CN101513675A - Preparation method of ultrafine copper powder for conductive paste - Google Patents
Preparation method of ultrafine copper powder for conductive paste Download PDFInfo
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- CN101513675A CN101513675A CNA2009100430437A CN200910043043A CN101513675A CN 101513675 A CN101513675 A CN 101513675A CN A2009100430437 A CNA2009100430437 A CN A2009100430437A CN 200910043043 A CN200910043043 A CN 200910043043A CN 101513675 A CN101513675 A CN 101513675A
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Abstract
The invention discloses a preparation method of ultrafine copper powder for conductive paste. The preparation method comprises the following steps: firstly, coating copper oxide with a compound, reducing the coated copper oxide at high temperature to prepare copper powder, and finally densifying the obtained copper powder at high temperature. The preparation method overcomes preparation cost defect and product performance defect of preparing the copper powder by a gas-phase method and a liquid-phase reduction method, and help produce the ultrafine copper powder which has controllable grain size, good dispersibility, high density and mature crystal form, and meet production requirements for electrodes of multilayer ceramic capacitors. The preparation method has simple equipment and short process flow, and is applicable to industrialized production of the copper powder.
Description
Technical field
The present invention relates to a kind of preparation method of copper powder, especially a kind of preparation method of ultrafine copper powder for conductive paste.
Background technology
Metal dust is important basic raw material, both can directly disperse to use, and also can and sinter block materials into its press forming, can also make film material etc.As, superfine cupper powder can be made effective catalyst, electrically-conducting paint, also can be used as conducing composite material raw material, electrode material, additive etc.
With hyundai electronics industry is example, and multilayer ceramic capacitor in the hyundai electronics industry (Multilayer ceramiccapacitors is called for short MLCC) has become the main product of capacitor industry, is widely used in communication, computer and consumer electronics product.One of main developing direction of MLCC shows as the lowpriced metallization of electrode, promptly adopts the base metal of low price to replace noble metals such as expensive palladium, silver to reduce cost, and interior electrode is at the cost that can save behind the lowpriced metallization more than 50%.Copper is cheap and easy to get, has high melt point and good electrical conductivity, and high frequency stability is better than gold, silver, and is compatible with most of scolders, and not diffusion or reaction in ceramic dielectric when sintering to the not influence of ceramic dielectric performance, is comparatively desirable electrode material.The MLCC electrode requires it to have smaller particle size with copper powder, narrow diameter distribution, sphericity height, character such as degree of crystallinity height, purity height, good in oxidation resistance, tap density height; Therefore, wish to develop copper powder with above-mentioned characteristic.
At present, the preparation method of copper powder has physics method and chemical method two big classes.The physics method comprises high-energy ball milling method, gas phase steam method, plasma method etc.; Chemical method comprises electrolysis, slaine gas phase reduction process, atomizing-oxidation-reduction method (AOR), sprays thermal decomposition method, liquid phase reduction, hydrogen heat reducing metal oxide method etc.The method of the comparatively main flow of preparation copper powder mainly contains vapor phase method and liquid phase reduction at present.
The basic principle of vapor phase method is that copper is added thermosetting steam, promptly gets copper powder after the steam cooling.The formation process three phases of powder: the copper evaporation produces steam phase, copper diffusion of vapor and also condenses nucleation stage and the nucleus growth stage.Wherein can control the generation and the growth of particle, obtain product through Overheating Treatment at last in the particle stage that produces.The advantage of vapor phase method is that resulting powder is very regular sphere; It is very wide usually that yet vapor phase method gained copper powder size distributes, and be difficult to make the particle diameter distribution to improve.Vapor phase method needs specialized apparatus in addition, and investment is all bigger with energy consumption.
Liquid phase reduction is a kind of common method of preparation copper powder, with suitable reducing agent mantoquita is reduced in liquid phase, is drying to obtain copper powder through washing.Compare with additive method, liquid phase reduction has that equipment is simple, flow process is short, the advantage that cost is low.Adopt Cu
2+Direct-reduction process, because reaction is complicated, the particle nucleation is fast, and growth course is short, and the copper powder size that causes producing distributes very wide, and the pattern of prepared copper powder is wayward.In addition, when preparation submicron order or nanoscale copper powder, in reaction and dry run, usually take place to reunite and oxidation.
