slurry, particularly use high crystallization nano-nickel powder, stabilized with yttrium oxide nano zirconium oxide powder as raw material and be used to make the slurry of microwave multiple-layer sheet ceramic capacitor.
Background technology
The conditional electronic slurry generally is a conductive silver paste, conduction palladium slurry, conduction gold paste, noble metal slurries such as resistance slurry.But nearly ten years, base metal nickel electrocondution slurry development cheaply was swift and violent, and its main application is a multiple-layer sheet ceramic capacitor.Along with the miniaturization of complete machine, the increasing sharply of mobile electronic device, the development of multiple-layer sheet ceramic capacitor is also very rapid.Traditional noble metal slurry has made the user bear obviously aspect cost.The multiple-layer sheet ceramic capacitor of base metal nickel electrode has not only reduced the cost of multiple-layer sheet ceramic capacitor significantly, and has solved high lamination better at technical elements, filming, big capacity, undersized problem.Therefore the base metal nickel electric slurry has obtained development at full speed nearly ten years the insides.
The base metal nickel slurry of China began to research and develop low frequency multilayer ceramic capacitor nickel electrode slurry in 2003, and progressively was applied in the multiple-layer sheet ceramic capacitor.In fact up to the present, still there is such nickel electrode slurry of 70% need be from external import.And effectively do not broken through for the base metal nickel internal electrode slurry of the mentioned microwave multiple-layer sheet ceramic capacitor of the present invention all the time.Its main cause is the matching problem that can not effectively solve ceramic body and metal nickel powder, can not solve the internal stress problem that the additive phase transformation causes, thereby causes ceramic capacitor inner micro-crack to occur.These micro-cracks will finally cause the inefficacy of ceramic capacitor.
Disclose the electronic ceramic parts of a kind of electrocondution slurry and lamination among the Chinese patent CN1171242C, this kind electrocondution slurry also contains conduction nickel powder, organic carrier, compd A and compd B; Compd A is at least a in the organic complex salt of metal salts of organic acids, oxide powder, metal that is selected from calcium and/or magnesium and/or the alkoxide; Compd B is titaniferous and/or zirconium, have can hydrolysis the reactive group compound.The advantage of this conductive nickel slurry is that the interlayer that can solve common low frequency multilayer ceramic capacitor splits problem, has improved the heat-resisting cataclysm and the moisture resistance load property of ceramic capacitor.
Also disclose the electronic ceramic parts of a kind of electrocondution slurry and lamination among the Chinese patent CN1171243C, this kind electrocondution slurry also contains conduction nickel powder, organic carrier, compd A and compd B; Compd A is at least a in the organic complex salt of metal salts of organic acids, oxide powder, metal that is selected from calcium and/or magnesium and/or the alkoxide; Compd B then be contain aluminium and/or silicon, have can hydrolysis the reactive group compound.The purpose of this conductive nickel slurry is that the interlayer that solves common low frequency multilayer ceramic capacitor splits problem equally, has improved the heat-resisting cataclysm and the moisture resistance load property of ceramic capacitor.
A kind of electrocondution slurry is disclosed among the Chinese patent application CN1598982A.This kind electrocondution slurry also contains conduction nickel powder, ceramic additive, organic carrier.Ceramic additive is BaTi
0.8Zr
0.2O
3, BaTiO
3, CaZrO
3In one or several.The purpose of this conductive nickel slurry remains the interlayer that solves common low frequency multilayer ceramic capacitor and splits problem.
More than three China apply for a patent the slabbing problem that has all solved emphatically between layer and the layer, still can not effectively solve the dielectric layer micro-crack problem (non-interlayer splits) that the internal stress of microwave multilayer ceramic capacitor causes.Although in fact solved the problem of splitting between layer and the layer, still need more difficult metal part of deep solution and ceramic body stress problem partly.The change in volume that this because phase transformation causes must cause the long-term existence of internal stress, has caused the micro-crack of dielectric layer to produce.From above three patent formulations, all do not consider problem and difficulty that this is more deep.
