CN102699345A - Preparation method of micron-sized high-activity spherical silver powder - Google Patents
Preparation method of micron-sized high-activity spherical silver powder Download PDFInfo
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- CN102699345A CN102699345A CN2012101553262A CN201210155326A CN102699345A CN 102699345 A CN102699345 A CN 102699345A CN 2012101553262 A CN2012101553262 A CN 2012101553262A CN 201210155326 A CN201210155326 A CN 201210155326A CN 102699345 A CN102699345 A CN 102699345A
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Abstract
The invention relates to a high-activity spherical silver powder for solar and micro-electronic devices, and particularly relates to a preparation method of micron-sized high-activity spherical silver powder. The preparation method is characterized by comprising the following steps of: adding a formaldehyde solution with the mass percentage of 20-37% and stearic acid into a silver-ammonia solution prepared from silver nitrate, sodium hydroxide, liquid ammonia with the mass percentage of 20-25% and de-ionized water to react to obtain spherical silver powder slurry; uniformly mixing silver powder obtained by solid-liquid separation and drying treatment with inorganic bonding powder, adding a surfactant and dispersing at a high speed; and then, carrying out heat treatment in an environment of 180-400 DEG C for 4-16 hours, and washing and drying to obtain the micron-sized high-activity spherical silver powder. The micron-sized high-activity spherical silver powder prepared by the method disclosed by the invention has a narrow granularity distribution range and good activity; the surface of the micron-sized high-activity spherical silver powder is provided with the inorganic bonding powder, so that the micron-sized high-activity spherical silver powder is particularly suitable for the solar and micro-electronic device industry.
Description
Technical field
The present invention relates to solar energy and microelectronic component with high activity property ball shape silver powder, especially a kind of preparation method of micron order activity spherical silver powder.
Background technology
Silver powder is to belong to be used for preparing stable moulding electronic product material, in electronics industry, has important role.Ball shape silver powder is the key component of interior electrode of electronic devices and components and front electrode of solar battery material as conducting function phase important in the high-temperature sintering electronic slurry.But along with electronic device develops to microminiaturized and high performance direction; Ball shape silver powder is also had higher requirement, comprise that the performance indications such as sintering activity, sphericity, degree of crystallinity, size distribution, tap density, purity of spherical silver powder particles are had higher requirement.
At present, the preparation method of silver powder comprises physics method and chemical method, and the physics method mainly comprises gas evaporation condensation method, physico-chemical process, polishing etc.; Chemical method mainly comprises liquid phase reduction, sol-gal process, electrochemical deposition method, electrolysis, spray heating decomposition and other thermal process.The physics method exists shortcomings such as investment is big, cost is high, productive rate is low, and at present, the production majority of silver powder is main with liquid phase reduction in the electronics industry, and minority adopts the thermal process preparation.The liquid phase reduction production technology is simple, technical parameter is controlled easily, cost is low, with short production cycle, suitable suitability for industrialized production, but the defective of product ubiquity degree of crystallinity difference; If adopt the silver powder degree of crystallinity of thermal process preparation high, but sintering activity is low.
The shortcoming that above-mentioned liquid phase reduction exists is: degree of crystallinity is poor; The shortcoming that above-mentioned thermal process exists is: sintering activity is low.
Summary of the invention
The preparation method who the purpose of this invention is to provide the simple and easy control of a kind of technology, degree of crystallinity is high, sintering activity is good, is easy to realize industrialized a kind of micron order activity spherical silver powder.
A kind of preparation method of micron order activity spherical silver powder; Its special feature is; Comprise the steps: the formalin of mass fraction 20～37% and stearic acid are added in the silver ammino solution by the ammoniacal liquor of silver nitrate, NaOH, mass fraction 20～25% and deionized water configuration; Reaction obtains the ball shape silver powder slurries, through Separation of Solid and Liquid, and after silver powder that the oven dry processing obtains and inorganic bond powder mix, add surfactant and high speed dispersion again; Then in 180～400 ℃ environment heat treatment wash after 4～16 hours, drying, promptly get micron order activity spherical silver powder.
