CN109841405B - Silver-terminated electrode slurry for low-temperature sintered MLCC - Google Patents
Silver-terminated electrode slurry for low-temperature sintered MLCC Download PDFInfo
- Publication number
- CN109841405B CN109841405B CN201910310856.1A CN201910310856A CN109841405B CN 109841405 B CN109841405 B CN 109841405B CN 201910310856 A CN201910310856 A CN 201910310856A CN 109841405 B CN109841405 B CN 109841405B
- Authority
- CN
- China
- Prior art keywords
- silver powder
- silver
- powder
- mlcc
- microcrystalline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses silver terminal electrode paste for low-temperature sintered MLCC (multilayer ceramic capacitor), which comprises 65.0-85.0 wt.% of silver powder, 2.0-6.0 wt.% of glass powder and 9.0-33.0 wt.% of organic carrier; the weight ratio of the nano silver powder to the microcrystalline silver powder in the silver powder is (0.5-2.0): 1, the weight ratio of the nano silver powder to the microcrystalline silver powder to the flaky silver powder is (2.0-7.0): 1. the glass powder comprises 38.0-55.0 wt% of ZnO and SiO2 5.0～25.0wt.％、B2O3 5.0～40.0wt.％、Al2O3 5.0～20.0wt.％、K2O1.0-6.0 wt.% and Cu2O2.0-6.0 wt.%; the slurry can solve the problem of gaps generated at the joint caused by the Kenkard effect when the inner and outer electrodes are sintered at high temperature while ensuring good compactness of the silver layer.
Description
Technical Field
The invention relates to the technical field of MLCC (multilayer ceramic capacitor), in particular to silver terminal electrode slurry for low-temperature sintered MLCC.
Background
MLCC silver end electrode pastes generally comprise three parts: the organic carrier has the main functions of dispersing the metal powder and the glass powder, so that the slurry has certain viscosity, leveling property and thixotropy and is suitable for dip coating of capacitor elements; the glass powder is used as a binding phase and mainly plays a role in connecting the metal electrode and the capacitor porcelain body in the sintering process, so that good adhesion between the outer electrode and the porcelain body is ensured; the metal powder forms a metal continuous electrode after high-temperature sintering, and the metal continuous electrode is communicated with the inner electrode and is used as a terminal electrode material of the capacitor.
The internal compactness of the terminal electrodes and the connectivity of the internal and external electrodes determine the reliability of the capacitor:
the inside compactness is relatively poor, and the plating solution corrodes easily, in the welding process in later stage, can produce the electric capacity phenomenon of inefficacy, seriously influences product quality.
The reason for poor connectivity of the inner electrode and the outer electrode is that a regular gap exists at the joint of the inner electrode and the outer electrode, and the gap is mainly caused by the composition of palladium and silver metals of the inner electrode and the outer electrode in the high-temperature sintering process of the electrodes. Although this void phenomenon is common, the presence of such voids is a certain risk for aging and adhesion of the capacitor.
Therefore, it is necessary to improve the above two disadvantages to ensure the reliability of the capacitor.
Disclosure of Invention
Aiming at the defects in the problems, the invention provides the silver terminal electrode slurry for the low-temperature sintering MLCC, which can solve the problem of gaps generated at the joint caused by the Kenkdahl effect when the inner electrode and the outer electrode are sintered at high temperature while ensuring the compactness of a silver layer, and improve the performance and the reliability of the capacitor.
