CN104148665B - Preparation method of crystalized sliver powder - Google Patents
Preparation method of crystalized sliver powder Download PDFInfo
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- CN104148665B CN104148665B CN201410346916.2A CN201410346916A CN104148665B CN 104148665 B CN104148665 B CN 104148665B CN 201410346916 A CN201410346916 A CN 201410346916A CN 104148665 B CN104148665 B CN 104148665B
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Abstract
The invention discloses a preparation method of crystalized sliver powder. The preparation method includes the steps of dissolving dispersant and silver nitrate in deionized water to obtain first solution, dissolving dispersant, surfactant, ascorbic acid and pH modifier in water to obtain second solution, adding the first solution into the second solution or the second solution into the first solution while stirring, adding the pH modifier to maintain pH of a reaction system stable during the whole course, controlling the temperature of the reaction system to be 25-45 DEG C, and performing washing and drying to obtain the crystalized sliver powder after reaction is over. By the use of the preparation method, the problem in mononuclear crystallization of the slivered powder is effectively solved; the tap density of the prepared sliver powder can be larger than 5.5g/cm<3> per specification.
Description
Technical field
The present invention relates to a kind of preparation method of crystallization argentum powder, crystallizes the system of argentum powder in particular to high-tap density
Preparation Method.
Technical background
In recent years, electronics industry is developed rapidly, developing rapidly in particular with heliotechnics, conductive silver paste conduct
Produce the basic and key function material of various electronic devices and components and receive much concern, following new electronic device and production technology skill
Art will need new argentum powder silver paste technology.In solar energy electronic slurry, more than 90%, the quality of quality of cathode silver is directly for argentum powder content
Affect the electrical property of slurry.At present, China has become the first big manufacturing country of world's solar-energy photo-voltaic cell, China's photovoltaic
Component major part material realizes production domesticization, but front electrode silver plasm material is still monopolized by offshore company, and one of its reason is
China can not still produce high-performance argentum powder.Research and development high-performance argentum powder（Such as：High-tap density, single dispersing, particle diameter, morphology controllable）It is
The needs of argentum powder industry development.
At present chemical reduction method is most common to be prepared on a large scale argentum powder method.And chemical reduction method prepares the key point of argentum powder
It is pattern, particle diameter and the dispersibility for how controlling argentum powder.Patent application 200680024526.7 discloses a kind of highly crystalline silver
The preparation method of powder and the highly crystalline argentum powder, primary particle size are 0.07 μm ~ 4.5 μm, but the argentum powder on-monocrystalline nucleation, and degree of crystallinity is not
Height, particle diameter distribution width, tap density be not high, it is difficult to meets solar energy silver paste requirement.Patent application 201310036975.5 is public
A kind of preparation method of high tap density monodisperse silver powder is opened, has lured agent to mix by adding micro base metal during the course of the reaction
Use, argentum powder monokaryon crystallisation problems are efficiently solved in preparation process, can prepare single specification argentum powder tap density can be big
In 5.5g/cm3, but base metal lures being introduced into for agent introduce impurity in final argentum powder, so as to affect argentum powder performance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high-tap density mono-dispersed and crystalline argentum powder, the argentum powder microcosmic shape
Looks are spherical in polyhedron, can meet middle and high end silver paste demand, and under high solids content, printing-sintering has low shrinkage factor, so as to
Reach high printing precision.
The present invention seeks to be achieved through the following technical solutions：
A kind of preparation method of crystallization argentum powder, comprises the following steps：
（1）Silver nitrate and dispersant are dissolved in into deionized water and prepare the 1st aqueous solution；
（2）Dispersant, surfactant, ascorbic acid and pH adjusting agent are dissolved in into water and prepare the 2nd aqueous solution；
（3）Under agitation in the 2nd aqueous solution add the 1st aqueous solution or in the 1st aqueous solution add the 2nd aqueous solution, instead
Add pH adjusting agent during answering to maintain reaction system pH is 0.7 ~ 2.0, is reacted at 25 DEG C ~ 45 DEG C, reacts Jing after terminating and washes
Wash and be dried to obtain crystallization argentum powder；
The dispersant is selected from gelatin, polyvinylpyrrolidone, N-Methyl pyrrolidone, polyvinyl alcohol, triethanolamine, lemon
Lemon acid trisodium, Radix Acaciae senegalis；
The surfactant is selected from Oleic acid, linoleic acid, myristic acid, lauric acid, palmitic acid, stearic acid.
Above-mentioned steps（2）And step（3）The pH adjusting agent of middle addition is selected from nitric acid, acetic acid, sodium hydroxide, ammonia.
Above-mentioned dispersant dosage is 1 ~ 25g/L, wherein it is 1 to add mass ratio in the 1st aqueous solution and the 2nd aqueous solution:30～
30:1。
Step（1）In, silver nitrate concentration is 50～200g/L.
Step（2）In, surfactant addition for silver nitrate quality 1～5%；Ascorbic acid addition is for completely also
1.0 ~ 1.5 times of the theoretical usage amount of orthonitric acid silver, the concentration of ascorbic acid is 50～150g/L.
Step（3）In, mixing speed is 100 ~ 200r/min, and the response time is 10 ~ 40 minutes.
The present invention has advantages below：
（1）The present invention during the course of the reaction, by adding pH adjusting agent maintaining stablizing for reaction system pH.Other conditions
It is constant, compare high pH, ascorbic acid has lower reducing power at a low ph, and the silver-colored nucleus formed so as to initial reaction stage can be with
Grow by crystal orientation in the later stage, solve argentum powder monokaryon crystallisation problems；
（2）The argentum powder microscopic appearance for preparing is that polyhedron is spherical, with high tap density, good dispersibility
And good sintering character.Adapt to high this solid content of similar solaode electric slurry, printing precision height, shrinkage factor will
Low silver paste is sought, there is excellent electrical property after sintering film forming；
（3）By adjusting dispersant in the 1st and the 2nd aqueous solution, coordinate suitable surfactant and reaction temperature
Degree, makes that obtained crystallization argentum powder size is adjustable, and dispersion, uniformity are good；
（4）The single specification tap density of crystal argentum powder prepared by the present invention can be more than 5.5g/cm3, can by control condition
Prepare 0.2 ~ 4 μm of different size monodisperse silver powder；
（5）Present invention process is simple, the equal environmental friendliness of all reagents, the crystal argentum powder good stability of preparation, it is easy to industry
Production is amplified.
Description of the drawings
Fig. 1 is the SEM figures of 1 gained argentum powder of the embodiment of the present invention；
Fig. 2 is the SEM figures of 2 gained argentum powder of the embodiment of the present invention；
Fig. 3 is the SEM figures of 3 gained argentum powder of the embodiment of the present invention.
Specific embodiment
The preparation method for crystallizing argentum powder is further described below in conjunction with specific embodiment.
Embodiment 1
5kg silver nitrate, 40g polyvinylpyrrolidones are added in 30L deionized waters（PVP), liquid temperature is heated to by stirring
30 DEG C, the 1st aqueous solution is obtained.Weigh in 3.3kg ascorbic acid addition 35L deionized waters, add 800g polyvinylpyrrolidones
（PVP), 50g Oleic acid, plus nitric acid adjustment pH be 0.8, stirring liquid temperature is heated to into 30 DEG C, obtain the 2nd aqueous solution.Under agitation,
The 1st aqueous solution is added in the 2nd aqueous solution in 30min, in whole process, maintains reaction system pH to exist by adding ammonia
0.8.Temperature of reaction system is controlled in course of reaction for 30 DEG C, mixing speed is 120r/min.After completion of the reaction, persistently stir
15min.Stand after terminating stirring, settle silver ion, then, filter off reactant liquor, washing, 70 DEG C of drying obtain crystallizing argentum powder
（See Fig. 1）, gained argentum powder tap density 5.35g/cm3, 2.1 μm of mean diameter.
Embodiment 2
To in 40L deionized waters, add 5kg silver nitrate, 40g gelatin, stirring that liquid temperature is heated to 35 DEG C, be obtained the 1st water-soluble
Liquid.Weigh in 3.1kg ascorbic acid addition 45L deionized waters, addition 100g gelatin, 100g Oleic acid, plus nitric acid adjustment pH is
1.2, liquid temperature is heated to 35 DEG C by stirring, obtains the 2nd aqueous solution.Under agitation, the 1st aqueous solution is added to into the 2nd in 30min water-soluble
In liquid, in whole process, reaction system pH is maintained 1.0 by adding ammonia.Temperature of reaction system is controlled in course of reaction for 35
DEG C, mixing speed is 150r/min.After completion of the reaction, persistently stir 15min.Stand after terminating stirring, settle silver ion, so
Afterwards, reactant liquor is filtered off, washing, 70 DEG C of drying obtain crystallizing argentum powder（See Fig. 2）, gained argentum powder tap density 5.70g/cm3, put down
Equal 1.4 μm of particle diameter.
Embodiment 3
5kg silver nitrate, 1kg polyvinylpyrrolidones are added in 50L deionized waters（PVP）, stir and liquid temperature be heated to
45 DEG C, the 1st aqueous solution is obtained.Weigh in 3.1kg ascorbic acid addition 50L deionized waters, add 800g polyvinylpyrrolidones
（PVP), 100g gelatin, 100g Oleic acid, plus nitric acid adjustment pH be 1.5, stirring liquid temperature is heated to into 45 DEG C, obtain the 2nd aqueous solution.
Under stirring, add the 2nd aqueous solution toward the 1st aqueous solution under stirring in 15min, in whole process, remain anti-by adding ammonia
System pH is answered 1.5.Temperature of reaction system is controlled in course of reaction for 45 DEG C, mixing speed is 200r/min.After completion of the reaction,
15min is stirred persistently.Stand after terminating stirring, settle silver ion, then, filter off reactant liquor, washing, 70 DEG C of drying are obtained
Crystallization argentum powder（See Fig. 3）, gained argentum powder tap density 4.5g/cm3, 0.4 μm of mean diameter.
Comparative example 1
Comparative example 1 and 1 similar process of embodiment, difference are to adjust reduction system with ammonia（2nd aqueous solution）
PH is 4.0, and it is 3.9 ~ 4.1 that reaction system pH is controlled in course of reaction, and gained argentum powder characteristic is shown in Table 1.
When comparative example 1 reacts at relatively high ph, the embodiment 1 of low pH reactions, its prepared argentum powder particle diameter distribution are compared
Wider, small particle argentum powder increases, while argentum powder is reunited seriously, tap density is relatively low, it is difficult to actually used, and design parameter is shown in Table 1.
Comparative example 2
Comparative example 2 and 2 similar process of embodiment, difference is, silver nitrate system in comparative example 2（1st water
Solution）Dispersant gelatin is added without, gained argentum powder characteristic is shown in Table 2.
When silver nitrate system in comparative example 2（1st aqueous solution）Dispersant gelatin is added without, its prepared argentum powder particle diameter becomes
Greatly, inhomogeneities increase, and dispersibility is poor, and design parameter is shown in Table 2.
Comparative example 3
Comparative example 3 and 3 similar process of embodiment, difference is, comparative example 3 during the course of the reaction without
PH adjusting agent, gained argentum powder characteristic are shown in Table 3.
The initial pH of 3 reaction system of comparative example is identical with comparative example 3, and difference is that comparative example 3 is anti-
PH is not controlled during answering stable, contrasted with embodiment 3, its prepared argentum powder particle diameter is significantly increased, and tap density is relatively low, it is difficult to be real
Border uses, and design parameter is shown in Table 3.
Claims (1)
1. it is a kind of crystallization argentum powder preparation method, it is characterised in that comprise the following steps：
（1）5kg silver nitrate and 40g polyvinylpyrrolidones are dissolved in into 30L deionized waters, liquid temperature is heated to 30 DEG C, is matched somebody with somebody by stirring
The 1st aqueous solution is obtained；
（2）Weigh in 3.3kg ascorbic acid addition 35L deionized waters, add 800g polyvinylpyrrolidones and 50g Oleic acid,
Plus nitric acid adjustment solution ph is 0.8, liquid temperature is heated to 30 DEG C by stirring, obtains the 2nd aqueous solution；
（3）The 1st aqueous solution is added in the 2nd aqueous solution in 30min under agitation, by adding ammonia dimension in whole process
PH value of reaction system is held 0.8, it is 120r/min that temperature of reaction system is controlled in course of reaction for 30 DEG C, mixing speed, is reacted
After finishing, 15min is persistently stirred, stand after terminating stirring, settle silver ion, then filter off reactant liquor, wash, 70 DEG C of bakings
It is dry, obtain crystallizing argentum powder, gained argentum powder tap density 5.35g/cm3, 2.1 μm of mean diameter.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| CN1709619A (en) * | 2004-06-18 | 2005-12-21 | 同和矿业株式会社 | Spherical silver power and method for producing same |
| CN101462164A (en) * | 2009-01-09 | 2009-06-24 | 贵阳晶华电子材料有限公司 | High-tap density micro aluminum powder and method for producing the same |
| CN101733410A (en) * | 2009-12-31 | 2010-06-16 | 广东风华高新科技股份有限公司 | Preparation method of high dispersibility superfine silver powder with adjustable grain diameter |
| CN102343441A (en) * | 2011-09-22 | 2012-02-08 | 上海交通大学 | Method for preparing monodispersed silver powder with high tap density and low agglomeration |
| CN102554265A (en) * | 2012-03-16 | 2012-07-11 | 上海交通大学 | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size |
| CN103551586A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Preparation method of micron spherical silver powder for electroconductive silver paste |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0211709A (en) * | 1988-06-28 | 1990-01-16 | Tanaka Kikinzoku Kogyo Kk | Production of silver colloid |
-
2014
- 2014-07-22 CN CN201410346916.2A patent/CN104148665B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| CN1709619A (en) * | 2004-06-18 | 2005-12-21 | 同和矿业株式会社 | Spherical silver power and method for producing same |
| CN101462164A (en) * | 2009-01-09 | 2009-06-24 | 贵阳晶华电子材料有限公司 | High-tap density micro aluminum powder and method for producing the same |
| CN101733410A (en) * | 2009-12-31 | 2010-06-16 | 广东风华高新科技股份有限公司 | Preparation method of high dispersibility superfine silver powder with adjustable grain diameter |
| CN102343441A (en) * | 2011-09-22 | 2012-02-08 | 上海交通大学 | Method for preparing monodispersed silver powder with high tap density and low agglomeration |
| CN102554265A (en) * | 2012-03-16 | 2012-07-11 | 上海交通大学 | Preparation method of mono-dispersed highly crystalline silver powder with adjustable particle size |
| CN103551586A (en) * | 2013-09-22 | 2014-02-05 | 江苏瑞德新能源科技有限公司 | Preparation method of micron spherical silver powder for electroconductive silver paste |
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