Summary of the invention
The objective of the invention is deep solution metal part and ceramic body stress problem partly, reduce the change in volume that phase transformation causes, reach the purpose that reduces internal stress, the micro-crack that reduces dielectric layer produces, the capacitor reliability of raising microwave ceramics.
Technical scheme of the present invention is: a kind of base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor, comprise that weight percentage is the high-crystallinity nano-nickel powder of 40-50%, weight percentage is the yttria-stabilized zirconia nano-powder of 2-10%, weight percentage is the organic carrier of 40-58%, and described organic carrier is made up of the cellulosic resin of 2-6% and the dihydroterpineol of 38-52%.
Preferably, the nano-nickel powder of described high-crystallinity is to adopt the preparation of physical vapor method, and its granularity D50 is 0.4-1.0um.
Preferably, the granularity of described yttria-stabilized zirconia nano-powder is 5-200nm.
Preferably, described cellulosic resin is ethyl cellulose or hydroxyethylcellulose, and viscosity is 10-50mpa.s.
The present invention has selected the nano-nickel powder of high crystallization for use, the narrower D50:0.4～1.0um of particle size range, and have high anti-oxidation characteristics.Because it is higher that the sintering temperature of microwave class ceramic capacitor than the temperature height of common low frequency class capacitor, causes nickel to starch required bearing temperature ability.The nickel powder of high-crystallinity has higher heatproof degree, the contraction in the time of can effectively reducing by 1330 degree sintering, the cracking of minimizing interlayer.Because it is a variety of that the manufacture method of nickel powder has, and wet method and dry method are arranged, the differentiation of physics method and chemical method, the characteristic of the nickel powder that every kind of method obtained is different, so that the nickel powder of high-crystallinity is selected for use is very crucial.We have selected the nickel powder of physical vapor method herein, have high degree of crystallinity and good sphericity.Nickel powder particle size range D50:0.4-1.0um, it is excessive in the contraction of low temperature that granularity is crossed low then nickel slurry, causes lamination easily; The too high then surface roughness height of interior electrode of granularity causes the withstand voltage decline of ceramic capacitor.The addition of the high crystallization nickel powder of nanometer is 40-50%, and the nickel ratio is too low, will cause internal electrode discontinuous, poorly conductive, it is poor that internal and external electrode connects, and the capacitance of multiple-layer sheet ceramic capacitor will descend, loss value will rise, thereby microwave property can not effectively be embodied; The nickel ratio is too high, will cause thickness of electrode blocked up, and ceramic body shrinkage and metallic nickel shrinkage do not match, thereby causes the appearance of lamination, equally also can cause internal stress to increase.
The selected nano zirconium oxide powder of the present invention is the stabilized with yttrium oxide modification, particle size range 5～200 nanometers, the little characteristics of change in volume when having phase transformation simultaneously.Can selecting for use of yttria-stabilized zirconia nano-powder be the most key, determined effectively solve the micro-crack that internal stress causes.ZrO through stabilized with yttrium oxide
2Volume is relatively stable in whole process, thereby therefore can not produce the appearance that bigger internal stress has overcome the later stage micro-crack in the later stage.Patent is before this directly selected for use and ceramic body CaZrO mostly
3Identical or close ceramic additive is perhaps selected ZrO for use
2Deng ceramic masses; The interlayer that this type of ceramic additive can to a certain degree solve multilayer ceramic capacitor really splits problem, still but can not solve the micro-crack problem that dielectric layer and metallic nickel stress cause.The additional proportion of yttria-stabilized zirconia nano-powder is 2-10%, and ratio is too high, will cause internal electrode discontinuous, poorly conductive, it is poor that internal and external electrode connects, and the capacitance of multiple-layer sheet ceramic capacitor will descend, loss value will rise, thereby microwave property can not effectively be embodied; Ratio is low excessively, will cause in the electrode tenor too high, and ceramic body shrinkage and metallic nickel shrinkage do not match, thereby cause the appearance of lamination, equally also can cause internal stress to increase, and causes the generation of micro-crack.