Also there are a lot of researchers to study the hydrogen heat reducing copper oxides and prepare copper powder.But, in research process, run into some difficult problems.At first, in the process of the oxide of hydrogen reducing copper, in copper powder particle, stay a large amount of holes because oxygen in the oxide and H-H reaction have produced after the water of a large amount of oxygen rooms and their reaction generations is escaped with gaseous form, caused the tap density of copper powder and degree of crystallinity very low; Secondly, in the high-temperature hydrogen reduction process, agglomeration easily takes place in prepared copper powder.
Summary of the invention
It is controlled that technical problem to be solved by this invention provides a kind of acquisition particle diameter, and have the preparation method of smaller particle size, narrow diameter distribution, degree of crystallinity height, good dispersion, ultrafine copper powder for conductive paste that tap density is high.
In order to solve the problems of the technologies described above, the preparation method of ultrafine copper powder for conductive paste provided by the invention comprises: a, obtain having smaller particle size, the oxide of the copper of narrow diameter distribution, good dispersion; B, the oxide of copper is coated processing; C, the oxide cladding of copper is carried out high temperature reduction; D, the powder particle of gained of will reducing carry out the high-temperature shrinkage densification; E, washing clad are collected finished product, it is characterized in that: a, be that the oxide powder of copper of 0.1～5.0 μ m, good dispersion and pure water add in the reactor and evenly disperse with average grain diameter, make the suspension of solid content 1-50g/L; B, be that metal salt solution and the aqueous slkali of 1～50g/L slowly adds in the reactor, continue stirring reaction 10-200min, make its precipitation be coated on the oxide powder surface of copper content; Suspension after being covered to complete is carried out Separation of Solid and Liquid, and with pure water washing cladding for several times, it is dry to clean the back with absolute ethyl alcohol again; C, dried cladding being inserted reduction furnace, is to reduce 0.1-10h with reducing agent under 120～500 ℃ in temperature; D, then 300～1000 ℃ the insulation 0.5-10h shrink densified; E, treat that furnace temperature reduces to room temperature, take out porcelain boat,, more for several times, clean the back drying with absolute ethyl alcohol at last and obtain copper powder with the pure water washing with the coating of dilute sulfuric acid cleaning powder surface.
The oxide of described copper is cupric oxide or cuprous oxide.
Described coating compound can be Mg (OH)
2, Fe (OH)
3Or Al (OH)
3, but being not limited to the compound of enumerating here, the compound of the metal that is difficult to reduce than copper all can be used as the coating compound.
Described Mg (OH)
2, Fe (OH)
3Perhaps Al (OH)
3The dosage of metal hydroxides is---Cu is 1: 1～100: 1 with the ratio of the amount of substance of Mg, Fe or Al in the maintenance system.
Described reducing agent is H
2, CO, methane or natural gas reducibility gas.
Adopt the preparation method of the ultrafine copper powder for conductive paste of technique scheme, its advantage is: 1. easily cause the reunion of copper powder to harden at high temperature reduction, be difficult to obtain the copper powder of polymolecularity.The present invention has adopted the compound of a kind of easy coating and easily washing that Cu oxide has been carried out coating and has handled, and has prevented the agglomeration phenomenon of copper powder under the condition of high temperature.2. in common hydrogen reduction technology, owing to lost oxygen in reduction process, and the water escape process that generates in reaction stayed hole, causes the copper powder particle structure not fine and close, rough, and tap density is lower; In addition, the copper powder of loose structure may infiltrate copper particle inside by organic matter when being prepared into slurry, influence electric conductivity.The present invention has carried out the high-temperature shrinkage densification to the gained powder after reduction obtains copper powder, solve the densified problem of powder of copper powder simply and effectively, has improved the crystal maturity of copper powder particle simultaneously; Degree of crystallinity height, good in oxidation resistance, copper powder that tap density is high have been obtained.3. owing to can not make the pattern of Cu oxide initial phase that bigger change takes place in the high temperature reduction process, the present invention changes the pattern control of copper powder production process into the pattern of ripe Cu oxide preparation process control relatively; Thereby can control the pattern of copper powder better, obtain thinner, the particle diameter narrower stabilized uniform copper powder that distributes.