The invention discloses silver terminal electrode slurry for low-temperature sintering MLCC, which comprises the following components in percentage by weight: 65.0-85.0 wt.% of silver powder, 2.0-6.0 wt.% of glass powder and 9.0-33.0 wt.% of organic carrier; wherein:
the silver powder comprises nano silver powder, microcrystalline silver powder and flake silver powder, the average particle size of the nano silver powder is 0.50-0.90 mu m, the average particle size of the microcrystalline silver powder is 1.5-3.0 mu m, the average particle size of the flake silver powder is 4.0-10.0 mu m, and the weight ratio of the nano silver powder to the microcrystalline silver powder is (0.5-2.0): 1, the weight ratio of the nano silver powder to the microcrystalline silver powder to the flaky silver powder is (2.0-7.0): 1;
the glass powder comprises 38.0-55.0 wt% of ZnO and SiO2 5.0～25.0wt.％、B2O35.0～40.0wt.％、Al2O3 5.0～20.0wt.％、K2O1.0-6.0 wt.% and Cu2O 2.0～6.0wt.％。
As a further improvement of the invention, the preparation method of the silver powder comprises the following steps:
adding a surfactant in an amount of 0.5-1.0 wt.% of the silver powder, and dispersing in an alcohol solution in advance;
adding the silver powder obtained by mixing the nano silver powder, the microcrystalline silver powder and the flake silver powder into the alcohol solution, and carrying out ultrasonic vibration dispersion for pretreatment;
and drying the solvent, and vibrating and sieving to obtain the pretreated silver powder.
As a further improvement of the invention, the glass powder further comprises 2.0-6.0 wt.% of one or more of the following oxides:
BaO, CaO, MgO and TiO2。
As a further improvement of the invention, the preparation method of the glass powder comprises the following steps:
and mixing the inorganic powder of the glass powder by a mixer, sintering at high temperature, quenching with water, and ball-milling to obtain the glass powder with the average particle size of 1.5-3.0 mu m.
As a further improvement of the invention, the sintering temperature of the glass powder is 400-600 ℃.
As a further improvement of the invention, the organic carrier comprises one or more of ethyl cellulose, hydroxyethyl cellulose and acrylic resin.
As a further improvement of the invention, the method also comprises the following steps: solvents, coupling agents, thixotropic agents and plasticizers.
As a further improvement of the invention, the sintering temperature of the silver terminal electrode slurry is 600-700 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the prepared silver electrode slurry does not contain lead, has excellent performance, the sintering temperature is 600-700 ℃, the whole sintering time is 55-75 min, the sintering time in a high-temperature area is 8-15 min, and the sintered chip product has excellent adhesive force and good silver layer compactness; meanwhile, the problem of gaps generated at the joint caused by the Kenkdael effect when the inner and outer electrodes are sintered at high temperature is solved, and the product performance and reliability are improved.
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 invention is described in further detail below:
the invention aims to adjust the proportion of silver powder with different particle diameters and silver powder with different scales on the premise of using a proper organic carrier, ensuring that the slurry has proper thixotropy and the obtained product has good appearance of an end head, and simultaneously selecting glass with proper sintering temperature to obtain the silver paste with the sintering temperature of 600-700 ℃, so that the chip product has qualified appearance and electrical property, excellent silver layer adhesive force and good compactness, effectively solves the problem of gaps generated at a connecting part due to the Kerkinjel effect when an inner electrode and an outer electrode are sintered at high temperature, and improves the product performance and reliability.
Therefore, the invention provides silver terminal electrode slurry for low-temperature sintering MLCC, which comprises the following components in percentage by weight: 65.0-85.0 wt.% of silver powder, 2.0-6.0 wt.% of glass powder and 9.0-33.0 wt.% of organic carrier; wherein:
the silver powder comprises nano silver powder (spherical), microcrystalline silver powder and flake silver powder, and is preferably a mixture consisting of the nano silver powder, the microcrystalline silver powder and the flake silver powder; the average grain diameter of the nano silver powder is 0.50-0.90 mu m, the average grain diameter of the microcrystalline silver powder is 1.5-3.0 mu m, the average grain diameter of the flaky silver powder is 4.0-10.0 mu m, and the weight ratio of the nano silver powder to the microcrystalline silver powder is (0.5-2.0): 1, the weight ratio of the nano silver powder to the microcrystalline silver powder to the flaky silver powder is (2.0-7.0): 1.
based on the composition of the silver powder, the preparation method of the silver powder comprises the following steps:
adding a surfactant in an amount of 0.5-1.0 wt.% of silver powder, and dispersing in an alcohol solution in advance; adding the silver powder obtained by mixing the nano silver powder, the microcrystalline silver powder and the flake silver powder into an alcohol solution, and carrying out ultrasonic vibration dispersion for pretreatment; and drying the solvent, and vibrating and sieving to obtain the pretreated silver powder.