The use amount of organic carrier of the present invention is 40%-58%: the dihydroterpineol that comprises cellulosic resin and environmental protection smell gentleness.The adding of organic carrier can be satisfied the needs of the silkscreen process in the multiple-layer sheet ceramic capacitor production so that nickel internal electrode slurry has suitable rheological characteristic and thixotropy; The adding of organic carrier simultaneously makes electrode size be more suitable for processing, and the viscosity in the course of processing changes littler.The adding of organic carrier also can reach and disperse and the effect of bonding metal nickel powder, ceramic additive, makes these solid matters can form a stable dispersion.Organic carrier also can be realized the bonding of multilayer ceramic capacitor layer and interlayer, forms a firm integral body behind the whole lamination of process.And these organic carriers, almost all decompose and get rid of through after the Degumming Procedures of ceramic capacitor as the intermediate material of a course of processing, and the final performance to ceramic capacitor does not impact.The selection principle of resin is that viscosity is suitable, the needs of the suitable silk screen printing of viscosity after adding solvent and other materials and rolling slurry; Requiring to decompose substantially below 325 degree binder removal simultaneously finishes.Too high viscosity causes and can't print smoothly and levelling, thereby the patterned surface after the printing is coarse, influences performance; Crossing figure after low viscosity causes printing, to ooze the limit serious, influences performance equally.
Beneficial effect of the present invention is: at the stress problem of microwave multiple-layer sheet ceramic capacitor metal part with the ceramic body part, the present invention can reduce the change in volume that phase transformation causes, reach the purpose that reduces internal stress, the micro-crack that reduces dielectric layer produces, and improves the reliability of microwave ceramic capacitance device; Thereby make microwave multiple-layer sheet ceramic capacitor also can use the technology of base metal nickel electrode, substitute silver-colored palladium noble metal technology in the past, save social resources, reduce production costs greatly, realize industrialization rapidly.
Description of drawings
The high-crystallinity nano-nickel powder microscopic appearance figure that the employing physical vapor method that Fig. 1 uses for the present invention prepares;
Fig. 2 is for adopting the nano-nickel powder microscopic appearance figure of chemical gas-phase method preparation;
Fig. 3 is for adopting the ceramic capacitor section petrographic microscope figure of preparing electrode paste of the present invention;
Fig. 4 is for adopting the ceramic capacitor section petrographic microscope figure of Comparative Examples 2 described preparing electrode paste.
Embodiment
The base metal nickel internal electrode slurry of a kind of microwave multiple-layer sheet ceramic capacitor of the present invention, comprise that weight percentage is the high-crystallinity nano-nickel powder of 40-50%, the yttria-stabilized zirconia nano-powder of 2-10%, the organic carrier of 40-58%, described organic carrier is made up of the cellulosic resin of 2-6% and the dihydroterpineol of 38-52%.
Introduce a kind of implementation method in the method for preparing electrode slurry of the present invention below, comprise the steps:
1. with the dihydroterpineol of 2-6% ethyl cellulose, 15%-20% in 68 degree heating 60 minutes and in process, stir and make it fully dissolve twice, obtain organic carrier A;
2. high-crystallinity nano-nickel powder, stabilized with yttrium oxide nano zirconium oxide powder are proportionally fully mixed and obtain mixture B;
3. in mixture B, add the organic carrier that accounts for the dihydroterpineol of total amount 8-12% and occupy airborne body A20%, fully mix and obtain mixture C;
4. with mixture C roll compacting 3 times in three rolling pulp grinders, add organic carrier that occupies airborne body A80% and the dihydroterpineol that accounts for total amount 15-20% then, roll compacting 2 times in three rolling pulp grinders once more obtains base metal nickel internal electrode slurry of the present invention.
