CN103737013A - Method for preparing nanometer spherical copper powder - Google Patents
Method for preparing nanometer spherical copper powder Download PDFInfo
- Publication number
- CN103737013A CN103737013A CN201310705150.8A CN201310705150A CN103737013A CN 103737013 A CN103737013 A CN 103737013A CN 201310705150 A CN201310705150 A CN 201310705150A CN 103737013 A CN103737013 A CN 103737013A
- Authority
- CN
- China
- Prior art keywords
- copper
- copper powder
- nanometer spherical
- preparation
- oxalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method for preparing copper powder for the field of nanometer spherical electrocondution slurry, catalysts, ceramic capacitors and the like, in particular to a method for preparing nanometer spherical copper powder. The method is characterized by including the following steps that firstly, a precursor of the copper powder is prepared, wherein soluble copper salt reacts with a precipitating agent to generate precursor precipitation of the copper salt; secondly, a cladding body of the copper powder is prepared, the acquired precursor precipitation of the copper salt is used as a crystal nucleus, a cladding layer formed by a cladding agent is formed on the surface of the crystal nucleus through a physical crystallization method or a chemical crystallization method, and then centrifugal separation, filtration and drying are conducted; thirdly, acquired drying materials are kept warm for 0.5-2 hours in the reducing atmosphere or the vacuum atmosphere at the temperature ranging from 250 DEG C to 350 DEG C, and then the drying materials are processed for 2-6 hours at the high temperature ranging from 400 DEG C to 850 DEG C; fourthly, the cladding layer of the acquired materials is removed through acid washing or alkali washing, and the materials are dried and decentralized. The method for preparing the nanometer copper powder is low in cost, simple in operation, free of pollution and controllable in granularity.
Description
Technical field
The present invention relates to the preparation method of the fields such as a kind of nanometer spherical electrocondution slurry, catalyst, ceramic capacitor copper powder, especially a kind of preparation method of nanometer spherical copper powders.
Background technology
Along with electron trade high speed development, multilayer ceramic capacitor (Multilayer Ceramic Capacitors, MLCC) as one of critical material, have that volume is little, higher than electric capacity, insulaion resistance is high, leakage current is little and dielectric loss is low etc. that advantage is widely used in concussion, coupling, filtering and the bypass circuit in various complete electronic sets, especially high-frequency circuit, makes market also more and more to MLCC demand.Tradition MLCC electrode adopts the noble metals such as silver palladium alloy or pure palladium metal, along with the rise of argent, palladium price, adopting cheap copper base metal, copper as electrode material, to cause people's extensive concern, is also one of development ceramic capacitor technology main trend.It is spherical or class is spherical, chemical purity is high, good dispersion that MLCC requires with copper powder, and without reuniting, epigranular, good conductivity, has higher tap density, degree of crystallinity is high, specific area is moderate.
At present, copper powder preparation method is a lot, according to the difference of feed states, can be divided into liquid phase method, solid phase method and vapor phase method, but the prepared copper powder of these methods exists the features such as inhomogeneous, the easy reunion of particle diameter, pattern be irregular in various degree.It is high that vapor phase method is prepared copper powder sphericity, but its needed raw material gas price costliness, equipment complexity, cost high, yield poorly; Copper powder size prepared by solid phase method distributes wide, easily introduces impurity; Although liquid phase method device therefor is simple, the copper powder degree of crystallinity that the method is produced is low, and crystal formation is imperfect, and non-oxidizability is poor.
Summary of the invention
The object of this invention is to provide a kind of preparation method of with low cost, simple to operate, pollution-free, nanometer spherical copper powders that granularity is controlled.
A preparation method for nanometer spherical copper powders, its special feature is, comprises the steps:
(1) prepare copper powder presoma: adopt soluble copper salt and precipitating reagent reaction to generate mantoquita presoma precipitation;
(2) prepare copper powder cladding: with the mantoquita presoma obtaining, be precipitated as nucleus, by physical crystal method or chemical precipitation method, on its surface, form the clad being comprised of covering, then centrifugation is filtered, dried;
(3) by the oven dry thing obtaining 250-350 ℃ of insulation 0.5-2 hour, subsequently 400～850 ℃ of high-temperature process 2-6 hour in reducing atmosphere or vacuum atmosphere;
(4) by the material obtaining through pickling or alkali cleaning remove clad, oven dry, dispersion treatment both nanometer spherical copper powders.