Wherein the surfactant can be span 85 or Tween 80, and the ultrasonic vibration dispersion time is 30 min.
The glass powder comprises 38.0-55.0 wt% of ZnO and SiO2 5.0～25.0wt.％、B2O35.0～40.0wt.％、Al2O3 5.0～20.0wt.％、K2O1.0-6.0 wt.% and Cu2O 2.0～6.0wt.％；On the basis, the catalyst also can comprise 2.0-6.0 wt.% of one or more of the following oxides: BaO, CaO, MgO and TiO2。
Based on the composition of the glass powder, the preparation method of the glass powder comprises the following steps:
mixing inorganic powder (components of the glass powder) of the glass powder by a mixer, sintering at high temperature, quenching with water, and ball-milling to obtain the glass powder with the average particle size of 1.5-3.0 mu m.
Wherein the sintering temperature of the glass powder formed by the components is 400-600 ℃.
The organic carrier comprises one or more of ethyl cellulose, hydroxyethyl cellulose and acrylic resin.
The paste of the present invention may further contain a solvent, a coupling agent, a thixotropic agent and a plasticizer in addition to the silver powder, the glass frit and the organic vehicle. Wherein the solvent is one of terpineol, benzyl alcohol, diethylene glycol ethyl ether, butyl carbitol acetate, cyclohexanone, butyl carbitol and ethylene glycol monobutyl ether, the surfactant is one of span 85 and tween 80, the coupling agent is one of KH-550, KH-560 and KH-570, the thixotropic agent is one of hydrogenated castor oil, lecithin and polyethylene glycol, and the plasticizer is dibutyl phthalate.
The preparation process of the silver terminal electrode slurry for the low-temperature sintered MLCC comprises the following steps:
the silver electrode slurry is prepared according to a conventional production process flow, pretreated silver metal powder and glass powder are mixed in advance according to a formula proportion, added into an organic carrier for multiple times, mechanically mixed, fully ground and rolled by a three-roll grinder to obtain slurry with a certain fineness requirement, and qualified inspection is carried out to form the silver electrode finished product slurry.
Examples
Adding a surfactant according to the formula of the 1-5 serial numbers in the table 1 in an amount of 0.5-1.0 wt.% of silver powder, and dispersing in an alcohol solution in advance; adding the silver powder obtained by mixing the nano silver powder, the microcrystalline silver powder and the flake silver powder into an alcohol solution, and carrying out ultrasonic vibration dispersion for pretreatment; and drying the solvent, and vibrating and sieving to obtain the pretreated silver powder.
According to the formula of the serial numbers 1-7 in the table 2, inorganic powder (components of the glass powder) of the glass powder is mixed by a mixer, sintered at high temperature and quenched by water, and ball-milled to the glass powder with the average particle size of 1.5-3.0 μm.
According to the silver powder and glass frit compositions of tables 1 and 2, 7 sets of formulations shown in table 3 were prepared; and processing the slurry processing chips with the numbers 1-7 in the table 3 to verify the electrical property and the mechanical property of the product so as to evaluate the performance of the slurry.
