CN101818364A - Method for preparing nano copper powder - Google Patents
Method for preparing nano copper powder Download PDFInfo
- Publication number
- CN101818364A CN101818364A CN200910022137A CN200910022137A CN101818364A CN 101818364 A CN101818364 A CN 101818364A CN 200910022137 A CN200910022137 A CN 200910022137A CN 200910022137 A CN200910022137 A CN 200910022137A CN 101818364 A CN101818364 A CN 101818364A
- Authority
- CN
- China
- Prior art keywords
- copper
- negative electrode
- anode
- cathode
- solution
- 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
Images
Landscapes
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for preparing nano copper powder, which comprises the following steps of: compounding copper sulfate, lauryl sodium sulfate and polyoxyethylene sorbitan monooleate in a molar ratio of 1:0.5-2:0.05-0.3, dissolving the mixture in water, blending the aqueous solution and lauryl mercaptan-containing benzene solution in a molar ratio of copper sulfate to lauryl mercaptan of 1:0.5-2, and uniformly stirring; pouring the emulsion fluid into an electrolytic bath, taking pure copper as an anode and stainless steel as a cathode, and regulating the pH value to between 0.5 and 4; supplying direct current to the anode and the cathode to ensure that the lauryl mercaptan dissolved in an electrolyte performs in-situ clad on precipitated copper atoms, the generated copper powder loosely attaches to the surface of the cathode, copper ions near the anode are continuously migrated to the place near the cathode under the action of diffusion and directional migration of electric charge at the same time, and the electrolytic time is 30 to 120 minutes; adding the cathode to which the copper powder is attached into absolute ethyl alcohol, and putting the cathode in an ultrasonic cleaner for desorption by using ultrasonic waves for 5 to 20 minutes to obtain dark purple copper solution; and filtering the solution, and drying the filtrate for 1 to 3 hours at the temperature of between 60 and 100 DEG C in a vacuum environment to obtain brown powder, namely a nano copper composite.
Description
Technical field
The present invention relates to the electrochemical preparation method of copper nanoparticle.
Background technology
With the copper nanoparticle purity height of electrolytic process preparation, shape is dendroid mostly, and good suppression performance and sintering character are arranged at present, has obtained at aspects such as powder metallurgy, nuclear power, chemical industry and novel alloy materials using widely.Granularity is thicker but the made copper powder of electrolytic process is compared with liquid phase reduction, size composition disperses, when the copper powder of certain particle size fraction of needs, must adopt the method for classification (screening) to meet the demands, this has just prolonged the production cycle, increased the cost of product, made again and bring disadvantageous effect to sintering character by powder active reduction in turnover and treating processes.The copper nanoparticle of common electrochemical process preparation is the unstable state material, and they are the sex change with the ambiance reaction easily, easily interaction and reuniting between particle, and its dispersion liquid is difficult to stable for extended periods of time usually, has limited its range of application greatly.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of copper nanoparticle.
The present invention is a kind of preparation method of copper nanoparticle, the steps include:
(1) be that 1: 0.5～2: 0.05～0.3 ratio is composite in the mol ratio of copper sulfate and sodium lauryl sulphate, polyoxyethylene 20 sorbitan monooleate, be dissolved in the water, in the ratio that in the copper sulfate and the mol ratio of lauryl mercaptan is 1: 0.5～2 the above-mentioned aqueous solution is mixed with the benzole soln that contains lauryl mercaptan, under magnetic stirring apparatus and action of ultrasonic waves, stir;
(2) milk sap that stirs being injected electrolyzer, is anode with the fine copper, and stainless steel is a negative electrode, and anode is 1: 2～5 with the area ratio of negative electrode, and the pole piece spacing is 30～70mm, with the vitriol oil or ammoniacal liquor the pH value is adjusted to 0.5～4;
(3) feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface.Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and current density is 0.01A/cm
2～0.2A/cm
2, electrolysis time is 30～120 minutes;
(4) negative electrode that will adhere to copper powder is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 5～20 minutes, obtains the intense violet color copper solutions.With the solution that obtains filter, in 60 ℃～100 ℃ vacuum environment dry 1～3 hour, can obtain the brown ceramic powder nano copper composition.
Beneficial effect of the present invention is: the present invention is the electrochemical preparation method that adopts protected by organic monomolecular layer, adsorbs the organic supramolecular modifier of one deck densification in the surface chemistry of inorganic nano nuclear, and the stability that effectively improves it is with dispersed.The nanometer spherical copper grain diameter of preparing is about 20nm～60nm.