Described in step (1), soluble copper salt is copper sulphate, copper chloride or copper nitrate, and precipitating reagent is ammonium oxalate, oxalic acid, ammonium carbonate or carbonic hydroammonium.
The mantoquita presoma obtaining in step (1) is precipitated as cupric oxalate or basic copper carbonate.
In step (1), also will add the one to three kind in polyethylene of dispersing agent alcohol PVA, polyvinylpyrrolidone PVP, alcohols, lauryl sodium sulfate, softex kw and benzene sulfonic acid sodium salt, addition is calculated and is added 15-200g with the copper of every mole.
In step (1), controlling reaction temperature is 15-70 ℃, and the reaction time is 20-40 minute.
In step (2), covering adopts magnesium oxalate, zinc oxalate, calcium oxalate, potash, sodium carbonate, magnesium carbonate or calcium carbonate, and the mol ratio of covering and copper powder precursor is 0.5-4:1.
In step (4), dispersion treatment refers to and adopts gas shock or ball milling method to disperse.
In step (4), pickling adopts watery hydrochloric acid, nitric acid, sulfuric acid or the acetic acid that concentration is 1%-15%, and pickling time is 3-15 minute; Alkali cleaning adopts NaOH, the potassium hydroxide solution that concentration is 10%-30%, at 30-50 ℃ of temperature, washs 2-6 hour.
The invention provides a kind of preparation method of with low cost, simple to operate, pollution-free, copper nanoparticle that granularity is controlled, prepared copper powder has: spherical or class is spherical, chemical purity is high, good dispersion, without reunion, epigranular, good conductivity, the feature such as tap density is high, better crystallinity degree, specific area are moderate, is especially suitable as electrode multilayered ceramic capacitors material.
The specific embodiment
It is mainly to realize by following measures that the present invention prepares nanometer spherical copper powder:
1, adopt the reaction of soluble copper salt and precipitating reagent to generate mantoquita presoma precipitation, for guaranteeing that copper ion reacts completely, precipitating reagent is theoretical amount 1.05 times;
2, take mantoquita sediment precursor as nucleus, by physical crystal method or use chemical precipitation method, on its surface, form clad, will be coated sediment filtering drying;
3, thing 250-350 ℃ of insulation 0.5-2 hour, subsequently 400～850 ℃ of high-temperature process 2-6 hour in reproducibility or vacuum atmosphere oven will be dried in step 2;
4, by material after treatment in step 3 through pickling or alkali cleaning remove clad, oven dry, dispersion treatment both MLCC spherical copper powder;
5, described in step 1 of the present invention, soluble copper salt does not limit, and can be any one or several soluble copper salt mixtures, for example copper sulphate, copper chloride or copper nitrate, and precipitating reagent is ammonium oxalate, oxalic acid, ammonium carbonate, carbonic hydroammonium etc.
6, step 1 of the present invention is produced in the process of copper powder presoma as to prevent that the reunion of copper powder presoma in course of reaction from adding one or more (being no more than at most three kinds) such as polyethylene of dispersing agent alcohol (PVA), polyvinylpyrrolidone (PVP), alcohols, lauryl sodium sulfate, softex kw, benzene sulfonic acid sodium salts, and addition adds 15-200g to be advisable with the copper of every mole.
7, to produce general control reaction temperature in the process of copper powder presoma be 15-70 ℃ to step 1 of the present invention.
8, not significantly restriction of covering in step 2 of the present invention, water insoluble as long as covering and its decompose rear oxidation thing, not with hydrogen reaction, and its fusing point or its oxide fusing point are higher than high-temperature process temperature.Preferably magnesium oxalate, zinc oxalate, calcium oxalate, potash, sodium carbonate, magnesium carbonate, calcium carbonate are as covering.
9, there is no particular limitation to the use amount of covering for the method for coating of the mantoquita sediment precursor described in step 2 of the present invention, if but covering use is very few, can cause coated not thorough, the copper powder of preparing has adhesion, if covering is used too much, can add to the difficulties and can increase cost to follow-up process of removing covering, thereby preferably the mol ratio of covering and copper powder precursor is 0.5～4, more preferably 0.8-2.0.