The present invention has carried out copper powder production technology oxide to copper before reduction to coat processing, has increased powder high-temperature shrinkage densified after reduction reaction, and efficiently solves the problem of the particle diameter pattern control of copper powder particle; Successfully obtain polymolecularity and high compactness superfine cupper powder, started a kind of new technology new approaches that prepare superfine cupper powder.
In sum, the present invention is that a kind of acquisition particle diameter is controlled, and has the preparation method of smaller particle size, narrow diameter distribution, degree of crystallinity height, good dispersion, ultrafine copper powder for conductive paste that tap density is high.
Description of drawings
Fig. 1 is preparation technology's flow chart of the present invention;
Fig. 2 is the SEM photo of the copper powder of embodiment 1;
Fig. 3 is the XRD testing result of the copper powder of embodiment 1;
Fig. 4 is the SEM photo of the copper powder that provides of comparative example 1;
Fig. 5 is the SEM photo of the copper powder that provides of comparative example 2.
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing and example, but the protection domain that the present invention requires is not limited to the scope that following embodiment represents.
Embodiment 1:
Referring to Fig. 1, be the spherical cuprous oxide powder and the evenly dispersion in reactor of 600mL pure water of 1.2 μ m, good dispersion with the 15g average grain diameter, with 6g/L MgCl
2The about 250mL of the aqueous solution slowly adds in the reactor, continue to stir, and then slowly drips more than the pH value to 10 of NaOH solution conditioned reaction system of 2.5mol/L, continues stirring reaction 30min, at Mg (OH)
2Make its precipitation be coated on the cuprous oxide surface in the generative process.Suspension after being covered to complete is carried out Separation of Solid and Liquid, and with pure water washing cladding for several times, it is dry to clean the back with absolute ethyl alcohol again.Dried cladding being tiled in inserting tube furnace in the porcelain boat, is to use H under 150 ℃ in temperature
2Reduction 3h then shrinks densified at 600 ℃ of insulation 1h.Treat that furnace temperature reduces to room temperature, take out porcelain boat,, more for several times, clean the back drying with absolute ethyl alcohol at last and obtain copper powder with the pure water washing with the coating of dilute sulfuric acid cleaning powder surface.As a result, copper powder has kept original pattern of cuprous oxide, and average grain diameter is 1 μ m, and the grain diameter of affirmation more than at least 80% is between 0.9～1.1 μ m, and powder dispersity is good, and no agglomeration phenomenon produces.Fig. 2 has provided the SEM photo of this copper powder, and Fig. 3 is the XRD testing result of this copper powder.
Embodiment 2:
Referring to Fig. 1, be the spherical cupric oxide powder and the evenly dispersion in reactor of 600mL pure water of 1 μ m, good dispersion with the 15g average grain diameter, with the 300mL Mg (OH) that makes in advance
2Colloidal solution (wherein, Mg (OH) with the water composition
2Content be 5g/L) slowly add in the reactor, continue to stir coat 30min.Then use H
2The temperature of reduction is 200 ℃, and the temperature of high-temperature shrinkage is 700 ℃, and other steps are identical with embodiment 1, obtain copper powder.As a result, copper powder has kept original pattern of cupric oxide, and average grain diameter is 0.8 μ m, confirms grain diameter at least 80% or more between 0.7～0.9 μ m, favorable dispersibility, no agglomeration phenomenon generation.
Embodiment 3:
Referring to Fig. 1, be the cuprous oxide powder and the evenly dispersion in reactor of 600mL pure water of 1.2 μ m, good dispersion with the 15g average grain diameter, be the Fe (OH) of 300mL with the volume that makes in advance
3Colloidal solution (wherein, Fe (OH) with the water composition
3Content be 10g/L) slowly add in the reactor, continue to stir coat 30min.Then use H
2The temperature of reduction is 150 ℃, and the temperature of high-temperature shrinkage is 600 ℃, and other steps are identical with embodiment 1, obtain copper powder.As a result, copper powder has kept original pattern of cuprous oxide, and average grain diameter is 1 μ m, confirms grain diameter at least 80% or more between 0.9～1.1 μ m, favorable dispersibility, no agglomeration phenomenon generation.
Embodiment 4:
Referring to Fig. 1, except the coating that will be added changes Al (OH) into
3The colloid of content 8g/L outside, with the embodiment 3 the same copper powders that obtain, result, copper powder has kept original pattern of cuprous oxide, and average grain diameter is 1 μ m, and the grain diameter of affirmation more than at least 80% is between 0.9～1.1 μ m, favorable dispersibility, no agglomeration phenomenon produces.
