CN106854768B - electrodeposition preparation method of superfine copper powder - Google Patents
electrodeposition preparation method of superfine copper powder Download PDFInfo
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- CN106854768B CN106854768B CN201611022171.XA CN201611022171A CN106854768B CN 106854768 B CN106854768 B CN 106854768B CN 201611022171 A CN201611022171 A CN 201611022171A CN 106854768 B CN106854768 B CN 106854768B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
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Abstract
The invention discloses an electrodeposition preparation method of superfine copper powder. The method comprises the steps of preparing a copper sulfate solution by taking industrial copper sulfate as a raw material, adding concentrated ammonia water, sulfuric acid and a dispersing agent to stabilize copper ions, changing the precipitation potential of copper, increasing the reaction force among solid particles, then performing electrodeposition to stably precipitate the copper to obtain copper powder, finally washing the copper powder, placing the washed copper powder in an antioxidant solution, stirring at room temperature to perform surface modification, then washing and drying to obtain the superfine copper powder with stable properties. The invention takes industrial copper sulfate as raw material, so the cost is lower and the raw material source is wider; copper ions can be uniformly separated out at the cathode, and superfine copper powder with small, uniform and narrow distribution grain size is obtained, wherein the median grain size is about 0.925 mu m, and the superfine copper powder can be placed in the air for more than 150 days without being oxidized.
Description
Technical field
It is specifically a kind of using industrial cupric sulfate to be raw material, ultra-fine the present invention relates to a kind of preparation method of metal powder
The electrodeposition preparation method of copper powder.
Background technique
With the development of industrial technology, submicron particle is increasingly becoming emerging high-tech product and sophisticated industry basis material
Material.Superfine cupper powder becomes the base that purposes is wide, potentiality are big, economic value added is high due to the characteristics such as its intensity is high, conducts electricity very well
Plinth functional powder material is widely used in the bath of the necks such as metallurgy, electronics, medicine and machinery.
Copper powder particle size and inoxidizability are the main indicator of gauge copper mealiness energy, and influence the main of copper powder price
Factor.Currently, more mature copper powder preparation method has atomization, chemical reduction method and electrolysis method.Atomization and electronation
Method, for raw material, keeps production cost high dependent on cathode copper or with fine copper etc.；Electrolysis method generally uses fine copper plate to do anode,
Titanium plate does cathode, and sulfate system does electrolyte, and the anode scrap after electrolysis need to constantly replace and founding again, the copper powder of generation
Grain is larger, and micron order is not achieved, and size distribution is uneven, it is serious to reunite, and leads to entire production technology large labor intensity, cost
Height, obtained copper powder economic value added are low.Application No. is 200510007317.9 Chinese invention patents to provide a kind of electrodeposition
The method of production copper powder expands the raw material sources of copper powder, fundamentally reduces copper using copper sponge or copper scap as raw material
The production cost of powder, but copper powder size made from this method is still larger, up to 70 μm or so, and its antioxygenic property also without
Method is protected, and causes its economic value added still lower.
Summary of the invention
The object of the present invention is to provide a kind of low production cost, copper powder particle size is small and is evenly distributed, copper powder inoxidizability
The electrodeposition preparation method of superfine cupper powder that can be high, to further increase the economic value added of copper powder.
The purpose of the present invention is what is realized by following scheme: using industrial cupric sulfate as raw material, configuring copper-bath, so
Concentrated ammonia liquor, sulfuric acid and dispersing agent are added afterwards and stablizes copper ion, changes the deposition potential of copper, increase the reaction force between solid particle
After carry out electrodeposition, make copper stablize be precipitated obtain copper powder, finally by copper powder washing be placed in antioxidant solution, stir at room temperature
Carry out that surface is modified washes, is dried in vacuo again, to obtain superfine cupper powder.Specifically includes the following steps:
(1) configuration of electrolytic cell
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 4-5 cm；
(2) preparation of copper-containing solution
Using industrial cupric sulfate as raw material, it is configured to the copper-bath that copper ion concentration is 90-150 g/L and filtering；It takes
Complexing agent, sulfuric acid and dispersing agent is added in filtrate, be configured to copper ion concentration be 5-40 g/L, ammonia concn be 80-160 g/L,
The solution that sulfuric acid concentration is 60-200 g/L, dispersion dosage is 0.01-3%, heating water bath is to being pumped into electrolytic cell after 30-60 DEG C；
(3) the electrodeposition preparation of copper powder
It is passed through direct current, controls cathode-current density 600-2500 A/m2；In electrolytic deposition process, followed using peristaltic pump
The feed liquor of ring liquid and out hydraulic control system, and the copper-bath that copper ion concentration is 90-150 g/L is added into circulation fluid, with
The stabilization of electrodeposition environment is maintained, additional amount is the 1-5% of global cycle liquid product per hour；
(4) powder operation is scraped
In electrolytic deposition process, every 5-8 min progress once scrapes powder operation, to reduce the partial size of copper powder；
(5) copper powder anti-oxidant treatment
After electrodeposition operation, extracts liquid after electrodeposition out, copper powder is washed with deionized to neutrality residual in copper powder thoroughly to remove
The electrolyte ion stayed is placed in the ethanol solution of antioxidant, and it is modified to carry out surface by stirring at room temperature；Change
After copper powder after property is washed with deionized again, vacuum drying.
