CN1313231C - Preparaction method of Ni-powder - Google Patents
Preparaction method of Ni-powder Download PDFInfo
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- CN1313231C CN1313231C CNB2004100644096A CN200410064409A CN1313231C CN 1313231 C CN1313231 C CN 1313231C CN B2004100644096 A CNB2004100644096 A CN B2004100644096A CN 200410064409 A CN200410064409 A CN 200410064409A CN 1313231 C CN1313231 C CN 1313231C
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- nickel
- solution
- powder
- salt solution
- hydrazine compound
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Abstract
The nickel powder is obtained by preparing a nickel salt solution containing copper ions, preparing a hydrazine compound solution, adding an organic compound which is composed of N, C, O and H and has an OH group in the moleculen into a nickel salt solution and/or the hydrazine compound solution, then mixing the nickel salt solution and the hydrazine compound solution and subjecting the mixture to oxidation reduction reaction. The nickel powder of a grain size 100 to 300 nm can be obtained while suppressing the variation in the grain size and having good reproducibility.
Description
Technical field
The present invention relates to a kind of manufacture method of nickel by powder, particularly for example in the manufacture method that is suitable as the nickel by powder that conductive compositions contains for the internal electrode that forms multi-layer ceramic capacitor in the employed conductive paste.
Background technology
For example use conductive paste for the internal electrode that forms multi-layer ceramic capacitor.Contain the metal dust as conductive compositions in the conductive paste, be nickel by powder and used at present as such metal dust more.
In such multi-layer ceramic capacitor, in order to realize miniaturization and high capacity, effective method is the lamination number that makes the thickness of internal electrode thin as far as possible, increases the internal electrode of per unit volume.For this reason, need make the metal dust that contains in the conductive paste is that the physical size of nickel by powder particle is as far as possible little.
Can obtain the little nickel by powder of as described above particle size, can liquid phase method for example be arranged practical method, and proposed following this liquid phase method that utilizes and made method as metal dusts such as nickel by powder.
Promptly, when use is suitable for synthetic stacked capacitor and will synthesizes nickel by powder about 0.5 micron with the hydrazine compound of nickel by powder, the nickel salt solution that handlebar contains complexant (complex formation agent) drips in the reductant solution of trained pH value, makes nickel salt reduction and separates out the manufacture method (for example with reference to Japanese patent laid-open 11-302709 communique) of the nickel by powder of nickel.
In addition, the manufacture method of the metal dust that comprises following each operation is arranged also, that is, prepare the operation of reductant solution; Preparation is dissolved in nickel salt and mantoquita the operation of the metal salt solution in the solvent; Reductant solution and metal salt solution are mixed, make the mantoquita reduction separate out copper, and be nuclear, make the nickel salt reduction, separate out the operation of nickel with this copper.(for example opening the 2002-53904 communique) with reference to the Japan Patent spy
But, the nickel salt solution that contains complexant as above-mentioned handle drips in the method in the reductant solution, if will synthesize the less nickel by powder of particle diameter, then need reduce the addition of complexant, the complexant that uses the unstable coordination ion of generation in strong alkali solution or raising reducing agent, amount of sodium hydroxide/concentration for the reduction that promotes nickel particles.But, the powder that generates under this condition is considered to carry out simultaneously owing to reacting extremely fierceness, karyogenesis and particle growth, so at particle diameter is in particular for the occasion below 0.2 micron below 0.3 micron, form the beading powder easily, become the powder of uncomfortable cooperation stacked capacitor with nickel by powder.
In addition, make as nuclear reduction nickel salt in the method that nickel by powder separates out at the copper of separating out with reduction as described above, can only obtain the powder of the less average grain diameter of 50～100 nanometers, if will obtain being suitable for the powder of average grain diameter 100～300 nanometers of multi-layer ceramic capacitor, the control that can face particle diameter is difficult, the bigger problem of deviation of particle diameter.Also have, in this method, even, also there is the problem of the repeatability difference of this particle diameter in the scope of 50～100 nanometers in average grain diameter.