10, described in step 4 of the present invention, be separated into and adopt gas shock or ball milling method to carry out.
11, the copper powder obtaining according to method of the present invention, is characterized in that obtained copper powder is spherical or class is spherical; Purity is high; By regulating reaction temperature and mixing speed, copper powder particle size range can be controlled between 0.2-3 μ m; Tap density is at 3.0～5.0g/cm
3; Oxidation resistance temperature is high; Good dispersion, nothing reunion etc.
Embodiment 1:
Take copper sulphate 100g, by 1.05 times of theoretical amount, take oxalic acid ammonia, and configure 1mol/L copper-bath and 0.75mol/L oxalic acid ammonia solution, the mixed aqueous solution of 1.0mol/L copper sulphate at 60 ℃ and 100g/L alcohol 0.2L has at the uniform velocity been joined to 60 ℃, 0.75mol/L ammonium oxalate and 0.2L, in the stirring reactor of the mixed aqueous solution of 100g/L alcohol (speed of agitator is 150rpm), add after reaction 20min, obtain the presoma cupric oxalate of copper powder.
Then, will be take copper mole as benchmark, magnesium chloride is its 1.5 times, oxalic acid ammonia amount need to take according to chemical reaction, the ammonium oxalate aqueous solution that is configured to 1.0mol/L at the magnesium chloride brine of 5mol/L at 40 ℃ and 80 ℃ at the uniform velocity adds in reaction vessel simultaneously, adds rear reaction 30min, then uses pure water cyclic washing 3 times, then 150 ℃ of oven dry in electric dry oven of centrifugation, obtain being enclosed with the cupric oxalate of magnesium oxalate.
Then, the cupric oxalate that is enclosed with magnesium oxalate is slowly warmed up to 450 ℃ of insulation 1h in vacuum atmosphere, then passes into CO gas, be warmed up to 700 ℃ of insulation 2h, then CO gas displacement is become to argon gas, cooling below 40 ℃.Finally with 2% watery hydrochloric acid, wash the product 9-10 minute after high-temperature process, centrifugation, lotion 3-4 time, and through 100 ℃ of oven dry, ball milling 2 hours, obtains spherical copper powder.Its average grain diameter is 2.4 μ m, and tap density is 4.77g/cm
3.
Embodiment 2:
Take copper nitrate 200g, by 1.05 times of theoretical amount, take oxalic acid ammonia, and configure 0.75mol/L copper nitrate solution and 0.75mol/L oxalic acid ammonia solution, 40 ℃ of mixed aqueous solutions that contain 0.75mol/L copper nitrate, 30g/L PVP are at the uniform velocity added in the stirring reactor of 40 ℃ of mixed aqueous solutions that contain 0.75mol/L ammonium oxalate, 30g/L PVP (speed of agitator is 200rpm), add reaction after 30 minutes, obtain the presoma cupric oxalate of copper powder.
Then, will be take copper mole as benchmark, calcium chloride is its 1.8 times, oxalic acid ammonia amount need to take according to chemical reaction, be configured to 40 ℃, the calcium chloride water of 4mol/L and the ammonium oxalate aqueous solution of 60 ℃ of 1.2mol/L and at the uniform velocity add in reaction vessel, add rear reaction 30min, then use pure water cyclic washing 4 times simultaneously, then 150 ℃ of oven dry in electric dry oven, obtain being enclosed with the cupric oxalate of calcium oxalate.
Then, the cupric oxalate that is enclosed with calcium oxalate is slowly warmed up to 350 ℃ of insulation 1h in vacuum atmosphere, then passes into CO gas, be warmed up to 680 ℃ of insulation 4h, then CO gas displacement is become to argon gas, subsequently that it is cooling below 40 ℃.Finally with 5% nitric acid, wash the product 7-8 minute after high-temperature process, centrifugation, lotion 3-4 time, and after 100 ℃ of oven dry, ball milling 4 hours, obtains spherical copper powder.Its average grain diameter is 1.81 μ m, and tap density is 4.23g/cm
3.