By weight, wherein:
Wherein high speed dispersion is meant that the rotating speed of dispersion machine is 2000～3500 rev/mins.
Wherein surfactant is the N-methyl pyrrolidone ethanolic solution of mass fraction 5～50% or the dodecyl sodium sulfate ethanolic solution of mass fraction 5～30%.
Wherein the preparation method of inorganic bond powder is following:
(1) with the SiO of 22-25mol%
2, the B of 15-18mol%
2O
3, the ZnO of 5-8mol%, surplus is Bi
2O
3After the mixing, by 1: the weight ratio of 4-5 joins in the absolute ethyl alcohol and mixes, 50-60 ℃ of drying; Put into crucible then and founded 1 hour,, ground 72-90 hour with planetary ball mill again through high-temperature water quenching at 1250 ℃; Again through 50-60 ℃ of drying, obtain particle diameter smaller or equal to 0.23 micron powder;
(2) with the ZnO powder of 90-100nm purity at least 99.99% and the In of 80-90nm purity at least 99.99%
2O
3High-purity powder is by 5-6: 1 mass ratio mixes, at 1-1.2t/cm
2Pressure depress to bulk, 1550 ℃ sintering 3-4 hour, then through fragmentation and ball milling, obtaining the meta particle diameter is the zno-based composite granule of 0.1 μ m;
With two kinds of powders of above-mentioned steps (1) and step (2) preparation by mass ratio 9-20: promptly obtain required inorganic bond powder after 1 mixing.
Good and the surface of micron order activity spherical silver powder particles particle size distribution narrow (referring to accompanying drawing 1,2), the activity property that adopts the inventive method to prepare has the inorganic bond powder, is particularly suitable for solar energy and microelectronic component industry and uses.
Description of drawings
The SEMX10000 shape appearance figure of the ball shape silver powder that Fig. 1 makes for the inventive method embodiment 2;
The particle size distribution figure of the spherical silver powder particles that Fig. 2 makes for the inventive method embodiment 2.
The specific embodiment
Embodiment 1:
The preparation of reactant liquor: in deionized water 3000g, add silver nitrate 80g, mass fraction 24% ammoniacal liquor 150g, NaOH 1.2g, adjust to 50 ℃ to solution temperature while stirring, stirred again 3 minutes.
Silver powder reduction is separated out: with 0.1g stearic acid and 320g mass fraction be 26% formalin with at the uniform velocity adding in the above-mentioned solution simultaneously for 30 seconds, after the end to be added, stirred again 10 minutes, it is abundant that silver particles is grown.
Reduction silver powder is handled: after above-mentioned finishing dealing with, left standstill 10 minutes, spend the deionised water filtration and make Separation of Solid and Liquid, get solid 50 ℃ of dryings, it is for use to obtain ball shape silver powder.
The inorganic bond powder preparing:
1, with the SiO of 25mol%
2, the B of 15mol%
2O
3, the Bi of 52mol%
2O
3With the ZnO of 8mol% altogether 100g join in the 500g absolute ethyl alcohol and mix with the active machine of high speed, 50 ℃ of dryings are put into crucible then and were founded 1 hour at 1250 ℃; Through high-temperature water quenching; Ground 72 hours with planetary ball mill,, obtain particle diameter smaller or equal to 0.2 micron powder again through 50 ℃ of dryings.
2,100nm purity is not less than 99.99% ZnO powder and 80nm purity and is not less than 99.99% In
2O
3High-purity powder mixes by 5: 1 mass ratio, at 1.2t/cm
2Pressure depress to bulk, 1550 ℃ of sintering 3 hours, then through fragmentation and ball milling, obtaining the meta particle diameter is the zno-based composite granule of 0.1 μ m.
It is for use that two kinds of powders of above-mentioned 1,2 two kind of method preparation are promptly obtained required inorganic bond powder after by mass ratio mixing in 10: 1.