Dispersing agent is polyvinyl alcohol, triethanolamine or polyvinylpyrrolidone in above-mentioned steps (2).
Antioxidant is lauryl mercaptan or odium stearate, mass fraction 0.1-0.5% in step (5)；Whip modified turns
Speed is 100-300 r/min, and the time is 15-30 min；Modified, copper powder after washing drying pressure is 0.05-0.1 Mpa, is done
Dry temperature is 40-70 DEG C.
Compared with prior art, the invention has the following advantages:
(1) the electrodeposition preparation method of superfine cupper powder of the present invention is using industrial cupric sulfate as raw material, and cost is lower, raw material sources
It is more extensive.
(2) present invention makes Cu by the way that ammonium hydroxide is added into copper-bath2+Relatively stable [Cu is generated with complexing
(NH3)4]2+, change Cu2+Copper ion is precipitated uniformly in cathode in deposition potential on cathode, and it is smaller, equal to obtain partial size
Even and narrow distribution superfine cupper powder.
(3) it is about 0.925 μm using the superfine cupper powder median of method preparation in the present invention, can places in air
150 days or more and it is not oxidized, property stablize.
Detailed description of the invention
Fig. 1 is the superfine cupper powder particle size distribution figure of method preparation in the embodiment of the present invention 1.
In figure, abscissa indicates that partial size, ordinate indicate particle diameter distribution, and curve a is calculus cloth curve, and curve b is tired
Count distribution curve.
Specific embodiment
For a better understanding of the present invention, the present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 4 cm；With
Industrial cupric sulfate is raw material, is configured to the copper-bath that copper ion concentration is 90 g/L and filtering；Take filtrate be added concentrated ammonia liquor,
Sulfuric acid and polyvinyl alcohol, are configured to that copper ion concentration is 5 g/L, ammonia concn is 80 g/L, sulfuric acid concentration is 60 g/L, poly- second
The solution that enol amount is 0.01%, heating water bath is to being pumped into electrolytic cell after 30 DEG C；It is passed through direct current, controls cathode-current density
For 600 A/m2；In electrolytic deposition process, the feed liquor and hydraulic control system out of circulation fluid are carried out using peristaltic pump, and add into circulation fluid
Copper ion concentration is the copper-bath of 90 g/L, and to maintain the stabilization of electrodeposition environment, additional amount is global cycle liquid per hour
Long-pending 5%；In electrolytic deposition process, every 5 min progress once scrapes powder operation, to reduce the partial size of copper powder；After electrodeposition operation, extraction electricity
Liquid after product copper powder is washed with deionized to neutrality thoroughly to remove remaining electrolyte ion in copper powder and be placed on quality point
In lauryl mercaptan-ethanol solution that number is 0.1%, it is modified that 15 min progress surface is stirred with 100 r/min at room temperature；
Modified copper powder be washed with deionized again after in 0.1 Mpa of pressure, temperature is to be dried in vacuo at 65 DEG C.
Granularmetric analysis shows that the copper powder size prepared using the above method is smaller, is evenly distributed and narrow, median D50=
0.877 μm (curve a, b in Fig. 1).
Stability test in air at room temperature shows that copper powder property in 155 days is stablized.