Embodiment 3:
Take copper chloride 150g, by 1.05 times of theoretical amount, take oxalic acid, and configure 0.5mol/L copper-bath and 0.5mol/L oxalic acid solution, 30 ℃ of mixed aqueous solutions that contain 0.5mol/L copper chloride, 120g/L PEG are at the uniform velocity added in the stirring reactor of 35 ℃ of mixed aqueous solutions that contain 0.5mol/L oxalic acid, 100g/L PEG (speed of agitator is 100rpm), add reaction after 40 minutes, obtain the presoma cupric oxalate of copper powder.
Then, will will be take copper mole as benchmark with copper, magnesium chloride is its 2 times, oxalic acid ammonia amount need to take according to chemical reaction, be configured to the magnesium chloride brine of 40 ℃ of 5mol/L and the oxalic acid aqueous solution of 60 ℃ of 1.0mol/L and at the uniform velocity add in reaction vessel, add rear reaction 40min, then use pure water cyclic washing 2 times simultaneously, then 150 ℃ of oven dry in electric dry oven, obtain being enclosed with the cupric oxalate of magnesium oxalate.
Then, the cupric oxalate that is enclosed with magnesium oxalate is slowly warmed up to 300 ℃ of insulation 2h in vacuum atmosphere, then passes into CO gas, be warmed up to 700 ℃ of insulation 3h, then CO gas displacement is become to argon gas, subsequently that it is cooling below 40 ℃.Product 3-4 minute after last 10% watery hydrochloric acid washing high-temperature process, centrifugation, lotion 3-4 time, and after 85 ℃ of oven dry, after gas shock, obtain spherical copper powder.Its average grain diameter is 1.53 μ m, and tap density is 3.98g/cm
3.
Embodiment 4:
Take copper chloride 150g, by 1.05 times of theoretical amount, take potash, and configure 0.5mol/L copper-bath and 0.5mol/L solution of potassium carbonate, 25 ℃ of mixed aqueous solutions that contain 0.5mol/L copper chloride, 100g/L alcohol are at the uniform velocity added in the stirring reactor of 40 ℃ of mixed aqueous solutions that contain 0.5mol/L potash, 80g/L alcohol (speed of agitator is 150rpm), add after reaction 30min, obtain the presoma cupric oxalate of copper powder.
Then, will be take copper mole as benchmark, zinc chloride is its 1.5 times, oxalic acid ammonia amount need to take according to chemical reaction, be configured to the solder(ing)acid of 40 ℃ of 3mol/L and the ammonium oxalate aqueous solution of 60 ℃ of 1.5mol/L and at the uniform velocity add in reaction vessel, add rear reaction 30min, then use pure water cyclic washing 3 times simultaneously, then 150 ℃ of oven dry in electric dry oven, obtain being enclosed with the copper carbonate of zinc oxalate.
Then, the copper carbonate that is enclosed with zinc oxalate is slowly warmed up to 300 ℃ of insulation 1h in vacuum atmosphere, then passes into CO gas, be warmed up to 600 ℃ of insulation 4h, then CO gas displacement is become to argon gas, subsequently that it is cooling below 40 ℃.Finally use 60 ℃, the product after 30% sodium hydroxide solution washing high-temperature process 2 hours, centrifugation, lotion 3-4 time, and after 90 ℃ of oven dry, ball milling obtains spherical copper powder for 1 hour.Its average grain diameter is 1.02 μ m, and tap density is 3.88g/cm
3.
Embodiment 5:
Take copper nitrate 250, by 1.05 times of theoretical amount, take carbonic hydroammonium, and configure 0.8mol/L copper nitrate solution and 0.6mol/L ammonium bicarbonate soln, 25 ℃ of mixed aqueous solutions that contain 0.8mol/L copper nitrate, 100g/L polypropylene glycol are at the uniform velocity added in the stirring reactor of 40 ℃ of mixed aqueous solutions that contain 0.6mol/L carbonic hydroammonium, 80g/L polypropylene glycol (speed of agitator is 200rpm), add reaction after 30 minutes, obtain the presoma copper carbonate of copper powder.
