CN103831444B - A kind of preparation method of high crystallization flake silver powder - Google Patents
A kind of preparation method of high crystallization flake silver powder Download PDFInfo
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- CN103831444B CN103831444B CN201410087807.3A CN201410087807A CN103831444B CN 103831444 B CN103831444 B CN 103831444B CN 201410087807 A CN201410087807 A CN 201410087807A CN 103831444 B CN103831444 B CN 103831444B
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Abstract
The present invention relates to a kind of preparation method of high crystallization flake silver powder, with silver nitrate and micro-palladium nitrate for additive, take diethylene glycol as the precursor solution of solvent composition, precursor solution is added drop-wise to diethylene glycol be solvent containing hybrid reaction in the reducing solution of PEG-20000 and hydrogen peroxide; Continuing to drip wherein with diethylene glycol is the silver ammino solution of solvent, continues reaction to reacting completely, and gained precipitation is high crystallization flake silver powder after cleaning-drying.Compared with prior art, the silver powder that the present invention prepares has the advantages such as tap density is high, particle size dispersion narrow range, smooth surface, oil absorbency are low.
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, media electronic slurry important conducting function material---the demand of super fine silver powder constantly increases, and also increasingly strict to the requirement of performance as size and distribution, pattern, specific area etc. of argent powder.The form of current silver powder roughly has spherical, flakey, dendroid and sheet.When flake silver powder conducts electricity as filler, it is face or linear contact lay each other,
Spherical silver powder is point cantact, so flake silver powder is much lower than the resistance of spherical silver powder, even still there is higher electrical conductivity compared with when low silver content and thinner printed coating, 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 the sheet of light, to the printing effect of electronic circuit, comprise uniformity, flatness etc. all to have clear improvement, and noble metal dosage 30% ~ 50% can be saved.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 the advantage of its uniqueness.Abundant solar radiation is inexhaustible, pollution-free, cheap, and can use by safe and free.Along with the progress of science and technology, require that the transformation efficiency constantly improving solar cell obtains more electric energy, therefore require to innovate from the structure of solar cell, technique and material.Especially in the preparation of solar energy back silver slurry, flake silver powder is best in quality directly affects transformation efficiency.
At present, prepare flake silver powder in the world, great majority are spherical or irregular silver powder prepared by first chemistry or Physical, are then obtained by ball-milling technology.As application publication number: CN102794453A, in its preparation process, Ball-milling Time is grown and in mechanical milling process, is introduced a large amount of additive and makes the reduction of silver powder purity, preparation technology's at substantial electric energy etc. many unfavorable.
Summary of the invention
Object of the present invention is exactly the preparation method providing that a kind of tap density is high, particle size dispersion narrow range, smooth surface, oil absorbency are low to overcome defect that above-mentioned prior art exists and be easy to 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) with silver nitrate and micro-palladium nitrate for additive, take diethylene glycol as the precursor solution of solvent composition, precursor solution is added drop-wise to diethylene glycol be solvent containing hybrid reaction in the reducing solution of PEG-20000 and hydrogen peroxide;
(2) continuing to drip wherein with diethylene glycol is the silver ammino solution of solvent, continues reaction to reacting completely, and 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 10 of silver nitrate
-2-10
-3doubly.
Hydrogen peroxide containing silver nitrate mole 8 ~ 10 times in described reducing solution and silver nitrate mole 10
-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 DEG C, joins in reducing solution by precursor solution at 0.5-30min, and question response terminates rear continuation and stirs, stand-by.
Silver ammino solution is added drop-wise in the mixed solution that step (1) obtains by step (2) in 20-60min, has reacted rear sedimentation 30-90min, and remove supernatant reactant liquor, what obtain is precipitated as flake silver powder.
The precipitate with deionized water cleaning obtained is to electrical conductivity 10-20us/cm, then with anhydrous propanone or alcohol washes 2-4 time, finally 50-60 DEG C in air dry oven, dry 10-20 hour, prepare high crystallization flake silver powder.
