CN103831444A - Preparation method for high-crystallized flake silver powders - Google Patents
Preparation method for high-crystallized flake silver powders Download PDFInfo
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- CN103831444A CN103831444A CN201410087807.3A CN201410087807A CN103831444A CN 103831444 A CN103831444 A CN 103831444A CN 201410087807 A CN201410087807 A CN 201410087807A CN 103831444 A CN103831444 A CN 103831444A
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Abstract
The invention relates to a preparation method for high-crystallized flake silver powders. The preparation method includes: adding a polymeric precursor solution to a reduction solution taking diethylene glycol as a solvent and containing PEG-20000 and hydrogen peroxide for hybrid reaction, wherein silver nitrate and trace palladium nitrate are taken as additives, and the polymeric precursor solution is composed by the solvent of the diethylene glycol; continuously adding dropwise a silver ammonia solution taking the diethylene glycol as the solvent into the polymeric precursor solution till reaction is complete, wherein obtained sediment is cleaned and dried to form the high-crystallized flake silver powders. Compared with those by the prior art, the silver powders prepared by the preparation method have the advantages of high tap density, narrow particle-size dispersion scope, smooth surface, low oil adsorption and the like.
Description
Technical field
The present invention relates to electronic equipment preparation field, especially in electric slurry silver powder and the method for technical field of solar batteries, especially relate to a kind of preparation method of high crystallization flake silver powder.
Background technology
Along with Precious Metal is widely used in the packaging technology of hybrid microcircuit, the performance of noble metal powder receives increasingly extensive concern, wherein as conductor, resistance, medium electric slurry important conducting function material---the demand of super fine silver powder constantly increases, and as also increasingly strict in the requirement of particle diameter and distribution, pattern, specific area etc. to the performance of argent powder.At present the form of silver powder roughly has spherical, flakey, dendroid and sheet.When flake silver powder conducts electricity as filler, it is face or line contact each other,
Spherical silver powder is a contact, so flake silver powder is much lower than the resistance of spherical silver powder, even when compared with low silver content and thinner printed coating, still there is higher electrical conductivity, be therefore widely used in the electronic devices and components such as carbon-film potentiometer termination, thin film switch, wave filter.The physical property of flake silver powder is the key factor of impact silver slurry electrical property, when the particle diameter of flake silver powder reaches submicron order yardstick, when pattern is bright sheet, to the printing effect of electronic circuit, comprise that uniformity, flatness etc. all have clear improvement, and can save noble metal dosage 30%～50%.Along with the deterioration of natural environment and gradually reducing of the traditional fuel energy, people are day by day urgent to reproducible clean energy resource demand.
Meanwhile, photovoltaic generation becomes renewable and clean energy resource of greatest concern with its unique advantage.Abundant solar radiation is inexhaustible, pollution-free, cheapness, and can safe and free use.Along with scientific and technological progress, require the transformation efficiency that constantly improves solar cell to obtain more electric energy, therefore require to innovate from structure, technique and the material of solar cell.The preparation of especially starching at solar energy back silver, the flake silver powder direct transformation efficiency that affects best in quality.
At present, prepare in the world flake silver powder, great majority are spherical or irregular silver powder prepared by first chemistry or Physical, then obtain by ball-milling technology.As application publication number: CN102794453A, in its preparation process, Ball-milling Time is long and in mechanical milling process, to introduce that a large amount of additives reduce silver powder purity, preparation technology expends a large amount of electric energy etc. many unfavorable.
Summary of the invention
Object of the present invention is exactly to provide in order to overcome the defect that above-mentioned prior art exists that a kind of tap density is high, particle size dispersion narrow range, smooth surface, oil absorbency are low and are easy to the preparation method of the high crystallization flake silver powder of large-scale production.
Object of the present invention can be achieved through the following technical solutions:
A preparation method for high crystallization flake silver powder, adopts following steps:
(1) take silver nitrate and micro-palladium nitrate as additive, the precursor solution take diethylene glycol as solvent composition, is added drop-wise to hybrid reaction in the reducing solution that contains PEG-20000 and hydrogen peroxide take diethylene glycol as solvent by precursor solution;
(2) continue to drip wherein the silver ammino solution take diethylene glycol as solvent, continue reaction to reacting completely, gained precipitation is high crystallization flake silver powder after cleaning-drying.