The preparation of micron order activity spherical silver powder: take by weighing the inorganic bond powder 10g that makes and join in the 180g absolute ethyl alcohol with the ball shape silver powder that obtains through aforementioned reduction silver powder treatment step and stirred 30 minutes with 800 rev/mins with high speed dispersor; Add N-methyl pyrrolidone 15g then, continue to stir 50 minutes, 70 ℃ of dryings 120 minutes; In 320 ℃ environment, be incubated 18 hours then; Use absolute ethanol washing again, 50 ℃ of oven dry, obtaining specific area is 0.46m
2/ g, tap density is 4.6g/cm
3, the silver powder particles average grain diameter is 1.927 μ m, and size of microcrystal is 380 dusts, and the surface has the activity spherical silver powder of a certain amount of inorganic bond powder.
Embodiment 2:
The preparation of reactant liquor: in deionized water 3000g, add silver nitrate 90g, the ammoniacal liquor 200g of mass fraction 24%, NaOH 1.5g, adjust to 60 ℃ to solution temperature while stirring, stirred again 5 minutes.
Silver powder reduction is separated out: with 0.15g stearic acid and 400g mass fraction be 20% formalin with at the uniform velocity adding in the above-mentioned solution simultaneously for 25 seconds, after the end to be added, stirred again 15 minutes, it is abundant that silver particles is grown.
Reduction silver powder is handled: after above-mentioned finishing dealing with, left standstill 12 minutes, spend the deionised water filtration and make Separation of Solid and Liquid, get solid 60 ℃ of dryings, it is for use to obtain ball shape silver powder.
The inorganic bond powder preparing:
1, with the SiO of 21mol%
2, the B of 18mol%
2O
3, the Bi of 56mol%
2O
3With the ZnO of 5mol% altogether 100g join in the 400g absolute ethyl alcohol and mix with the active machine of high speed, 60 ℃ of dryings are put into crucible then and were founded 1 hour at 1250 ℃; Through high-temperature water quenching; Ground 90 hours with planetary ball mill,, obtain particle diameter smaller or equal to 0.23 micron powder again through 60 ℃ of oven dry.
2, with 90nm purity more than or equal to 99.99% ZnO powder and 90nm purity more than or equal to 99.99% In
2O
3High-purity powder mixes by 6: 1 mass ratio, at 1.0t/cm
2Pressure depress to bulk, 1550 ℃ of sintering 4 hours, then through fragmentation and ball milling, obtaining the meta particle diameter is the zno-based composite granule of 0.1 μ m.
It is for use that two kinds of powders of above-mentioned 1,2 two kind of method preparation are promptly obtained required inorganic bond powder end after by mass ratio mixing in 9: 1.
The preparation of micron order activity spherical silver powder: take by weighing the inorganic bond powder 10g that makes and join in the 150g absolute ethyl alcohol with the ball shape silver powder that obtains through aforementioned reduction silver powder treatment step and stirred 20 minutes with 1000 rev/mins with high speed dispersor; Add dodecyl sodium sulfate 20g then, continue to stir 30 minutes, 60 ℃ of dryings 100 minutes; In 360 ℃ environment, be incubated 18 hours then; Use absolute ethanol washing again, 70 ℃ of oven dry, obtaining specific area is 0.56m
2/ g, tap density is 4.8g/cm
3, the silver powder particles average grain diameter is 1.98 μ m, and size of microcrystal is 395 dusts, and the surface has the activity spherical silver powder of a certain amount of inorganic bond powder.
Claims (5)
1. the preparation method of a micron order activity spherical silver powder; It is characterized in that; Comprise the steps: the formalin of mass fraction 20～37% and stearic acid are added in the silver ammino solution by the ammoniacal liquor of silver nitrate, NaOH, mass fraction 20～25% and deionized water configuration; Reaction obtains the ball shape silver powder slurries, through Separation of Solid and Liquid, and after silver powder that the oven dry processing obtains and inorganic bond powder mix, add surfactant and high speed dispersion again; Then in 180～400 ℃ environment heat treatment wash after 4～16 hours, drying, promptly get micron order activity spherical silver powder.
2. the preparation method of a kind of micron order activity spherical silver powder as claimed in claim 1 is characterized in that, by weight, and wherein:
3. the preparation method of a kind of micron order activity spherical silver powder as claimed in claim 1 is characterized in that: wherein high speed dispersion is meant that the rotating speed of dispersion machine is 2000～3500 rev/mins.