Usefulness of the present invention also is: (1) can prepare tiny, the evengranular nanometer powder of particle diameter.(2) dispersed better, solved the problem that dentrite that electrochemical process prepares and wet chemical nanometer powder are generally reunited.(3) solved the particulate problem of oxidation.
Prepare copper nanoparticle with existing protected by organic monomolecular layer and compare, this method have raw material be simple and easy to, simple, characteristics such as cost is low.Prepared copper nanoparticle is stable in the air, and particle diameter is even.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the copper nanoparticle of the inventive method preparation, and wherein scale is 200nm.
Embodiment
The present invention is a kind of preparation method of copper nanoparticle, the steps include:
(1) be that 1: 0.5～2: 0.05～0.3 ratio is composite in the mol ratio of copper sulfate and sodium lauryl sulphate, polyoxyethylene 20 sorbitan monooleate, be dissolved in the water, in the ratio that in the copper sulfate and the mol ratio of lauryl mercaptan is 1: 0.5～2 the above-mentioned aqueous solution is mixed with the benzole soln that contains lauryl mercaptan, under magnetic stirring apparatus and action of ultrasonic waves, stir;
(2) milk sap that stirs being injected electrolyzer, is anode with the fine copper, and stainless steel is a negative electrode, and anode is 1: 2～5 with the area ratio of negative electrode, and the pole piece spacing is 30～70mm, with the vitriol oil or ammoniacal liquor the pH value is adjusted to 0.5～4;
(3) feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface.Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and current density is 0.01A/cm
2～0.2A/cm
2, electrolysis time is 30～120 minutes;
(4) negative electrode that will adhere to copper powder is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 5～20 minutes, obtains the intense violet color copper solutions.With the solution that obtains filter, in 60 ℃～100 ℃ vacuum environment dry 1～3 hour, can obtain the brown ceramic powder nano copper composition.
Be embodiment more specifically below:
Embodiment 1:
Get anhydrous cupric sulfate 5g, be dissolved in the 500mL distilled water.
Get the 1g sodium lauryl sulphate, the 5mL tween 80, the 15mL lauryl mercaptan, 20mL benzene stirs under magnetic stirring apparatus and ultrasonic wave effect.
Above-mentioned two kinds of solution being mixed, mix under the effect of magnetic stirring apparatus, is 0.5 with vitriol oil titration to pH value.
With prepared milk sap is electrolytic solution, and fine copper is an anode, and stainless (steel) wire is a negative electrode, and anode is 1: 2 with the area ratio of negative electrode, and the pole piece spacing is 30mm, and cathode current density is 0.01A/cm
2Feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface; Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and electrolysis time is 30 minutes.
The negative electrode that will adhere to copper powder after electrolysis is finished is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 5 minutes, obtains the intense violet color copper solutions.With the solution that obtains filter, in 60 ℃ of vacuum environments dry 3 hours, can obtain the brown ceramic powder nano copper composition.
Embodiment 2:
Get anhydrous cupric sulfate 12.5g, be dissolved in the 500mL distilled water.
Get the 1g sodium lauryl sulphate, the 5mL tween 80, the 15mL lauryl mercaptan, 20mL benzene stirs under magnetic stirring apparatus and ultrasonic wave effect.
Above-mentioned two kinds of solution being mixed, mix under the effect of magnetic stirring apparatus, is 4 with vitriol oil titration to pH value.
With prepared milk sap is electrolytic solution, and fine copper is an anode, and stainless (steel) wire is a negative electrode, and anode is 1: 5 with the area ratio of negative electrode, and the pole piece spacing is 45mm, and cathode current density is 0.2A/cm
2Feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface; Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and electrolysis time is 60 minutes.
The negative electrode that will adhere to copper powder after electrolysis is finished is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 15 minutes, obtains the intense violet color copper solutions.With the solution that obtains filter, in 80 ℃ of vacuum environments dry 2 hours, can obtain the brown ceramic powder nano copper composition.As shown in Figure 1, adopt the transmission electron microscope picture of the copper nanoparticle of the inventive method preparation, wherein scale is 200nm.
Embodiment 3:
Get anhydrous cupric sulfate 7.5g, be dissolved in the 500mL distilled water.
Get the 1g sodium lauryl sulphate, the 5mL tween 80, the 15mL lauryl mercaptan, 20mL benzene stirs under magnetic stirring apparatus and ultrasonic wave effect.