Compared with prior art, tap density of the present invention is high, particle size dispersion narrow range, smooth surface, oil absorbency are low.More traditional aqueous phase hydrometallurgy compares, react in the organic phase of diethylene glycol because the present invention adopts, therefore, the polarity of reaction system is little, few to influence factor during crystal growth, thus make the Argent grain on chip grown have the good characteristics such as degree of crystallinity is high, smooth surface, tap density are large.Meanwhile, the method preparation technology is simple, facilitates large-scale production.
Detailed description of the invention
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 mixing reducing solution, hydrogen peroxide 68.5g, PEG-200002g, ammoniacal liquor 20g spend diethylene glycol and are mixed with mixing reducing solution.While high-speed stirred mixing reducing solution, precursor solution and mixing reducing solution Homogeneous phase mixing are reacted, controls reaction temperature at 50 DEG C, reaction time 10min.Continue after reacting completely to stir, and in 30min, silver ammino solution is dripped wherein.After sedimentation 50min, supernatant reactant liquor is gone to get its precipitation after anyway.After sedimentation 45min, supernatant reactant liquor is gone after anyway, then the silver powder washed with de-ionized water of precipitation to electrical conductivity 10 μ s/cm, then clean 2 times with absolute alcohol.By the silver powder in air dry oven 60 DEG C cleaned, dry 11 hours, finally will namely obtain high crystallization flake silver powder after drying.Institute film-making silver tap density: 4.3g/cc, size distribution: D
100.8umD
501.1umD
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 mixing reducing solution, hydrogen peroxide 100g, PEG-200001.5g, ammoniacal liquor 45g spend diethylene glycol and are mixed with mixing reducing solution.While high-speed stirred mixing reducing solution, precursor solution and mixing reducing solution Homogeneous phase mixing are reacted, controls reaction temperature at 30 DEG C, reaction time 30min.Continue after reacting completely to stir, and in 45min, silver ammino solution is dripped wherein.After sedimentation 60min, supernatant reactant liquor is gone to get its precipitation after anyway.After sedimentation 65min, supernatant reactant liquor is gone after anyway, then the silver powder washed with de-ionized water of precipitation to electrical conductivity 15 μ s/cm, then clean 3 times with acetone.By the silver powder in air dry oven 56 DEG C cleaned, dry 13 hours, finally will namely obtain high crystallization flake silver powder after drying.Institute film-making silver tap density: 4.4g/cc, size distribution: D
100.7umD
501.3umD
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 mixing reducing solution, hydrogen peroxide 80g, PEG-200000.5g, ammoniacal liquor 15g spend diethylene glycol and are mixed with mixing reducing solution.While high-speed stirred mixing reducing solution, precursor solution and mixing reducing solution Homogeneous phase mixing are reacted, controls reaction temperature at 25 DEG C, reaction time 15min.Continue after reacting completely to stir, and in 20min, silver ammino solution is dripped wherein.After sedimentation 60min, supernatant reactant liquor is gone to get its precipitation after anyway.After sedimentation 90min, supernatant reactant liquor is gone after anyway, then the silver powder washed with de-ionized water of precipitation to electrical conductivity 16 μ s/cm, then clean 2 times with absolute alcohol.By the silver powder in air dry oven 60 DEG C cleaned, dry 18 hours, finally will namely obtain high crystallization flake silver powder after drying.Institute film-making silver tap density: 4.1g/cc, size distribution: D
100.6umD
501.0umD
901.4um.