Embodiment 5:
Referring to Fig. 1, be the spherical cuprous oxide powder and the evenly dispersion in reactor of 600mL pure water of 5.0 μ m, good dispersion with the 6g average grain diameter, with 6g/L MgCl
2The about 250mL of the aqueous solution slowly adds in the reactor, continue to stir, and then slowly drips more than the pH value to 10 of NaOH solution conditioned reaction system of 2.5mol/L, continues stirring reaction 10min, at Mg (OH)
2Make its precipitation be coated on the cuprous oxide surface in the generative process.Suspension after being covered to complete is carried out Separation of Solid and Liquid, and with pure water washing cladding for several times, it is dry to clean the back with absolute ethyl alcohol again.Dried cladding being tiled in inserting tube furnace in the porcelain boat, is to use H under 120 ℃ in temperature
2Reduction 7h then shrinks densified at 300 ℃ of insulation 10h.Treat that furnace temperature reduces to room temperature, take out porcelain boat,, more for several times, clean the back drying with absolute ethyl alcohol at last and obtain copper powder with the pure water washing with the coating of dilute sulfuric acid cleaning powder surface.
Embodiment 6:
Referring to Fig. 1, be the spherical cupric oxide powder and the evenly dispersion in reactor of 600mL pure water of 0.1 μ m, good dispersion with the 30g average grain diameter, with the 300mL Mg (OH) that makes in advance
2Colloidal solution (wherein, Mg (OH) with the water composition
2Content be 5g/L) slowly add in the reactor, continue to stir coat 200min.Then use H
2The temperature of reduction is 500 ℃, then shrinks densified at 1000 ℃ of insulation 0.5h.Treat that furnace temperature reduces to room temperature, take out porcelain boat,, more for several times, clean the back drying with absolute ethyl alcohol at last and obtain copper powder with the pure water washing with the coating of dilute sulfuric acid cleaning powder surface.
In order to specify advantage of the present invention place, the applicant has provided the prepared copper powder of comparative example and inventive method and has contrasted; Fully proved among the present invention, Cu oxide has been carried out coating earlier afterwards reduce and carry out superiority and the novelty of high temperature densification on method reducing the gained copper powder.
Comparative example 1:
The spherical cuprous oxide powder that with the 15g average grain diameter is 0.65 μ m, good dispersion is to use H under 150 ℃ in temperature
2Reduction 3h then shrinks densified at 600 ℃ of insulation 1h.As a result, copper powder is owing to be subjected to thermal sintering, and serious the reunion, dispersiveness is very poor.Fig. 4 has provided the SEM photo of this copper powder.
Comparative example 2:
With the 15g average grain diameter is the cuprous oxide powder and the evenly dispersion in reactor of 600mL pure water of 0.65 μ m, good dispersion, and the coating process is identical with embodiment 3.Then use H
2The temperature of reduction is 200 ℃, does not carry out high-temperature shrinkage, obtains copper powder.As a result, copper powder has kept original pattern of cuprous oxide, and average grain diameter is 0.65 μ m, confirms grain diameter at least 85% or more between 0.6～0.7 μ m, favorable dispersibility, no agglomeration phenomenon generation.But it is rough, obviously has hole, and Zhi Bei copper powder crystal is fine and close inadequately like this, causes tap density less.Fig. 5 has provided the SEM photo of this copper powder.
Claims (5)
1, a kind of preparation method of ultrafine copper powder for conductive paste comprises: a, obtain having smaller particle size, the oxide of the copper of narrow diameter distribution, good dispersion; B, the oxide of copper is coated processing; C, the oxide cladding of copper is carried out high temperature reduction; D, the powder particle of gained of will reducing carry out the high-temperature shrinkage densification; E, washing clad are collected finished product, it is characterized in that:
A, be that the oxide powder of copper of 0.1～5.0 μ m, good dispersion and pure water add in the reactor and evenly disperse with average grain diameter, make the suspension of solid content 1-50g/L;
B, be that metal salt solution and the aqueous slkali of 1～50g/L slowly adds in the reactor, continue stirring reaction 10-200min, make its precipitation be coated on the oxide powder surface of copper content; Suspension after being covered to complete is carried out Separation of Solid and Liquid, and with pure water washing cladding for several times, it is dry to clean the back with absolute ethyl alcohol again;
C, dried cladding being inserted reduction furnace, is to reduce 0.1-10h with reducing agent under 120～500 ℃ in temperature;
D, then 300～1000 ℃ the insulation 0.5-10h shrink densified;
E, treat that furnace temperature reduces to room temperature, take out porcelain boat,, more for several times, clean the back drying with absolute ethyl alcohol at last and obtain copper powder with the pure water washing with the coating of dilute sulfuric acid cleaning powder surface.