4. the preparation method of a kind of micron order activity spherical silver powder as claimed in claim 1 is characterized in that: wherein surfactant is the N-methyl pyrrolidone ethanolic solution of mass fraction 5～50% or the dodecyl sodium sulfate ethanolic solution of mass fraction 5～30%.
5. the preparation method of a kind of micron order activity spherical silver powder as claimed in claim 1 is characterized in that, wherein the preparation method of inorganic bond powder is following:
(1) with the SiO of 22-25mol%
2, the B of 15-18mol%
2O
3, the ZnO of 5-8mol%, surplus is Bi
2O
3After the mixing, by 1: the weight ratio of 4-5 joins in the absolute ethyl alcohol and mixes, 50-60 ℃ of drying; Put into crucible then and founded 1 hour,, ground 72-90 hour with planetary ball mill again through high-temperature water quenching at 1250 ℃; Again through 50-60 ℃ of drying, obtain particle diameter smaller or equal to 0.23 micron powder;
(2) with the ZnO powder of 90-100nm purity at least 99.99% and the In of 80-90nm purity at least 99.99%
2O
3High-purity powder is by 5-6: 1 mass ratio mixes, at 1-1.2t/cm
2Pressure depress to bulk, 1550 ℃ sintering 3-4 hour, then through fragmentation and ball milling, obtaining the meta particle diameter is the zno-based composite granule of 0.1 μ m;
With two kinds of powders of above-mentioned steps (1) and step (2) preparation by mass ratio 9-20: promptly obtain required inorganic bond powder after 1 mixing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962473A (en) * | 2012-12-06 | 2013-03-13 | 云南铜业科技发展股份有限公司 | Method for preparing silver powder for touch screen silver paste |
| CN110114175A (en) * | 2016-10-13 | 2019-08-09 | LS-Nikko铜制炼株式会社 | High temperature sintering type silver powder and its manufacturing method |
| CN110303148A (en) * | 2019-06-14 | 2019-10-08 | 湖南诺尔得材料科技有限公司 | The preparation method of subsphaeroidal silver powder |
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| US20030034732A1 (en) * | 1999-12-21 | 2003-02-20 | Masaki Aoki | Plasma display panel and method for production thereof |
| KR100713241B1 (en) * | 2006-06-28 | 2007-05-02 | 주식회사 씨에라인더스트리 | Method of manufacturing silver powder by chemical reduction |
| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| JP2010062018A (en) * | 2008-09-04 | 2010-03-18 | Taiyo Ink Mfg Ltd | Conductive paste and electrode using it |
| CN102081988A (en) * | 2010-12-27 | 2011-06-01 | 张振中 | Reinforced back electric field A1 slurry of silicon solar battery |
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2012
- 2012-05-18 CN CN201210155326.2A patent/CN102699345B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030034732A1 (en) * | 1999-12-21 | 2003-02-20 | Masaki Aoki | Plasma display panel and method for production thereof |
| KR100713241B1 (en) * | 2006-06-28 | 2007-05-02 | 주식회사 씨에라인더스트리 | Method of manufacturing silver powder by chemical reduction |
| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| JP2010062018A (en) * | 2008-09-04 | 2010-03-18 | Taiyo Ink Mfg Ltd | Conductive paste and electrode using it |
| CN102081988A (en) * | 2010-12-27 | 2011-06-01 | 张振中 | Reinforced back electric field A1 slurry of silicon solar battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102962473A (en) * | 2012-12-06 | 2013-03-13 | 云南铜业科技发展股份有限公司 | Method for preparing silver powder for touch screen silver paste |
| CN110114175A (en) * | 2016-10-13 | 2019-08-09 | LS-Nikko铜制炼株式会社 | High temperature sintering type silver powder and its manufacturing method |
| CN110114175B (en) * | 2016-10-13 | 2022-06-14 | LS-Nikko铜制炼株式会社 | High-temperature sintered silver powder and method for producing same |
| CN110303148A (en) * | 2019-06-14 | 2019-10-08 | 湖南诺尔得材料科技有限公司 | The preparation method of subsphaeroidal silver powder |
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