Embodiment 2
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 4 cm；With
Industrial cupric sulfate is raw material, is configured to the copper-bath that copper ion concentration is 120 g/L and filtering；Take filtrate that dense ammonia is added
Water, sulfuric acid and polyvinyl alcohol, are configured to that copper ion concentration is 10 g/L, ammonia concn is 100 g/L, sulfuric acid concentration is 80 g/
L, the solution that polyvinyl alcohol amount is 3%, heating water bath is to being pumped into electrolytic cell after 40 DEG C；It is passed through direct current, control cathode current is close
Degree is 1800 A/m2；In electrolytic deposition process, the feed liquor and hydraulic control system out of circulation fluid are carried out using peristaltic pump, and into circulation fluid
The copper-bath that copper ion concentration is 100 g/L is added, to maintain the stabilization of electrodeposition environment, additional amount is global cycle per hour
The 4% of liquid product；In electrolytic deposition process, every 5 min progress once scrapes powder operation, to reduce the partial size of copper powder；After electrodeposition operation, take out
Copper powder is washed with deionized to neutrality and is placed on matter thoroughly to remove remaining electrolyte ion in copper powder by liquid after electrodeposition out
It measures in lauryl mercaptan-ethanol solution that score is 0.5%, stirs 20 min at room temperature with 300 r/min and carry out surface
It is modified；Modified copper powder be washed with deionized again after in 0.05 Mpa of pressure, temperature is to be dried in vacuo at 40 DEG C.
Granularmetric analysis shows that the copper powder size prepared using the above method is smaller, is evenly distributed and narrow, median D50=
0.882 μm。
Stability test in air at room temperature shows that copper powder property in 160 days is stablized.
Embodiment 3
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 4.5 cm；
Using industrial cupric sulfate as raw material, it is configured to the copper-bath that copper ion concentration is 120 g/L and filtering；Take filtrate that dense ammonia is added
Water, sulfuric acid and triethanolamine, are configured to that copper ion concentration is 15 g/L, ammonia concn is 120 g/L, sulfuric acid concentration is 120 g/
L, the solution that triethanolamine amount is 0.05%, heating water bath is to being pumped into electrolytic cell after 40 DEG C；It is passed through direct current, control cathode electricity
Current density is 1600 A/m2；In electrolytic deposition process, the feed liquor and hydraulic control system out of circulation fluid are carried out using peristaltic pump, and to circulation
The copper-bath that copper ion concentration is 120 g/L is added in liquid, to maintain the stabilization of electrodeposition environment, additional amount is total per hour
The 3% of circulation fluid volume；In electrolytic deposition process, every 5 min progress once scrapes powder operation, to reduce the partial size of copper powder；Electrodeposition operation
Afterwards, liquid after extraction electrodeposition, copper powder is washed with deionized to neutrality thoroughly to remove in copper powder after remaining electrolyte ion
Being placed in concentration is in odium stearate-ethanol solution that mass fraction is 0.1%, at room temperature with 200 r/min stirring 30
It is modified that min carries out surface；Modified copper powder be washed with deionized again after in 0.08 Mpa, temperature is vacuum at 55 DEG C
It is dry.
Granularmetric analysis shows that the copper powder size prepared using the above method is smaller, is evenly distributed and narrow, median D50=
0.925 μm。
Stability test in air at room temperature shows that copper powder property in 170 days is stablized.
Embodiment 4
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 5 cm；With
Industrial cupric sulfate is raw material, is configured to the copper-bath that copper ion concentration is 150 g/L and filtering；Take filtrate that dense ammonia is added
Water, sulfuric acid and polyvinylpyrrolidone, are configured to that copper ion concentration is 30 g/L, ammonia concn is 150 g/L, sulfuric acid concentration is
150 g/L, the solution that polyvinylpyrrolidone amount is 1.5%, heating water bath is to being pumped into electrolytic cell after 50 DEG C；It is passed through direct current
Electricity, control cathode-current density are 2200 A/m2；The feed liquor that circulation fluid is carried out using peristaltic pump in electrolytic deposition process and hydraulic control out
System, and the copper-bath that copper ion concentration is 150 g/L is added into circulation fluid, to maintain the stabilization of electrodeposition environment, often
Hour additional amount is the 2% of global cycle liquid product；In electrolytic deposition process, every 6 min progress once scrapes powder operation, to reduce copper powder
Partial size；After electrodeposition operation, extracts liquid after electrodeposition out, copper powder is washed with deionized to neutrality remaining in copper powder thoroughly to remove
Electrolyte ion is placed in odium stearate-ethanol solution that mass fraction is 0.5%, at room temperature with 300 r/min
It is modified to stir 15 min progress surface；Modified copper powder be washed with deionized again after in 0.1 Mpa, temperature is at 45 DEG C
Vacuum drying.
Granularmetric analysis shows that the copper powder size prepared using the above method is smaller, is evenly distributed and narrow, median D50=
0.952 μm。
Stability test in air at room temperature shows that copper powder property in 170 days is stablized.