2, the preparation method of ultrafine copper powder for conductive paste according to claim 1 and 2 is characterized in that: the oxide of described copper is cupric oxide or cuprous oxide.
3, the preparation method of ultrafine copper powder for conductive paste according to claim 1 and 2 is characterized in that: described coating compound is Mg (OH)
2, Fe (OH)
3Or Al (OH)
3
4, the preparation method of ultrafine copper powder for conductive paste according to claim 3 is characterized in that: described Mg (OH)
2, Fe (OH)
3Perhaps Al (OH)
3The dosage of metal hydroxides is---Cu is 1: 1～100: 1 with the ratio of the amount of substance of Mg, Fe or Al in the maintenance system.
5, the preparation method of ultrafine copper powder for conductive paste according to claim 1 and 2 is characterized in that: described reducing agent is H
2, CO, methane or natural gas reducibility gas.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103302297A (en) * | 2013-06-07 | 2013-09-18 | 中国科学院过程工程研究所 | Superfine copper powder and preparation method thereof |
| CN103831431A (en) * | 2012-11-26 | 2014-06-04 | 苏州钻石金属粉有限公司 | Method for preparing conductive copper powder |
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| CN110797187A (en) * | 2018-08-01 | 2020-02-14 | Ｊｘ金属株式会社 | Laminate of ceramic layer and copper powder paste sintered body |
| CN111063488A (en) * | 2019-10-09 | 2020-04-24 | 南通宇华新材料科技有限公司 | Processing method of conductive paste with excellent acid resistance |
| CN112739478A (en) * | 2018-09-21 | 2021-04-30 | Ｊｘ金属株式会社 | Easily-crushable copper powder and method for producing same |
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| WO2006019144A1 (en) * | 2004-08-20 | 2006-02-23 | Ishihara Sangyo Kaisha, Ltd. | Copper microparticle and process for producing the same |
| JP4662760B2 (en) * | 2004-12-22 | 2011-03-30 | 三井金属鉱業株式会社 | Ultrafine copper powder, ultrafine copper powder slurry, and method for producing ultrafine copper powder slurry |
| CN100581694C (en) * | 2007-03-26 | 2010-01-20 | 中南大学 | Method for preparing monodisperse high-crystallinity copper powder |
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2009
- 2009-04-03 CN CN2009100430437A patent/CN101513675B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831431A (en) * | 2012-11-26 | 2014-06-04 | 苏州钻石金属粉有限公司 | Method for preparing conductive copper powder |
| CN103302297A (en) * | 2013-06-07 | 2013-09-18 | 中国科学院过程工程研究所 | Superfine copper powder and preparation method thereof |
| CN103302297B (en) * | 2013-06-07 | 2016-04-20 | 中国科学院过程工程研究所 | A kind of superfine cupper powder and preparation method thereof |
| CN110797187A (en) * | 2018-08-01 | 2020-02-14 | Ｊｘ金属株式会社 | Laminate of ceramic layer and copper powder paste sintered body |
| CN110797187B (en) * | 2018-08-01 | 2021-07-30 | Ｊｘ金属株式会社 | Laminate of ceramic layer and copper powder paste sintered body |
| CN110026560A (en) * | 2018-08-27 | 2019-07-19 | 南方科技大学 | Nano copper particle and its preparation method and application |
| CN112739478A (en) * | 2018-09-21 | 2021-04-30 | Ｊｘ金属株式会社 | Easily-crushable copper powder and method for producing same |
| CN111063488A (en) * | 2019-10-09 | 2020-04-24 | 南通宇华新材料科技有限公司 | Processing method of conductive paste with excellent acid resistance |
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