Summary of the invention
Therefore, the object of the present invention is to provide the manufacture method of the nickel by powder that can solve above-mentioned such problem.
In order to solve above-mentioned technical task, the manufacture method of nickel by powder of the present invention is characterized in that, comprising: preparation contains the operation of the nickel salt solution of copper ion; Prepare the operation of hydrazine compound solution; In nickel salt solution and/or hydrazine compound solution, add the operation that constitutes and in molecule, have the organic compound of OH base by N, C, O and H; And,, obtain the operation of nickel by powder by redox reaction with nickel salt solution and the mixing of hydrazine compound solution.
In the present invention, the copper ion amount in the nickel salt solution is preferably counted below 1% by the molar ratio with respect to nickel.
In addition, the addition of organic compound preferably, by counting 1～50% with respect to the molar ratio of the nickel that in nickel salt solution, contains.
In addition, above-mentioned organic compound preferably has C in molecular structure
nH
2nOrganic amine or the organic amide of OH (wherein, n 〉=1).As such organic amine, for example be fit to use central at least a of triethanolamine, diethanol amine, diisopropanolamine (DIPA), oxygen vinyl alkyl amine (oxyethylene alkyl amine) and polyoxyethylene alkyl amine (polyoxyethylene alkyl amine), as organic amide, for example be fit to use diethanol amine.
According to the present invention, when having copper ion, for example also exist organic amine or organic amide etc. to constitute and in molecule, have in the solution of organic compound of OH base by N, C, O and H, the redox reaction that causes based on the mixing by nickel salt solution and hydrazine compound solution obtains nickel by powder, therefore as by among the embodiment described later as can be known, produce the nickel by powder of particle diameter 100～300 nanometers when can suppress the particle diameter deviation with good repeatability.
The specific embodiment
When making nickel by powder, at first prepare to contain the nickel salt solution of copper ion according to these an embodiment of the invention.What wherein, use as nickel salt solution is the solution that contains just like nickelous sulfate, nickel acetate and/or nickel chloride.In addition, to contain copper ion in this nickel salt solution and add mantoquita in order to make, this mantoquita can be the material that is dissolved in separately in the nickel salt solution, is not dissolved in separately in the nickel salt solution but dissolved substances when adding complexant even also can be.
In addition, prepare hydrazine compound solution.As hydrazine compound solution as using hydrazine hydrate solution.
Then, interpolation constitutes and has the organic compound of OH base by N, C, O and H in molecule at least one side of above-mentioned nickel salt solution and hydrazine compound solution.As this organic compound, for example be fit to use in molecular structure, to have C
nH
2nOrganic amine or the organic amide of OH (wherein, n 〉=1).
As above-mentioned organic amine, triethanolamine [N (CH is for example arranged
2CH
2OH)
3], diethanol amine [HN (CH
2CH
2OH)
2], diisopropanolamine (DIPA) [NH ((CH
3)
2CHOH)
2], oxygen ethylidene alkylamine [RN (CH
2CH
2OH)
2R: alkyl] and polyoxyethylene alkyl amine [RN (CH
2CH
2O)
xH (CH
2CH
2O)
yH; R: alkyl] etc.In addition, as organic amide, diglycollic amide [RCON (CH is for example arranged
2CH
2OH)
2R: alkyl] etc.
As mentioned above, organic compound can add in the middle of any one party in nickel salt solution and the hydrazine compound solution.Add the effect that all can expect organic compound in any one solution in nickel salt solution and the hydrazine compound solution to.In addition, under the occasion of organic compound being added in the nickel salt solution, it is big that the particle diameter of the nickel by powder that obtains tends to become.
Then, nickel solution and hydrazine compound solution are mixed, make them that redox reaction take place, can obtain the nickel by powder of purpose thus.