Embodiment 5
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 5 cm；With
Industrial cupric sulfate is raw material, is configured to the copper-bath that copper ion concentration is 150 g/L and filtering；Take filtrate that dense ammonia is added
Water, sulfuric acid and polyvinylpyrrolidone, are configured to that copper ion concentration is 40 g/L, ammonia concn is 160 g/L, sulfuric acid concentration is
200 g/L, the solution that polyvinylpyrrolidone amount is 3%, heating water bath is to being pumped into electrolytic cell after 60 DEG C；It is passed through direct current, is controlled
Cathode-current density processed is 2500 A/m2；In electrolytic deposition process, the feed liquor and hydraulic control system out of circulation fluid are carried out using peristaltic pump, with
And added into circulation fluid copper ion concentration be 150 g/L copper-bath, to maintain the stabilization of electrodeposition environment, per hour plus
Enter 1% that amount is global cycle liquid product；In electrolytic deposition process, every 8 min progress once scrapes powder operation, to reduce the partial size of copper powder；Electricity
After product operation, extracts liquid after electrodeposition out, copper powder is washed with deionized to neutrality thoroughly to remove remaining electrolyte in copper powder
Ion is placed in odium stearate-ethanol solution that mass fraction is 0.25%, at room temperature with 100 r/min stirring 30
It is modified that min carries out surface；Modified copper powder be washed with deionized again after in 0.05 Mpa, temperature is that vacuum is dry at 70 DEG C
It is dry.
Granularmetric analysis shows that the copper powder size prepared using the above method is smaller, is evenly distributed and narrow, median D50=
0.987 μm。
Stability test in air at room temperature shows that copper powder property in 175 days is stablized.
Claims (3)
1. the electrodeposition preparation method of superfine cupper powder, which comprises the following steps:
(1) configuration of electrolytic cell
Make glass fibre electrolytic cell by oneself, using Pb-Ca-Sn alloy sheets as anode, pure copper sheet is cathode, and pole span is 4-5 cm；
(2) preparation of copper-containing solution
Using industrial cupric sulfate as raw material, it is configured to the copper-bath that copper ion concentration is 90-150 g/L and filtering；Take filtrate
Concentrated ammonia liquor, sulfuric acid and dispersing agent is added, is configured to that copper ion concentration is 5-40 g/L, ammonia concn is 80-160 g/L, sulfuric acid
The solution that concentration is 60-200 g/L, dispersion dosage is 0.01-3%, heating water bath is to being pumped into electrolytic cell after 30-60 DEG C；
(3) the electrodeposition preparation of copper powder
It is passed through direct current, controls cathode-current density 600-2500 A/m2；In electrolytic deposition process, circulation fluid is carried out using peristaltic pump
Feed liquor and out hydraulic control system, and add into circulation fluid the copper-bath that copper ion concentration is 90-150 g/L, per hour plus
Enter the 1-5% that amount is global cycle liquid product；
(4) powder operation is scraped
In electrolytic deposition process, every 5-8 min carries out once scraping powder operation；
(5) copper powder anti-oxidant treatment
After electrodeposition operation, liquid after electrodeposition is extracted out, it is 0.1- that copper powder, which is washed with deionized, and is placed on mass fraction to neutrality
In the ethanol solution of 0.5% lauryl mercaptan, surface is carried out by stirring at room temperature and is modified, the revolving speed of whip modified is
100-300 r/min, time are 15-30 min；After modified copper powder is washed with deionized again, vacuum drying.
2. the electrodeposition preparation method of superfine cupper powder according to claim 1, it is characterised in that: disperse described in step (2)
Agent is polyvinyl alcohol, triethanolamine or polyvinylpyrrolidone.
3. the electrodeposition preparation method of superfine cupper powder according to claim 1, it is characterised in that: modified described in step (5),
The drying pressure of copper powder is 0.05-0.09 Mpa after washing, and temperature is 40-70 DEG C.
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| CN110144604B (en) * | 2019-06-17 | 2020-06-09 | 阳谷祥光铜业有限公司 | Preparation process of electrodeposited copper powder |
| CN110697756A (en) * | 2019-10-26 | 2020-01-17 | 韩亚半导体材料(贵溪)有限公司 | Production process of high-purity copper oxide powder for integrated circuit |
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|---|---|---|---|---|
| CN100344795C (en) * | 2005-02-06 | 2007-10-24 | 金川集团有限公司 | Method for producing copper powder by electrodeposition |
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| JP2001181885A (en) * | 1999-12-20 | 2001-07-03 | Sumitomo Metal Mining Co Ltd | Method for producing electrolytic metal powder |
| CN101024252A (en) * | 2006-02-20 | 2007-08-29 | 培尔梅烈克电极股份有限公司 | Production method for electrolyzing metal powder |
| CN101818364A (en) * | 2009-04-03 | 2010-09-01 | 兰州理工大学 | Method for preparing nano copper powder |
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