Above-mentioned two kinds of solution being mixed, mix under the effect of magnetic stirring apparatus, is 1.5 with vitriol oil titration to pH value.
With prepared milk sap is electrolytic solution, and fine copper is an anode, and stainless (steel) wire is a negative electrode, and anode is 1: 3 with the area ratio of negative electrode, and the pole piece spacing is 70mm, and cathode current density is 0.1A/cm
2Feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface; Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and electrolysis time is 120 minutes.
The negative electrode that will adhere to copper powder after electrolysis is finished is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 20 minutes, obtains the intense violet color copper solutions.With the solution that obtains filter, in 100 ℃ of vacuum environments dry 1 hour, can obtain the brown ceramic powder nano copper composition.
Claims (1)
1. the preparation method of a copper nanoparticle the steps include:
(1) be that 1: 0.5～2: 0.05～0.3 ratio is composite in the mol ratio of copper sulfate and sodium lauryl sulphate, polyoxyethylene 20 sorbitan monooleate, be dissolved in the water, in the ratio that in the copper sulfate and the mol ratio of lauryl mercaptan is 1: 0.5～2 the above-mentioned aqueous solution is mixed with the benzole soln that contains lauryl mercaptan, under magnetic stirring apparatus and action of ultrasonic waves, stir;
(2) milk sap that stirs being injected electrolyzer, is anode with the fine copper, and stainless steel is a negative electrode, and anode is 1: 2～5 with the area ratio of negative electrode, and the pole piece spacing is 30～70mm, with the vitriol oil or ammoniacal liquor the pH value is adjusted to 0.5～4;
(3) feed direct current to electrode, anodic copper is constantly dissolved to be entered in the electrolytic solution, near the negative electrode in the solution cupric ion is constantly separated out and is deposited on the negative electrode, the lauryl mercaptan that is dissolved in the electrolytic solution carries out the original position coating to the copper atom of separating out, and the copper powder loosely that makes generation is attached to cathode surface; Simultaneously near the cupric ion the anode relies on the directional migration of diffusion and electric charge to move near the negative electrode continuously, thereby guarantees electrolyticly to carry out smoothly, and current density is 0.01A/cm
2～0.2A/cm
2, electrolysis time is 30～120 minutes;
(4) negative electrode that will adhere to copper powder is put into dehydrated alcohol, puts into ultrasonic cleaner and carries out ultrasonic, desorption, and ultrasonic time is 5～20 minutes, obtains the intense violet color copper solutions; With the solution that obtains filter, in 60 ℃～100 ℃ vacuum environment dry 1～3 hour, can obtain the brown ceramic powder nano copper composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910022137A CN101818364A (en) | 2009-04-03 | 2009-04-03 | Method for preparing nano copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910022137A CN101818364A (en) | 2009-04-03 | 2009-04-03 | Method for preparing nano copper powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101818364A true CN101818364A (en) | 2010-09-01 |
Family
ID=42653626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910022137A Pending CN101818364A (en) | 2009-04-03 | 2009-04-03 | Method for preparing nano copper powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101818364A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088371A (en) * | 2013-01-25 | 2013-05-08 | 重庆大学 | Method for preparing nano-copper cubic particles |
| CN104928724A (en) * | 2015-07-07 | 2015-09-23 | 昆明理工大学 | Method for electrolytically preparing dendritic fine copper powder in oxalic acid |
| CN106854768A (en) * | 2016-11-21 | 2017-06-16 | 西北矿冶研究院 | electrodeposition preparation method of superfine copper powder |
| CN107022772A (en) * | 2017-06-20 | 2017-08-08 | 广东工业大学 | A kind of nano copper slurry and preparation method thereof |
| CN108677220A (en) * | 2018-06-26 | 2018-10-19 | 中南大学 | A kind of electrolyte being used to prepare Nano metal powder |
| CN108728871A (en) * | 2018-06-26 | 2018-11-02 | 中南大学 | A method of copper nanoparticle is prepared using fluorocarbon surfactant |
| CN108914164A (en) * | 2018-08-09 | 2018-11-30 | 金陵科技学院 | A method of Anti-Oxidation Copper Nanopowders are prepared from contained waste liquid recycling |