Then, will be take copper mole as benchmark, calcium chloride is its 1.0 times, oxalic acid ammonia amount need to take according to chemical reaction, the ammonium oxalate aqueous solution of the calcium chloride water of 30 ℃ of 2mol/L and 40 ℃ of 1.0mol/L at the uniform velocity adds in reaction vessel by stoichiometric proportion, adds rear reaction 40min, then uses pure water cyclic washing 2 times, then 150 ℃ of oven dry in electric dry oven, obtain being enclosed with the copper carbonate of calcium oxalate.
Then, the copper carbonate that is enclosed with calcium oxalate is slowly warmed up to 350 ℃ of insulation 1.5h in vacuum atmosphere, then passes into CO gas, be warmed up to 750 ℃ of insulation 3h, then CO gas displacement is become to argon gas, pass into argon gas cooling below 40 ℃.Finally with 3% nitric acid, wash the product 5-6 minute after high-temperature process, centrifugation, lotion 3-4 time, and after 80 ℃ of oven dry, gas shock obtains spherical copper powder.Its average grain diameter is 0.5 μ m, and tap density is 3.28g/cm
3.
The invention discloses the preparation method of a kind of MLCC nanometer spherical copper powder and the copper powder that adopts the method to obtain, the method comprises first prepares cupric presoma precipitation, then with evenly coated this precursor of covering, carries out pyrolysis, finally remove clad, both obtained nanometer spherical copper powder.The spherical copper powder end of preparing by the method has good dispersion, specific surface is little, tap density is high, crystal formation is ripe, granule size is controlled, non-oxidizability is strong feature, can be used for electrode multilayered ceramic capacitors material.The method has the advantages that equipment is simple, technological process is short, cost is low in addition, can be used for the suitability for industrialized production of copper powder.
Claims (8)
1. a preparation method for nanometer spherical copper powders, is characterized in that, comprises the steps:
(1) prepare copper powder presoma: adopt soluble copper salt and precipitating reagent reaction to generate mantoquita presoma precipitation;
(2) prepare copper powder cladding: with the mantoquita presoma obtaining, be precipitated as nucleus, by physical crystal method or chemical precipitation method, on its surface, form the clad being comprised of covering, then centrifugation is filtered, dried;
(3) by the oven dry thing obtaining 250-350 ℃ of insulation 0.5-2 hour, subsequently 400～850 ℃ of high-temperature process 2-6 hour in reducing atmosphere or vacuum atmosphere;
(4) by the material obtaining through pickling or alkali cleaning remove clad, oven dry, dispersion treatment both nanometer spherical copper powders.
2. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, is characterized in that: described in step (1), soluble copper salt is copper sulphate, copper chloride or copper nitrate, and precipitating reagent is ammonium oxalate, oxalic acid, ammonium carbonate or carbonic hydroammonium.
3. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 2, is characterized in that: the mantoquita presoma obtaining in step (1) is precipitated as cupric oxalate or basic copper carbonate.
4. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, it is characterized in that: in step (1), also will add the one to three kind in polyethylene of dispersing agent alcohol PVA, polyvinylpyrrolidone PVP, alcohols, lauryl sodium sulfate, softex kw and benzene sulfonic acid sodium salt, addition is calculated and added 15-200g with the copper of every mole.
5. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, is characterized in that: in step (1), controlling reaction temperature is 15-70 ℃, and the reaction time is 20-40 minute.
6. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, it is characterized in that: in step (2), covering adopts magnesium oxalate, zinc oxalate, calcium oxalate, potash, sodium carbonate, magnesium carbonate or calcium carbonate, and the mol ratio of covering and copper powder precursor is 0.5-4:1.
7. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, is characterized in that: in step (4), dispersion treatment refers to and adopts gas shock or ball milling method to disperse.