In the manufacture method of this nickel by powder, the copper ion amount in the nickel salt solution is preferably counted below 1% by the molar ratio with respect to nickel.Be because: if the amount of copper ion surpasses 1%, then copper becomes impurity in the nickel by powder that obtains, contain in use that the electrical characteristics such as reliability to dielectric produce bad influence in the multi-layer ceramic capacitor that the conductive paste of this nickel by powder forms, perhaps the karyogenesis of copper is carried out excessively, it is too fast that reaction speed becomes, even for example add organic compounds such as organic amine or organic amide, also be difficult to control particle diameter.
In addition, the addition of organic compound preferably with respect to the nickel that in nickel salt solution, contains in molar ratio rate count 1～50%.If the addition of organic compound surpasses 50%, then can not expect to surpass the effect increase that 50% part is produced by this; On the other hand, if less than 1%, though then according to the kind of organic compound and difference can not be confirmed the effect that organic compound brings.
Below, the embodiment that implements in order to confirm effect of the present invention is described.
The 100g nickelous sulfate is dissolved in 200cm
3In the water, and add the 5 brochanite solution of 0.05 weight % or 0.5 weight % therein, the amount that makes copper ion is " the copper ion amount " of table 1, has prepared the nickel salt solution that contains copper ion of each sample like this." copper ion amount " used with respect to the molar ratio of nickel and represented in table 1.
In addition, be dissolved in 200cm with 80% hydrazine hydrate 100g and sodium hydroxide solution 100g with as the natrium citricum 10g of hydroxycarboxylic acid
3In the water, obtained hydrazine compound solution.
In addition, as the organic compound that constitutes and in molecule, have the OH base by N, C, O and H, as shown in " kind " hurdle in " organic compound " of table 1, use triethanolamine, diisopropanolamine (DIPA), diethanol amine, oxygen ethene lauryl amine and diglycollic amide respectively, they are added in the hydrazine compound solution of representing in " add object solution " hurdle as table 1 or nickel solution with the addition of representing in " addition " hurdle." addition " is to represent with respect to the molar ratio of the nickel that contains in the nickel salt solution.
Then, with the heating of above-mentioned nickel salt solution and hydrazine compound solution, make solution temperature reach 60 ℃ after, through 3 minutes, nickel salt solution is joined in the hydrazine compound solution, mix.Then, ageing is 10 minutes～30 minutes.In this operation, redox reaction takes place, nickel by powder is separated out with sediment in reactant liquor.
Then, after the cooling reactant liquor, with its supernatant for several times, clean nickel by powder with the pure water displacement.Then, behind the acetone replacing water, dry nickel by powder in the baking oven that is set at 80 ℃ of temperature.
To the nickel by powder of each sample of obtaining like this, use field-emission scanning type electron microscope, observe with 20000～50000 times multiplying powers.And, by the image of its observation of image analysis, obtain the particle diameter of nickel by powder, calculated " average grain diameter " and " particle diameter deviation " by this result is as shown in table 1." particle diameter deviation " is the CV value, according to (standard deviation/mean value) * 100[%] formula calculates.