In described precursor solution, the concentration of silver nitrate is 0.5～3g/L, and the mole of palladium nitrate is silver nitrate 10
-2-10
-3doubly.
In described reducing solution, contain hydrogen peroxide and the silver nitrate mole 10 of 8～10 times of silver nitrate moles
-2-10
-3pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent.
In described silver ammino solution, the concentration of silver nitrate is 17-35g/L, and the concentration of ammoniacal liquor is 55-150g/L.
Step (1) is under the condition of high-speed stirred, controls reaction temperature at 25-40 ℃, and precursor solution is joined in reducing solution at 0.5-30min, and question response finishes rear continuation and stirs, stand-by.
Step (2) is added drop-wise to silver ammino solution in the mixed solution that step (1) obtains in 20-60min, has reacted rear sedimentation 30-90min, removes supernatant reactant liquor, and what obtain is precipitated as flake silver powder.
The precipitate with deionized water obtaining is cleaned to electrical conductivity 10-20us/cm, then cleans 2-4 time with anhydrous propanone or alcohol, and finally 50-60 ℃ in air dry oven, is dried 10-20 hour, prepares high crystallization flake silver powder.
Compared with prior art, high, the particle size dispersion narrow range of tap density of the present invention, smooth surface, oil absorbency are low.The comparison of more traditional water hydrometallurgy, react in the organic phase of diethylene glycol because the present invention adopts, therefore, the polarity of reaction system is little, influence factor when crystal is grown is few, thus the good characteristics such as the on chip silver-colored particle that makes to grow has that degree of crystallinity is high, smooth surface, tap density are large.Meanwhile, the method preparation technology is simple, facilitates large-scale production.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
Reactor after cleaning and liquid pool deionized water are cleaned and are dried.Preparation precursor solution, makes solvent with diethylene glycol, wherein silver nitrate 0.8g/L palladium nitrate 20mg/L; Preparation silver ammino solution, makes solvent with diethylene glycol, wherein silver nitrate 30g/L, ammoniacal liquor 100g/L; Preparation mixes reducing solution, and hydrogen peroxide 68.5g, PEG-200002g, ammoniacal liquor 20g spend diethylene glycol and be mixed with mixing reducing solution.When high-speed stirred is mixed reducing solution, precursor solution and mixing reducing solution are evenly mixed and reacted, control reaction temperature at 50 ℃, reaction time 10min.After reacting completely, continue to stir, and in 30min, silver ammino solution is dripped wherein.After anyway, after sedimentation 50min, supernatant reactant liquor is reached to its precipitation.After anyway, after sedimentation 45min, supernatant reactant liquor is gone, then precipitation silver powder by washed with de-ionized water to electrical conductivity 10 μ s/cm, then with absolute alcohol clean 2 times.By clean silver powder in air dry oven 60 ℃, dry 11 hours, after being finally dried, obtain high crystallization flake silver powder.Institute film-making silver tap density: 4.3g/cc, size distribution: D
100.8umD
501.1um D
901.5um.
Embodiment 2
Reactor after cleaning and liquid pool deionized water are cleaned and are dried.Preparation precursor solution, makes solvent with diethylene glycol, wherein silver nitrate 2g/L palladium nitrate 14mg/L; Preparation silver ammino solution, makes solvent with diethylene glycol, wherein silver nitrate 20g/L, ammoniacal liquor 130g/L; Preparation mixes reducing solution, and hydrogen peroxide 100g, PEG-200001.5g, ammoniacal liquor 45g spend diethylene glycol and be mixed with mixing reducing solution.When high-speed stirred is mixed reducing solution, precursor solution and mixing reducing solution are evenly mixed and reacted, control reaction temperature at 30 ℃, reaction time 30min.After reacting completely, continue to stir, and in 45min, silver ammino solution is dripped wherein.After anyway, after sedimentation 60min, supernatant reactant liquor is reached to its precipitation.After anyway, after sedimentation 65min, supernatant reactant liquor is gone, then precipitation silver powder by washed with de-ionized water to electrical conductivity 15 μ s/cm, then with acetone clean 3 times.By clean silver powder in air dry oven 56 ℃, dry 13 hours, after being finally dried, obtain high crystallization flake silver powder.Institute film-making silver tap density: 4.4g/cc, size distribution: D
100.7um D
501.3um D
901.6um.