-
2009
- 2009-04-03 CN CN200910022137A patent/CN101818364A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103088371A (en) * | 2013-01-25 | 2013-05-08 | 重庆大学 | Method for preparing nano-copper cubic particles |
| CN103088371B (en) * | 2013-01-25 | 2015-03-11 | 重庆大学 | Method for preparing nano-copper cubic particles |
| CN104928724A (en) * | 2015-07-07 | 2015-09-23 | 昆明理工大学 | Method for electrolytically preparing dendritic fine copper powder in oxalic acid |
| CN104928724B (en) * | 2015-07-07 | 2017-07-07 | 昆明理工大学 | A kind of method of the electrolytic preparation dendroid fine copper powder in ethanedioic acid |
| CN106854768A (en) * | 2016-11-21 | 2017-06-16 | 西北矿冶研究院 | electrodeposition preparation method of superfine copper powder |
| CN106854768B (en) * | 2016-11-21 | 2019-03-26 | 西北矿冶研究院 | electrodeposition preparation method of superfine copper powder |
| CN107022772A (en) * | 2017-06-20 | 2017-08-08 | 广东工业大学 | A kind of nano copper slurry and preparation method thereof |
| CN108677220A (en) * | 2018-06-26 | 2018-10-19 | 中南大学 | A kind of electrolyte being used to prepare Nano metal powder |
| CN108728871A (en) * | 2018-06-26 | 2018-11-02 | 中南大学 | A method of copper nanoparticle is prepared using fluorocarbon surfactant |
| CN108728871B (en) * | 2018-06-26 | 2019-11-08 | 中南大学 | A method of copper nanoparticle is prepared using fluorocarbon surfactant |
| CN108677220B (en) * | 2018-06-26 | 2020-04-14 | 中南大学 | Electrolyte for preparing nano metal powder |
| CN108914164A (en) * | 2018-08-09 | 2018-11-30 | 金陵科技学院 | A method of Anti-Oxidation Copper Nanopowders are prepared from contained waste liquid recycling |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101818364A (en) | Method for preparing nano copper powder | |
| Velichenko et al. | Electrodeposition PbO2–TiO2 and PbO2–ZrO2 and its physicochemical properties | |
| Nekouie et al. | Effect of organic additives on synthesis of copper nano powders by pulsing electrolysis | |
| CN103639420B (en) | A kind of low melt type ionic liquid electrodeposition altogether prepares the method for copper nanoparticle | |
| CN101554664A (en) | Method for preparing nano-scale silver powder | |
| CN104947136B (en) | Method for preparing cuprous chloride nanocube electrode material by eutectic type ionic liquid electrolysis | |
| Nekouei et al. | Copper nanopowder synthesis by electrolysis method in nitrate and sulfate solutions | |
| Luo et al. | Efficient production of metal manganese achieved by cylindrical and rotary electrode | |
| Zhang et al. | Electrodeposition of gold nanoparticle arrays on ITO glass as electrode with high electrocatalytic activity | |
| CN104018189A (en) | Preparation method for novel nano-silver wire | |
| CN105671611B (en) | A kind of method that graphene surface directly loads nano-oxide | |
| CN107858527B (en) | A method of absorption prepares high purity copper and copper sulphate from copper facing sludge | |
| Ren et al. | An extrinsic faradaic layer on CuSn for high-performance electrocatalytic CO2 reduction | |
| Li et al. | Shape-controlled synthesis of nickel phosphide nanocrystals and their application as hydrogen evolution reaction catalyst | |
| CN101818365B (en) | Method for preparing nano stibium powder | |
| Mech et al. | On the influence of magnetic field on electrodeposition of Ni–TiO2 composites from a citrate baths | |
| CN105977496B (en) | Include slicker solder-rare earth-graphene lead storage battery grid alloy preparation method | |
| Zaki et al. | Surface properties of nanostructured gold coatings electrodeposited at different potentials | |
| CN101942679A (en) | Method for preparing, pretreating and dispersing superfine copper powder | |
| CN102367582A (en) | Method for preparing nanoscale metal particles by bimetallic electrode pulse direct-current bias electrodeposition | |
| Park et al. | Morphology controlled 1D Pt nanostructures synthesized by galvanic displacement of Cu nanowires in chloroplatinic acid | |
| CN113380999A (en) | Preparation method of silver-iron oxide porous nanocube negative electrode material for molten salt battery | |
| Velichenko et al. | Electrodeposition of PbO 2-ZrO 2 composite materials | |
| CN106854768B (en) | electrodeposition preparation method of superfine copper powder | |
| RU2723558C1 (en) | Method of producing nanostructured cobalt oxide on carbon support |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100901 |