Table 1
| The sample sequence number | Organic compound | Copper ion amount (%) | Average grain diameter (nm) | Particle diameter deviation (%) | ||
| Kind | Add object solution | Addition (%) | ||||
| 1 | Triethanolamine | Hydrazine compound solution | 1 | 0.01 | 110 | 15 |
| 2 | Triethanolamine | Hydrazine compound solution | 10 | 0.001 | 300 | 15 |
| 3 | Triethanolamine | Hydrazine compound solution | 10 | 0.005 | 210 | 15 |
| 4 | Triethanolamine | Hydrazine compound solution | 10 | 0.01 | 190 | 15 |
| 5 | Triethanolamine | Hydrazine compound solution | 10 | 1 | 100 | 20 |
| 6 | Triethanolamine | Hydrazine compound solution | 50 | 0.01 | 270 | 10 |
| 7 | Triethanolamine | Nickel salt solution | 10 | 0.01 | 250 | 20 |
| 8 | Diisopropanolamine (DIPA) | Hydrazine compound solution | 10 | 0.01 | 120 | 18 |
| 9 | Diisopropanolamine (DIPA) | Hydrazine compound solution | 10 | 0.005 | 150 | 18 |
| 10 | Diisopropanolamine (DIPA) | Hydrazine compound solution | 50 | 0.01 | 230 | 17 |
| 11 | Diethanol amine | Hydrazine compound solution | 10 | 0.01 | 150 | 15 |
| 12 | Diethanol amine | Hydrazine compound solution | 10 | 0.005 | 190 | 18 |
| 13 | Diethanol amine | Hydrazine compound solution | 50 | 0.01 | 250 | 17 |
| 14 | Oxygen ethene lauryl amine | Hydrazine compound solution | 1 | 0.01 | 120 | 18 |
| 15 | Diglycollic amide | Hydrazine compound solution | 40 | 0.01 | 250 | 16 |
| 16 | - | - | 0 | 0.0005 | 150 | 60 |
| 17 | - | - | 0 | 0.01 | 80 | 40 |
As shown in Table 1, sample 1～15 is when synthesizing nickel by powder, owing to used the organic compound that constitutes and in molecule, have the OH base by N, C, O and H, therefore compare with sample 17 with the sample 16 that does not use organic compound, can obtain the nickel by powder that average grain diameter is 100～300nm with the few state of particle diameter deviation.
In sample 1～15, duplicate 1 and sample 4 by changing the addition of organic compound triethanolamine, can be controlled average grain diameter as can be known.
In addition, duplicate 2～5 by changing the copper ion amount, can be controlled average grain diameter as can be known.
In addition, duplicate 4 and sample 7 are as can be known, no matter the interpolation object solution of triethanolamine is hydrazine compound solution or nickel salt solution, can both demonstrate the additive effect of triethanolamine, and compare when being hydrazine compound solution with interpolation solution, the average grain diameter that obtains when adding solution for nickel salt solution is bigger.
In addition, duplicate 1～7 and 8～15 as can be known, use diisopropanolamine (DIPA), diethanol amine, oxygen ethene lauryl amine or diglycollic amide as organic compound even replace triethanolamine, suppress too particle diameter deviation, obtain the nickel by powder that average grain diameter is 100～300nm.
The nickel by powder of implementing manufacture method of the present invention and obtaining, can be suitable as the nickel by powder that contains as conductive compositions in the conductive paste, such conductive paste can advantageously be used in and form as the internal electrode of multi-layer ceramic capacitor, the internal conductor membrane aspect of other multilayer ceramic electronic components.
Claims (4)
1. the manufacture method of a nickel by powder is characterized in that, comprising:
Preparation contains the operation of the nickel salt solution of copper ion;
Prepare the operation of hydrazine compound solution;
In described nickel salt solution and/or described hydrazine compound solution, be added with the operation of organic compounds; And
Then, described nickel salt solution and described hydrazine compound solution are mixed,, obtain the operation of nickel by powder by redox reaction,
Wherein, described organic compound be dissolved in described nickel salt solution and/or the described hydrazine compound solution and in molecular structure, have a C
nH
2nThe organic amine of OH or organic amide, described n 〉=1.
2. the manufacture method of nickel by powder according to claim 1, it is characterized in that: the amount of the described copper ion in the described nickel salt solution is counted below 1% by the molar ratio with respect to nickel.
3. the manufacture method of nickel by powder according to claim 1 and 2, it is characterized in that: the addition of described organic matter compound is by count 1～50% with respect to the molar ratio of the nickel that contains in described nickel salt solution.