8. the preparation method of a kind of nanometer spherical copper powders as claimed in claim 1, is characterized in that: in step (4), pickling adopts watery hydrochloric acid, nitric acid, sulfuric acid or the acetic acid that concentration is 1%-15%, and pickling time is 3-15 minute; Alkali cleaning adopts NaOH, the potassium hydroxide solution that concentration is 10%-30%, at 30-50 ℃ of temperature, washs 2-6 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310705150.8A CN103737013A (en) | 2013-12-20 | 2013-12-20 | Method for preparing nanometer spherical copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310705150.8A CN103737013A (en) | 2013-12-20 | 2013-12-20 | Method for preparing nanometer spherical copper powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103737013A true CN103737013A (en) | 2014-04-23 |
Family
ID=50494120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310705150.8A Pending CN103737013A (en) | 2013-12-20 | 2013-12-20 | Method for preparing nanometer spherical copper powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103737013A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014808A (en) * | 2014-05-29 | 2014-09-03 | 深圳航天科技创新研究院 | Method for preparing monodisperse superfine nickel powder through seeding growth method and micro-reaction system of method |
| CN105436512A (en) * | 2014-08-13 | 2016-03-30 | 南京理工大学 | Preparation method of nano-copper catalysts |
| CN105945302A (en) * | 2016-05-20 | 2016-09-21 | 金陵科技学院 | Preparation method for antioxidant copper nanopowder |
| CN109822090A (en) * | 2017-11-23 | 2019-05-31 | 中国科学院化学研究所 | A kind of preparation method of the copper nanoparticle of in-stiu coating organic matter |
| CN109970092A (en) * | 2017-12-27 | 2019-07-05 | 广州科城环保科技有限公司 | A kind of preparation method of high-bulk-density basic copper carbonate |
| CN110774395A (en) * | 2019-10-22 | 2020-02-11 | 含山县宏达门业家具有限公司 | Method for improving waterproof and corrosion-resistant performance of wooden door |
| CN110976901A (en) * | 2019-12-31 | 2020-04-10 | 湘潭大学 | Preparation method of nano copper powder |
| CN113000855A (en) * | 2021-03-23 | 2021-06-22 | 中国科学技术大学先进技术研究院 | Preparation method of micro-nano copper powder |
| CN113618075A (en) * | 2021-08-23 | 2021-11-09 | 孙珲 | Preparation method of filling high-purity nano material of ultralow-resistivity conductive paste |
| CN115611302A (en) * | 2022-10-22 | 2023-01-17 | 杭州富阳鸿源再生资源利用有限公司 | Preparation process of nano basic copper carbonate and nano basic copper carbonate |
| CN113000855B (en) * | 2021-03-23 | 2024-04-19 | 中国科学技术大学先进技术研究院 | Preparation method of micro-nano copper powder |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0977212A2 (en) * | 1998-07-31 | 2000-02-02 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| US20080138643A1 (en) * | 2006-10-10 | 2008-06-12 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing copper nanoparticles and copper nanoparticles manufactured using the same |
| CN101428348A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Process for producing spherical submicron metal with hydro-thermal treatment |
| CN102070206A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | Preparation method for nano nickel oxide |
| CN102441675A (en) * | 2011-12-07 | 2012-05-09 | 西北稀有金属材料研究院 | Preparation method for high-crystallinity silver powder |
| CN102699338A (en) * | 2012-05-18 | 2012-10-03 | 宁夏东方钽业股份有限公司 | Method for preparing spherical nickel powder |
-
2013
- 2013-12-20 CN CN201310705150.8A patent/CN103737013A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0977212A2 (en) * | 1998-07-31 | 2000-02-02 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
| US20080138643A1 (en) * | 2006-10-10 | 2008-06-12 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing copper nanoparticles and copper nanoparticles manufactured using the same |
| CN101428348A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Process for producing spherical submicron metal with hydro-thermal treatment |
| CN102070206A (en) * | 2009-11-19 | 2011-05-25 | 中国石油化工股份有限公司 | Preparation method for nano nickel oxide |
| CN102441675A (en) * | 2011-12-07 | 2012-05-09 | 西北稀有金属材料研究院 | Preparation method for high-crystallinity silver powder |
| CN102699338A (en) * | 2012-05-18 | 2012-10-03 | 宁夏东方钽业股份有限公司 | Method for preparing spherical nickel powder |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014808A (en) * | 2014-05-29 | 2014-09-03 | 深圳航天科技创新研究院 | Method for preparing monodisperse superfine nickel powder through seeding growth method and micro-reaction system of method |