Embodiment 4
A preparation method for high crystallization flake silver powder, adopts following steps:
(1) with silver nitrate and micro-palladium nitrate for additive, take diethylene glycol as the precursor solution of solvent composition, precursor solution is added drop-wise to diethylene glycol be solvent containing hybrid reaction in the reducing solution of PEG-20000 and hydrogen peroxide, during reaction under the condition of high-speed stirred, control reaction temperature at 25 DEG C, precursor solution is joined in reducing solution at 30min, question response terminates rear continuation and stirs, wherein, in precursor solution, the concentration of silver nitrate is 0.5g/L, and the mole of palladium nitrate is 10 of silver nitrate
-2doubly, the hydrogen peroxide containing silver nitrate mole 8 times in reducing solution and silver nitrate mole 10
-2pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent;
(2) continuing to drip wherein with diethylene glycol is the silver ammino solution of solvent, in silver ammino solution, the concentration of silver nitrate is 17g/L, the concentration of ammoniacal liquor is 55g/L, silver ammino solution is added drop-wise in 20min in mixed solution that step (1) obtains during reaction, react rear sedimentation 30min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder, by washed with de-ionized water to electrical conductivity 10us/cm, then with anhydrous propanone or alcohol washes 2 times, finally in air dry oven 50 DEG C, dry 20 hours, prepare high crystallization flake silver powder.
Embodiment 5
A preparation method for high crystallization flake silver powder, adopts following steps:
(1) with silver nitrate and micro-palladium nitrate for additive, take diethylene glycol as the precursor solution of solvent composition, precursor solution is added drop-wise to diethylene glycol be solvent containing hybrid reaction in the reducing solution of PEG-20000 and hydrogen peroxide, during reaction under the condition of high-speed stirred, control reaction temperature at 40 DEG C, precursor solution is joined in reducing solution at 0.5min, question response terminates rear continuation and stirs, wherein, in precursor solution, the concentration of silver nitrate is 3g/L, and the mole of palladium nitrate is 10 of silver nitrate
-3doubly, the hydrogen peroxide containing silver nitrate mole 10 times in reducing solution and silver nitrate mole 10
-3pEG-20000 doubly, and adopt ammoniacal liquor as pH stabilizing agent;
(2) continuing to drip wherein with diethylene glycol is the silver ammino solution of solvent, in silver ammino solution, the concentration of silver nitrate is 35g/L, the concentration of ammoniacal liquor is 150g/L, silver ammino solution is added drop-wise in 60min in mixed solution that step (1) obtains during reaction, react rear sedimentation 90min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder, by washed with de-ionized water to electrical conductivity 20us/cm, then with anhydrous propanone or alcohol washes 4 times, finally in air dry oven 60 DEG C, 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 as presoma, micro-palladium nitrate is additive, and diethylene glycol is solvent composition precursor solution, precursor solution is added drop-wise to diethylene glycol be solvent containing hybrid reaction in the reducing solution of PEG-20000 and hydrogen peroxide;
(2) continuing to drip wherein with diethylene glycol is the silver ammino solution of solvent, continues reaction to reacting completely, and 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, it 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 10 of silver nitrate
-2-10
-3doubly.
3. the preparation method of a kind of high crystallization flake silver powder according to claim 1, is characterized in that, the hydrogen peroxide containing silver nitrate mole 8 ~ 10 times in described reducing solution and silver nitrate mole 10
-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 DEG C, precursor solution is joined in reducing solution at 0.5-30min, question response terminates 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, silver ammino solution is added drop-wise in the mixed solution that step (1) obtains by step (2) in 20-60min, react rear sedimentation 30-90min, remove supernatant reactant liquor, what obtain is precipitated as flake silver powder.
7. the preparation method of a kind of high crystallization flake silver powder according to claim 1 or 6, it is characterized in that, the precipitate with deionized water cleaning obtained is to electrical conductivity 10-20us/cm, again with anhydrous propanone or alcohol washes 2-4 time, finally 50-60 DEG C in air dry oven, dry 10-20 hour, prepares high crystallization flake silver powder.
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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 |
| 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 |
Citations (5)
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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 |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060090597A1 (en) * | 2004-10-29 | 2006-05-04 | Goia Dan V | Polyol-based method for producing ultra-fine metal powders |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102133635A (en) * | 2011-05-02 | 2011-07-27 | 杨荣春 | Silver powder and manufacturing method thereof |
| 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 |
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