After preparing electrode paste is good, prepare ceramic capacitor according to the technological process for preparing multiple-layer sheet ceramic capacitor: batching is made ceramic size, and curtain coating becomes ceramic diaphragm; the silk screen printing internal electrode slurry, dislocation lamination, whole lamination; cut into living embryo; come unstuck gas-protecting sintering, rounding; the extreme copper of external electric; outer electrode burns copper, and electroless nickel layer and tin layer are made into complete multiple-layer sheet ceramic capacitor.
Introduce for example the performance of the multiple-layer sheet ceramic capacitor that adopts preparing electrode paste of the present invention below, and with the contrast of prior art.
Sequence number 1-9 is 9 kinds of prescriptions of electrode slurry of the present invention in the table 1, and raw material is: adopt the nano-nickel powder of the high-crystallinity of physical vapor method preparation, its granularity is D50:0.4-1.0um, as shown in Figure 1, the degree of crystallinity height, good sphericity is easily disperseed; Yttria-stabilized zirconia nano-powder, granularity are 5-200nm; Organic carrier is the mixture of ethyl cellulose and dihydroterpineol.The prescription of Comparative Examples 1 and Comparative Examples 2 is: adopt the nickel powder of chemical gas-phase method preparation and calcium zirconate to mix, be illustrated in figure 2 as nickel powder microscopic appearance figure, sphericity is good inadequately as can be seen, and degree of crystallinity is not high; With ethyl cellulose and terpinol is organic carrier.
Table 2 is for adopting the performance of the multiple-layer sheet ceramic capacitor of corresponding electrode pulp preparation in the table 1.Be illustrated in figure 3 as the section petrographic microscope figure of the multiple-layer sheet ceramic capacitor that adopts preparing electrode paste of the present invention, as can be seen, whole plane solid colour, surface stress is evenly distributed, and does not have micro-crack.Be illustrated in figure 4 as the section petrographic microscope figure of the multiple-layer sheet ceramic capacitor that adopts Comparative Examples 2 described preparing electrode paste, as can be seen, there is one deck ceramic dielectric w to have the phenomenon of turning white, shows that this layer ceramic dielectric and other ply stress are inconsistent, have micro-crack.
The prescription of table 1 electrode slurry of the present invention and Comparative Examples electrode slurry
Table 2 adopts the performance of the ceramic capacitor of corresponding electrode pulp preparation in the table 1
| Sequence number | Micro-crack | Electrical property | Reliability | The product rank |
| 1 | 1/20000 | Excellent | In | In |
| 2 | 3/20000 | Very | In | In |
| 3 | 0 | Very | Very | Very |
| 4 | 0 | Very | Very | Very |
| 5 | 0 | Excellent | Excellent | Excellent |
| 6 | 0 | Excellent | Excellent | Excellent |
| 7 | 0 | In | In | In |
| 8 | 0 | In | Very | In |
| 9 | 0 | Very | Very | Very |
| 10 | 13/20000 | Excellent | Difference | Difference |
| 11 | 48/20000 | Very | Difference | Difference |
Associative list 1, table 2 and Fig. 3, Fig. 4 select suitable nickel powder ratio as can be seen, suitable ceramic additive and ratio thereof, and suitable carriers kind and ratio can obtain superior in quality base metal nickel internal electrode slurry.This slurry can effectively solve the micro-crack problem of multiple-layer sheet ceramic capacitor inside, realizes the application of nickel electrode base metal material on the microwave multilayer ceramic capacitor, substitutes expensive silver-colored palladium noble metal electrode material, enhances competitiveness greatly.
Claims (4)
1, a kind of base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor, it is characterized in that: comprise that weight percentage is the high-crystallinity nano-nickel powder of 40-50%, weight percentage is the yttria-stabilized zirconia nano-powder of 2-10%, weight percentage is the organic carrier of 40-58%, and described organic carrier is made up of the cellulosic resin of 2-6% and the dihydroterpineol of 38-52%.
2, the base metal nickel internal electrode slurry of a kind of microwave multiple-layer sheet ceramic capacitor as claimed in claim 1 is characterized in that: the nano-nickel powder of described high-crystallinity is to adopt the preparation of physical vapor method, and its granularity is D50:0.4-1.0um.
3, the base metal nickel internal electrode slurry of a kind of microwave multiple-layer sheet ceramic capacitor as claimed in claim 1 is characterized in that: the granularity of described yttria-stabilized zirconia nano-powder is 5-200nm.
4, the base metal nickel internal electrode slurry of a kind of microwave multiple-layer sheet ceramic capacitor as claimed in claim 1 is characterized in that: described cellulosic resin is ethyl cellulose or hydroxyethylcellulose, and viscosity is 10-50mpa.s.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100942549A CN101567264A (en) | 2008-04-24 | 2008-04-24 | Base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100942549A CN101567264A (en) | 2008-04-24 | 2008-04-24 | Base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor |
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| CN101567264A true CN101567264A (en) | 2009-10-28 |
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| CNA2008100942549A Pending CN101567264A (en) | 2008-04-24 | 2008-04-24 | Base metal nickel internal electrode slurry of microwave multiple-layer sheet ceramic capacitor |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872679A (en) * | 2010-05-26 | 2010-10-27 | 广东风华高新科技股份有限公司 | Nickel inner electrode slurry |
| CN103008685A (en) * | 2011-09-02 | 2013-04-03 | 昭荣化学工业株式会社 | Metal powder production method, metal powder produced thereby, conductive paste and multilayer ceramic electronic component |
| US8512905B2 (en) | 2011-06-02 | 2013-08-20 | Samsung Electronics Co., Ltd. | Catalyst slurry, electrode prepared by using the catalyst slurry, and fuel cell including the electrode |
| CN108550977A (en) * | 2018-03-30 | 2018-09-18 | 深圳市振华微电子有限公司 | RFID antenna, RFID tag and RFID antenna production method |
| CN111295724A (en) * | 2017-11-02 | 2020-06-16 | 株式会社村田制作所 | Thermistor element and method for manufacturing the same |
-
2008
- 2008-04-24 CN CNA2008100942549A patent/CN101567264A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101872679A (en) * | 2010-05-26 | 2010-10-27 | 广东风华高新科技股份有限公司 | Nickel inner electrode slurry |
| CN101872679B (en) * | 2010-05-26 | 2012-09-05 | 广东风华高新科技股份有限公司 | Nickel inner electrode slurry |
| US8512905B2 (en) | 2011-06-02 | 2013-08-20 | Samsung Electronics Co., Ltd. | Catalyst slurry, electrode prepared by using the catalyst slurry, and fuel cell including the electrode |
| CN103008685A (en) * | 2011-09-02 | 2013-04-03 | 昭荣化学工业株式会社 | Metal powder production method, metal powder produced thereby, conductive paste and multilayer ceramic electronic component |
| US9162288B2 (en) | 2011-09-02 | 2015-10-20 | Shoei Chemical Inc. | Metal powder production method, metal powder produced thereby, conductive paste and multilayer ceramic electronic component |
| CN103008685B (en) * | 2011-09-02 | 2016-03-23 | 昭荣化学工业株式会社 | Metal powder production process and metal dust, electroconductive paste and the laminated ceramic electronic component produced by the method |
| CN111295724A (en) * | 2017-11-02 | 2020-06-16 | 株式会社村田制作所 | Thermistor element and method for manufacturing the same |
| CN108550977A (en) * | 2018-03-30 | 2018-09-18 | 深圳市振华微电子有限公司 | RFID antenna, RFID tag and RFID antenna production method |
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Application publication date: 20091028 |