4. the manufacture method of nickel by powder according to claim 1 is characterized in that: described organic compound is at least a in the middle of triethanolamine, diethanol amine, diisopropanolamine (DIPA), oxygen ethylidene alkylamine and polyoxyethylene alkyl amine and the diglycollic amide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003300945 | 2003-08-26 | ||
| JP2003300945 | 2003-08-26 | ||
| JP2004234996 | 2004-08-12 | ||
| JP2004234996A JP4244883B2 (en) | 2003-08-26 | 2004-08-12 | Method for producing nickel powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597198A CN1597198A (en) | 2005-03-23 |
| CN1313231C true CN1313231C (en) | 2007-05-02 |
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ID=34467147
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100644096A Active CN1313231C (en) | 2003-08-26 | 2004-08-24 | Preparaction method of Ni-powder |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4244883B2 (en) |
| CN (1) | CN1313231C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108349010A (en) * | 2015-10-19 | 2018-07-31 | 住友金属矿山株式会社 | The manufacturing method of nickel by powder |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3940817B2 (en) * | 2005-05-30 | 2007-07-04 | 松下電器産業株式会社 | Electrochemical electrode in which nickel-containing nanostructure having dendritic structure is applied to the active layer and method for producing the same |
| JP4957172B2 (en) | 2005-10-20 | 2012-06-20 | 住友金属鉱山株式会社 | Nickel powder and method for producing the same |
| CN100391663C (en) * | 2006-04-10 | 2008-06-04 | 李小毛 | Process for preparing nano nickel powder |
| JP2013014813A (en) * | 2011-07-06 | 2013-01-24 | Murata Mfg Co Ltd | Porous metal particle, and manufacturing method thereof |
| KR101565631B1 (en) * | 2012-06-04 | 2015-11-03 | 삼성전기주식회사 | Conductive paste composition for internal electrode, multilayer ceramic electronic capacitor and fabricating method thereof |
| JP5723843B2 (en) * | 2012-09-26 | 2015-05-27 | 三洋化成工業株式会社 | Aliphatic amine alkylene oxide adduct-containing composition |
| WO2014057735A1 (en) * | 2012-10-11 | 2014-04-17 | 株式会社村田製作所 | Metal powder manufacturing method |
| CN105522167B (en) * | 2015-12-28 | 2017-12-15 | 江苏理工学院 | The synthetic method of beading nickel micron particles |
| JP6746321B2 (en) * | 2016-02-05 | 2020-08-26 | 株式会社村田製作所 | Ni powder, method of manufacturing Ni powder, internal electrode paste, and electronic component |
| JP6573563B2 (en) * | 2016-03-18 | 2019-09-11 | 住友金属鉱山株式会社 | Nickel powder, nickel powder manufacturing method, internal electrode paste using nickel powder, and electronic component |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172306A (en) * | 1997-12-12 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | Fine nickel powder and its production |
| JP2002053904A (en) * | 2000-05-30 | 2002-02-19 | Murata Mfg Co Ltd | Method for producing metal powder, metal powder, electrically conductive past using the same, and laminated ceramic electronic parts using the same |
-
2004
- 2004-08-12 JP JP2004234996A patent/JP4244883B2/en active Active
- 2004-08-24 CN CNB2004100644096A patent/CN1313231C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11172306A (en) * | 1997-12-12 | 1999-06-29 | Mitsui Mining & Smelting Co Ltd | Fine nickel powder and its production |
| JP2002053904A (en) * | 2000-05-30 | 2002-02-19 | Murata Mfg Co Ltd | Method for producing metal powder, metal powder, electrically conductive past using the same, and laminated ceramic electronic parts using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108349010A (en) * | 2015-10-19 | 2018-07-31 | 住友金属矿山株式会社 | The manufacturing method of nickel by powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4244883B2 (en) | 2009-03-25 |
| CN1597198A (en) | 2005-03-23 |
| JP2005097729A (en) | 2005-04-14 |
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