Table 1 silver powder formulation table of the present invention
Table 2 glass powder formulation table of the present invention
TABLE 3 formulation composition of slurry of the invention and MLCC product Performance Table
According to the invention, the prepared silver electrode slurry contains no lead, has excellent performance, the sintering temperature is 600-700 ℃, the whole sintering time is 55-75 min, the sintering time in a high-temperature area is 8-15 min, and the sintered chip product has excellent adhesive force and good silver layer compactness; meanwhile, the problem of gaps generated at the joint caused by the Kenkdael effect when the inner and outer electrodes are sintered at high temperature is solved, and the product performance and reliability are improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The silver end electrode slurry for the low-temperature sintering MLCC is characterized by comprising the following components in parts by weight: 65.0-85.0 wt.% of silver powder, 2.0-6.0 wt.% of glass powder and 9.0-33.0 wt.% of organic carrier; wherein:
the silver powder comprises nano silver powder, microcrystalline silver powder and flake silver powder, the average particle size of the nano silver powder is 0.50-0.90 mu m, the average particle size of the microcrystalline silver powder is 1.5-3.0 mu m, the average particle size of the flake silver powder is 4.0-10.0 mu m, and the weight ratio of the nano silver powder to the microcrystalline silver powder is (0.5-2.0): 1, the weight ratio of the nano silver powder to the microcrystalline silver powder to the flaky silver powder is (2.0-7.0): 1;
the glass powder comprises 38.0-55.0 wt% of ZnO and SiO2 5.0～25.0wt.％、B2O35.0～40.0wt.％、Al2O3 5.0～20.0wt.％、K2O1.0-6.0 wt.% and Cu2O 2.0～6.0wt.％。
2. The silver end electrode paste for the low temperature sintered MLCC according to claim 1, wherein the silver powder is prepared by the method comprising:
adding a surfactant in an amount of 0.5-1.0 wt.% of the silver powder, and dispersing in an alcohol solution in advance;
adding the silver powder obtained by mixing the nano silver powder, the microcrystalline silver powder and the flake silver powder into the alcohol solution, and carrying out ultrasonic vibration dispersion for pretreatment;
and drying the solvent, and vibrating and sieving to obtain the pretreated silver powder.
3. The silver end electrode paste for the low temperature sintered MLCC according to claim 1, wherein the glass frit further comprises 2.0 to 6.0 wt.% of one or more of the following oxides:
BaO, CaO, MgO and TiO2。
4. The silver terminal electrode paste for a low-temperature sintered MLCC according to claim 1 or 3, wherein the glass frit is prepared by a method comprising:
and mixing the inorganic powder of the glass powder by a mixer, sintering at high temperature, quenching with water, and ball-milling to obtain the glass powder with the average particle size of 1.5-3.0 mu m.
5. The silver terminal electrode paste for a low temperature sintered MLCC according to claim 1 or 3, wherein the sintering temperature of the glass frit is 400 to 600 ℃.
6. The silver end electrode paste for the low temperature sintering MLCC according to claim 1, wherein the organic vehicle comprises one or more of ethyl cellulose, hydroxyethyl cellulose, and acrylic resin.
7. The silver termination paste for a low-temperature sintered MLCC according to claim 1, further comprising: solvents, coupling agents, thixotropic agents and plasticizers.