Embodiment 3
Reactor after cleaning and liquid pool deionized water are cleaned and are dried.Preparation precursor solution, makes solvent with diethylene glycol, wherein silver nitrate 2.5g/L palladium nitrate 50mg/L; Preparation silver ammino solution, makes solvent with diethylene glycol, wherein silver nitrate 18g/L, ammoniacal liquor 80g/L; Preparation mixes reducing solution, and hydrogen peroxide 80g, PEG-200000.5g, ammoniacal liquor 15g spend diethylene glycol and be mixed with mixing reducing solution.When high-speed stirred is mixed reducing solution, precursor solution and mixing reducing solution are evenly mixed and reacted, control reaction temperature at 25 ℃, reaction time 15min.After reacting completely, continue to stir, and in 20min, silver ammino solution is dripped wherein.After anyway, after sedimentation 60min, supernatant reactant liquor is reached to its precipitation.After anyway, after sedimentation 90min, supernatant reactant liquor is gone, then precipitation silver powder by washed with de-ionized water to electrical conductivity 16 μ s/cm, then with absolute alcohol clean 2 times.By clean silver powder in air dry oven 60 ℃, dry 18 hours, after being finally dried, obtain high crystallization flake silver powder.Institute film-making silver tap density: 4.1g/cc, size distribution: D
100.6umD
501.0um D
901.4um.
Embodiment 4
A preparation method for high crystallization flake silver powder, adopts following steps:
(1) take silver nitrate and micro-palladium nitrate as additive, precursor solution take diethylene glycol as solvent composition, precursor solution is added drop-wise to hybrid reaction in the reducing solution that contains PEG-20000 and hydrogen peroxide take diethylene glycol as solvent, when reaction, be under the condition of high-speed stirred, control reaction temperature at 25 ℃, precursor solution is joined in reducing solution at 30min, question response finishes rear continuation and stirs, wherein, in precursor solution, the concentration of silver nitrate is 0.5g/L, and the mole of palladium nitrate is silver nitrate 10
-2doubly, in reducing solution, contain hydrogen peroxide and the silver nitrate mole 10 of 8 times of silver nitrate moles
-2pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent;
(2) continue to drip wherein the silver ammino solution take diethylene glycol as solvent, in silver ammino solution, the concentration of silver nitrate is 17g/L, the concentration of ammoniacal liquor is 55g/L, when reaction, be silver ammino solution to be added drop-wise in 20min in the mixed solution that step (1) obtains, react rear sedimentation 30min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder, to electrical conductivity 10us/cm, then clean 2 times finally in air dry oven 50 ℃ with anhydrous propanone or alcohol by washed with de-ionized water, dry 20 hours, prepare high crystallization flake silver powder.
Embodiment 5
A preparation method for high crystallization flake silver powder, adopts following steps:
(1) take silver nitrate and micro-palladium nitrate as additive, precursor solution take diethylene glycol as solvent composition, precursor solution is added drop-wise to hybrid reaction in the reducing solution that contains PEG-20000 and hydrogen peroxide take diethylene glycol as solvent, when reaction, be under the condition of high-speed stirred, control reaction temperature at 40 ℃, precursor solution is joined in reducing solution at 0.5min, question response finishes rear continuation and stirs, wherein, in precursor solution, the concentration of silver nitrate is 3g/L, and the mole of palladium nitrate is silver nitrate 10
-3doubly, in reducing solution, contain hydrogen peroxide and the silver nitrate mole 10 of 10 times of silver nitrate moles
-3pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent;
(2) continue to drip wherein the silver ammino solution take diethylene glycol as solvent, in silver ammino solution, the concentration of silver nitrate is 35g/L, the concentration of ammoniacal liquor is 150g/L, when reaction, be silver ammino solution to be added drop-wise in 60min in the mixed solution that step (1) obtains, react rear sedimentation 90min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder, to electrical conductivity 20us/cm, then clean 4 times finally in air dry oven 60 ℃ with anhydrous propanone or alcohol by washed with de-ionized water, dry 10 hours, prepare high crystallization flake silver powder.
Claims (7)
1. a preparation method for high crystallization flake silver powder, is characterized in that, the method adopts following steps:
(1) take silver nitrate and micro-palladium nitrate as additive, the precursor solution take diethylene glycol as solvent composition, is added drop-wise to hybrid reaction in the reducing solution that contains PEG-20000 and hydrogen peroxide take diethylene glycol as solvent by precursor solution;
(2) continue to drip wherein the silver ammino solution take diethylene glycol as solvent, continue reaction to reacting completely, gained precipitation is high crystallization flake silver powder after cleaning-drying.
2. the preparation method of a kind of high crystallization flake silver powder according to claim 1, is characterized in that, in described precursor solution, the concentration of silver nitrate is 0.5～3g/L, and the mole of palladium nitrate is silver nitrate 10
-2-10
-3doubly.
3. the preparation method of a kind of high crystallization flake silver powder according to claim 1, is characterized in that, contains hydrogen peroxide and the silver nitrate mole 10 of 8～10 times of silver nitrate moles in described reducing solution
-2-10
-3pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent.
4. the preparation method of a kind of high crystallization flake silver powder according to claim 1, is characterized in that, in described silver ammino solution, the concentration of silver nitrate is 17-35g/L, and the concentration of ammoniacal liquor is 55-150g/L.
5. the preparation method of a kind of high crystallization flake silver powder according to claim 1, it is characterized in that, step (1) is under the condition of high-speed stirred, control reaction temperature at 25-40 ℃, precursor solution is joined in reducing solution at 0.5-30min, question response finishes rear continuation and stirs, stand-by.
6. the preparation method of a kind of high crystallization flake silver powder according to claim 1, it is characterized in that, step (2) is added drop-wise to silver ammino solution in the mixed solution that step (1) obtains in 20-60min, react rear sedimentation 30-90min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder.
7. according to the preparation method of a kind of high crystallization flake silver powder described in claim 1 or 6, it is characterized in that, the precipitate with deionized water obtaining is cleaned to electrical conductivity 10-20us/cm, clean 2-4 time with anhydrous propanone or alcohol again, finally 50-60 ℃ in air dry oven, dry 10-20 hour, prepares high crystallization flake silver powder.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110238385A (en) * | 2019-08-01 | 2019-09-17 | 河南金渠银通金属材料有限公司 | The preparation method of round pie chip super fine silver powder |
| CN116532656A (en) * | 2023-05-11 | 2023-08-04 | 湖北银科新材料股份有限公司 | High-conductivity high-dispersion flaky silver adhesive and preparation method thereof |
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| CN1401452A (en) * | 2001-08-17 | 2003-03-12 | 中国科学院过程工程研究所 | Preparation of hexagonal plate silver powder by chemical reduction process |
| JP2006111903A (en) * | 2004-10-13 | 2006-04-27 | Shoei Chem Ind Co | High crystalline flaky silver powder and its producing method |
| US20060090600A1 (en) * | 2004-10-29 | 2006-05-04 | Goia Dan V | Polyol-based method for producing ultra-fine copper powders |
| CN1925941A (en) * | 2004-02-10 | 2007-03-07 | 三井金属矿业株式会社 | Highly crystalline silver powder and method for production thereof |
| CN102133635A (en) * | 2011-05-02 | 2011-07-27 | 杨荣春 | Silver powder and manufacturing method thereof |
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Patent Citations (6)
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| CN1401452A (en) * | 2001-08-17 | 2003-03-12 | 中国科学院过程工程研究所 | Preparation of hexagonal plate silver powder by chemical reduction process |
| CN1925941A (en) * | 2004-02-10 | 2007-03-07 | 三井金属矿业株式会社 | Highly crystalline silver powder and method for production thereof |
| JP2006111903A (en) * | 2004-10-13 | 2006-04-27 | Shoei Chem Ind Co | High crystalline flaky silver powder and its producing method |
| US20060090600A1 (en) * | 2004-10-29 | 2006-05-04 | Goia Dan V | Polyol-based method for producing ultra-fine copper powders |
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| CN110238385A (en) * | 2019-08-01 | 2019-09-17 | 河南金渠银通金属材料有限公司 | The preparation method of round pie chip super fine silver powder |
| CN116532656A (en) * | 2023-05-11 | 2023-08-04 | 湖北银科新材料股份有限公司 | High-conductivity high-dispersion flaky silver adhesive and preparation method thereof |
| CN116532656B (en) * | 2023-05-11 | 2024-01-23 | 湖北银科新材料股份有限公司 | High-conductivity high-dispersion flaky silver adhesive and preparation method thereof |
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