| CN104014808B (en) * | 2014-05-29 | 2016-02-24 | 深圳航天科技创新研究院 | Crystal seeding growth prepares the method for monodisperse superfine nickel powder and micro-reaction system thereof |
| CN105436512A (en) * | 2014-08-13 | 2016-03-30 | 南京理工大学 | Preparation method of nano-copper catalysts |
| CN105945302A (en) * | 2016-05-20 | 2016-09-21 | 金陵科技学院 | Preparation method for antioxidant copper nanopowder |
| CN105945302B (en) * | 2016-05-20 | 2017-11-28 | 金陵科技学院 | A kind of preparation method of Anti-Oxidation Copper Nanopowders |
| CN109822090A (en) * | 2017-11-23 | 2019-05-31 | 中国科学院化学研究所 | A kind of preparation method of the copper nanoparticle of in-stiu coating organic matter |
| CN109970092A (en) * | 2017-12-27 | 2019-07-05 | 广州科城环保科技有限公司 | A kind of preparation method of high-bulk-density basic copper carbonate |
| CN109970092B (en) * | 2017-12-27 | 2021-09-21 | 广州科城环保科技有限公司 | Preparation method of high-bulk-density basic copper carbonate |
| CN110774395A (en) * | 2019-10-22 | 2020-02-11 | 含山县宏达门业家具有限公司 | Method for improving waterproof and corrosion-resistant performance of wooden door |
| CN110976901A (en) * | 2019-12-31 | 2020-04-10 | 湘潭大学 | Preparation method of nano copper powder |
| CN113000855A (en) * | 2021-03-23 | 2021-06-22 | 中国科学技术大学先进技术研究院 | Preparation method of micro-nano copper powder |
| CN113000855B (en) * | 2021-03-23 | 2024-04-19 | 中国科学技术大学先进技术研究院 | Preparation method of micro-nano copper powder |
| CN113618075A (en) * | 2021-08-23 | 2021-11-09 | 孙珲 | Preparation method of filling high-purity nano material of ultralow-resistivity conductive paste |
| CN115611302A (en) * | 2022-10-22 | 2023-01-17 | 杭州富阳鸿源再生资源利用有限公司 | Preparation process of nano basic copper carbonate and nano basic copper carbonate |
| CN115611302B (en) * | 2022-10-22 | 2023-12-05 | 杭州富阳鸿源再生资源利用有限公司 | Preparation process of nano basic copper carbonate and nano basic copper carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103737013A (en) | Method for preparing nanometer spherical copper powder | |
| CN112357975B (en) | Preparation method of hollow ternary cathode material precursor and prepared ternary cathode material precursor | |
| WO2022116692A1 (en) | Method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and application | |
| JP7376862B2 (en) | Wet synthesis method of NCMA high nickel quaternary precursor | |
| CN102756131B (en) | Preparation method for micro-order platy silver powder | |
| JP6044463B2 (en) | Nickel cobalt manganese composite hydroxide and method for producing the same | |
| CN101716685B (en) | Method for preparing spherical superfine silver powder by using chemical reduction method | |
| KR20160021112A (en) | Nickel-cobalt-manganese composite hydroxide, and production method therefor | |
| CN103100722B (en) | Preparation method of high tap density monodisperse silver powder | |
| CN102728852B (en) | Preparation method of oxide or meta-coated nickel ultrafine powder | |
| CN110997198B (en) | Silver particles and method for producing same | |
| CN102441675B (en) | Preparation method for high-crystallinity silver powder | |
| CN103008675B (en) | A kind of preparation method of nickel coated copper composite powder | |
| CN101333000B (en) | Process for synthesizing high pure electronic grade barium titanate by liquid phase method | |
| KR20090045508A (en) | An apparatus and a method for preparation of silver powder by double-jet type continuous solution reduction | |
| CN104070180B (en) | A kind of production method of solar cell conductive silver slurry high density silver powder | |
| WO2019237452A1 (en) | Method for preparing two-dimensional sheet-shaped cu-mof material | |
| JP3570591B2 (en) | Production method of copper powder | |
| CN105895894A (en) | Copper vanadate material as well as preparation method and electrochemical performance thereof | |
| CN102730735A (en) | Purification method for strontium carbonate | |
| CN102699338B (en) | Method for preparing spherical nickel powder | |
| CN102962470B (en) | Method for preparing spherical ultrafine nickel powder at room temperature | |
| KR100851815B1 (en) | A method of preparing nano silver powder | |
| CN103624249B (en) | A kind of preparation method of high tap density silver powder | |
| CN111492513B (en) | Positive electrode active material for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140423 |