8. The silver terminal electrode paste for the low temperature sintering MLCC according to claim 1, wherein the sintering temperature of the silver terminal electrode paste is 600-700 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910310856.1A CN109841405B (en) | 2019-04-18 | 2019-04-18 | Silver-terminated electrode slurry for low-temperature sintered MLCC |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910310856.1A CN109841405B (en) | 2019-04-18 | 2019-04-18 | Silver-terminated electrode slurry for low-temperature sintered MLCC |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109841405A CN109841405A (en) | 2019-06-04 |
| CN109841405B true CN109841405B (en) | 2021-02-19 |
Family
ID=66887165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910310856.1A Active CN109841405B (en) | 2019-04-18 | 2019-04-18 | Silver-terminated electrode slurry for low-temperature sintered MLCC |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109841405B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111403078B (en) * | 2020-03-26 | 2021-08-24 | 湖南省国银新材料有限公司 | Conductive silver paste for filter, preparation method and sintering method thereof |
| CN115188589B (en) * | 2021-04-02 | 2023-08-01 | 北京元六鸿远电子科技股份有限公司 | Copper external electrode slurry for MLCC printing |
| CN113782250B (en) * | 2021-08-26 | 2024-03-19 | 北京无线电测量研究所 | High-thixotropy low-temperature co-fired ceramic inner electrode silver paste and preparation method and application thereof |
| CN114709002A (en) * | 2022-03-31 | 2022-07-05 | 昆明理工大学 | 5G ceramic filter electrode silver paste with high adhesive force and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100380541C (en) * | 1997-10-06 | 2008-04-09 | Tdk株式会社 | Electronic device and method of producing same |
| CN101364455B (en) * | 2008-09-26 | 2011-09-28 | 广东风华高新科技股份有限公司 | Base metal copper electrode paste and preparation of obtained capacitor |
| CN101699565B (en) * | 2009-10-22 | 2011-11-09 | 广东风华高新科技股份有限公司 | Low-temperature sintering silver electrode slurry |
| CN101794639B (en) * | 2010-03-16 | 2011-10-05 | 彩虹集团公司 | Environment-friendly glass frit and preparation method thereof |
| CN102842353B (en) * | 2012-08-14 | 2015-05-13 | 廖晓峰 | Electrocondution slurry for chip component termination electrode |
| CN106098150A (en) * | 2016-08-30 | 2016-11-09 | 中国振华集团云科电子有限公司 | The inductor ends of low-temperature sintering low silver content is coated with formula of silver slurry and preparation method thereof |
-
2019
- 2019-04-18 CN CN201910310856.1A patent/CN109841405B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109841405A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109841405B (en) | Silver-terminated electrode slurry for low-temperature sintered MLCC | |
| US10529873B2 (en) | Aging resistant backside silver paste for crystalline silicon solar cells and preparation method thereof | |
| EP2306522B1 (en) | Method for the manfacture of solar cell electrodes | |
| US7485245B1 (en) | Electrode paste for solar cell and solar cell electrode using the paste | |
| US7648730B2 (en) | Paste for solar cell electrode and solar cell | |
| CN101692410B (en) | Silver paste of MLCC terminal electrode | |
| KR20060108550A (en) | Electroconductive thick film composition, electrode, and solar cell formed therefrom | |
| CN110047611B (en) | Conductive silver paste for low-temperature sintering LTCC | |
| JP5488282B2 (en) | Conductive paste | |
| CN104575663A (en) | Electrode slurry and preparation method thereof | |
| CN104112490A (en) | Electrode slurry and preparation method | |
| CN111564234A (en) | Titanate-based lead-free silver electrode slurry and preparation and use methods thereof | |
| JP2005504409A (en) | Silver conductor composition | |
| CN102831952B (en) | Conductive silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of conductive silver paste | |
| CN106601333A (en) | High temperature thick film electrode slurry and preparation method thereof | |
| JP2018152218A (en) | Conductive paste, chip electronic component and method for producing the same | |
| CN102831951B (en) | Silver paste for environmental-friendly lead-free silicon solar cell electrode and preparation method of silver paste | |
| US20130014816A1 (en) | Conductive paste, method for manufacturing solar cell electrodes and solar cell electrodes | |
| CN115083655A (en) | Conductive copper paste and preparation method and application thereof | |
| CN102831950B (en) | Conductive lead-free silver paste mixed with copper powder and aluminum powder for solar cell and preparation method of conductive lead-free silver paste | |
| CN115188589B (en) | Copper external electrode slurry for MLCC printing | |
| KR100360546B1 (en) | Conductive paste composition for outer electrode of chip inductor | |
| JP3965075B2 (en) | Copper paste composition for multilayer ceramic capacitor external electrode | |
| CN102831960B (en) | Lead-free conducting silver paste used for silicon solar cell and preparation method thereof | |
| CN109087723A (en) | A kind of gold electrocondution slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |