CN114749677B - Preparation method and application of micron copper powder - Google Patents
Preparation method and application of micron copper powder Download PDFInfo
- Publication number
- CN114749677B CN114749677B CN202210450054.2A CN202210450054A CN114749677B CN 114749677 B CN114749677 B CN 114749677B CN 202210450054 A CN202210450054 A CN 202210450054A CN 114749677 B CN114749677 B CN 114749677B
- Authority
- CN
- China
- Prior art keywords
- copper powder
- solution
- solvent
- mass ratio
- preparation
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a preparation method and application of micron copper powder, wherein the preparation method comprises the following steps: (1) Mixing a copper source, a dispersant and a solvent, and stirring to obtain a solution I; (2) Mixing a reducing agent and a solvent, and stirring to obtain a solution II; (3) Mixing the solution I and the solution II, and reacting to obtain a solution III; (4) Naturally settling the solution III, drying and grinding to obtain micron copper powder; in step (1) and step (2), the solvent comprises a combination of ethylene glycol and deionized water. The invention adopts the ethylene glycol and the water as the mixed solvent, greatly improves the reaction concentration of the system, increases the yield in the large-scale production process, reduces the dosage of the ethylene glycol and reduces the production cost; the preparation route is simple, the operability is strong, the prepared copper powder is low in resistivity and adjustable in particle size, a universal preparation strategy is provided for high-concentration and low-conductivity micron copper powder in a liquid phase system, and the preparation method is suitable for popularization and application.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method and application of micron copper powder.
Background
The laboratory efficiency of HJT (heterojunction solar cell) can reach more than 26%, and the average mass production efficiency of the large-scale production of manufacturers can reach 24%, which is higher than that of the last generation of PERC (emitter and back passivated cell), thus becoming the next generation of solar cell technology.
However, one of the problems facing HJT is the high manufacturing cost (0.93-0.98 yuan/watt), which is higher than PERC in cost in addition to labor cost. In the cost ratio, the cost of the silicon chip is removed, wherein the ratio is finally low-temperature silver paste. The HJT process can only use low-temperature silver paste due to the influence of temperature, and the low-temperature silver paste product mainly comes from import, and the price is 10-20% higher than that of the conventional silver paste, so that the great approach for reducing the HJT cost is to realize the localization of the low-temperature silver paste and replace part of precious metal silver by using cheap metal so as to really reduce the cost of the low-temperature silver paste. The silver-coated copper is formed by coating a silver shell on the surface of copper powder, so that the use amount of silver can be reduced while the conductivity of the slurry is ensured, and the silver-coated copper becomes an effective strategy for reducing the cost of HJT.
The preparation of the silver-coated copper can be divided into two steps: the first step is to prepare copper powder; the second step is to coat the silver layer on the copper surface. Obviously, the morphology and structure of copper powder will determine the morphology and performance of silver-coated copper, and thus the preparation of copper powder is particularly critical in the research and development of silver-coated copper slurry.
At present, the problems of low system concentration and high copper powder resistivity are faced in the process of preparing the copper powder by liquid phase reduction. Therefore, the research and development of the high-concentration and low-resistance copper powder in a liquid phase reduction system are significant.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of micron copper powder. Different from the traditional single solvent system, in order to improve the concentration of the reaction system, the invention adopts water and glycol as mixed solvents, and Cu of the system 2+ The concentration can be improved from 0.4mol/L to 2.0mol/L, the yield of the copper powder is over 90 percent, and the particle size of the copper powder is in the micron level (1-10 mu m), so that the method is suitable for popularization and application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of micron copper powder, which comprises the following steps:
(1) Mixing a copper source, a dispersant and a solvent, and stirring to obtain a solution I;
(2) Mixing a reducing agent and a solvent, and stirring to obtain a solution II;
(3) Mixing the solution I and the solution II, and reacting to obtain a solution III;
(4) Naturally settling the solution III, drying and grinding to obtain the micron copper powder;
wherein in step (1) and step (2), the solvent each independently comprises a combination of ethylene glycol and deionized water.
According to the invention, a mixed solvent system of ethylene glycol and water is selected, so that on one hand, the dissolving amount of reactants can be increased, and the reaction concentration of the system is greatly improved; on the other hand, the morphology, the particle size and the resistivity of the copper powder are regulated and controlled by changing the proportion of the ethylene glycol and the water and the concentration of the system. Particularly, the yield of the copper powder obtained by the preparation scheme adopted by the invention is over 90 percent.
In the invention, in the solvent in the step (1) and the step (2), the mass ratio of the ethylene glycol to the deionized water is 1 (0.5-2);
wherein "0.5-2" may be 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2, etc.
Preferably, in step (1) and step (2), the stirring temperature is 70-90 deg.C (for example, 70 deg.C, 72 deg.C, 74 deg.C, 76 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 84 deg.C, 86 deg.C, 88 deg.C, 90 deg.C, etc.), and the time is 0.5-1h (for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, etc.).
In the invention, in the step (1), the mass ratio of the copper source, the dispersant and the solvent is 1 (0.8-1.5) to 1.5-7.3;
wherein "0.8-1.5" can be 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, etc.;
"1.5-7.3" can be 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.3, etc.
Preferably, the copper source comprises any one of copper sulfate pentahydrate, anhydrous copper sulfate, copper nitrate hexahydrate or copper nitrate or a combination of at least two thereof, preferably copper sulfate pentahydrate.
In the present invention, in the step (1), the dispersant includes any one or a combination of at least two of polyvinylpyrrolidone, polyethylene glycol, D-ribose, or β -cyclodextrin, preferably a combination of polyvinylpyrrolidone and β -cyclodextrin.
The application adopts the combination of the polyvinylpyrrolidone and the beta-cyclodextrin, on one hand, the dissolving amount of reactants can be increased, thereby greatly improving the reaction concentration of the system; on the other hand, the resistivity of the copper powder can be reduced.
Preferably, the mass ratio of the polyvinylpyrrolidone to the beta-cyclodextrin is (10-1): 1;
wherein "10-1" can be 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc.
Preferably, the polyvinylpyrrolidone comprises any one of polyvinylpyrrolidone K15, polyvinylpyrrolidone K30 or polyvinylpyrrolidone K60 or a combination of at least two thereof, preferably polyvinylpyrrolidone K30.
Preferably, the polyethylene glycol comprises any one of PEG400, PEG1000, PEG2000, PEG4000 or PEG10000 or a combination of at least two thereof.
In the invention, in the step (2), the mass ratio of the reducing agent to the solvent is 1 (2.1-10.4);
wherein "2.1-10.4" may be 2.1, 3, 5, 6, 7, 8, 9, 10, 10.4, etc.
Preferably, in step (2), the reducing agent comprises any one of sodium hypophosphite, ascorbic acid, hydrazine hydrate or formaldehyde or a combination of at least two thereof, preferably a combination of sodium hypophosphite and ascorbic acid.
In the present invention, the reducing agent is a combination of sodium hypophosphite and ascorbic acid to improve the resistivity of the copper powder.
Preferably, the mass ratio of the sodium hypophosphite to the ascorbic acid is (10-1): 1;
wherein "10-1" can be 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc.
In the invention, in the step (3), the mass ratio of the copper source, the dispersant and the reducing agent in the solution III is (2.5-3.0): (3.0-3.5): 1;
wherein "2.5-3.0" can be 2.5, 2.6, 2.7, 2.8, 2.9, 3, etc.;
"3.0-3.5" may be 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, etc.
Preferably, in step (3), the molar concentration of the copper source in the solution III is 0.4-2mol/L (for example, it may be 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, etc.).
Preferably, in the step (3), the mass concentration of the dispersant in the solution III is 132-660g/L (for example, 132g/L, 198g/L, 264g/L, 330g/L, 396g/L, 462g/L, 528g/L, 600 g/L, etc.).
Preferably, in the step (3), the mass concentration of the reducing agent in the solution III is 38-194g/L (for example, 38g/L, 58g/L, 77g/L, 97g/L, 116g/L, 135g/L, 155g/L, 174g/L, 176g/L, 194g/L and the like can be realized).
In the present invention, in step (3), the reaction temperature is 90 to 110 ℃ (for example, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃,100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃ and the like) and the reaction time is 1.5 to 2.5h (for example, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h and the like).
In the present invention, in step (4), the temperature of the drying is 45-60 ℃ (for example, 45 ℃, 47 ℃, 49 ℃, 51 ℃, 53 ℃, 55 ℃, 57 ℃, 59 ℃, 60 ℃ and the like can be adopted), and the time is 5-6h (for example, 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h and the like can be adopted).
Preferably, in step (4), before the drying, the precipitate obtained by natural sedimentation of the solution III is washed by deionized water and absolute ethyl alcohol in sequence.
Preferably, in step (4), the average particle size of the micron copper powder is 1-10 μm (for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, etc.).
As a preferable technical scheme of the invention, the preparation method of the micron copper powder comprises the following steps:
(1) Mixing a copper source, a dispersant and a solvent, and stirring to obtain a solution I;
wherein the copper source comprises copper sulfate pentahydrate, the dispersing agent comprises the combination of polyvinylpyrrolidone K30 and beta-cyclodextrin in a mass ratio of (10-1): 1, and the solvent comprises the combination of ethylene glycol and deionized water in a mass ratio of 1: (0.5-2);
(2) Mixing a reducing agent and a solvent, and stirring to obtain a solution II;
wherein the reducing agent comprises a combination of sodium hypophosphite and ascorbic acid in a mass ratio of (10-1): 1, and the solvent comprises a combination of ethylene glycol and deionized water in a mass ratio of 1: (0.5-2);
(3) Mixing the solution I and the solution II, and reacting to obtain a solution III;
wherein the molar concentration of the copper source in the solution III is 0.4-2mol/L, the reaction temperature is 90-110 ℃, and the reaction time is 1.5-2.5h;
(4) Naturally settling the solution III, removing supernatant, sequentially cleaning and precipitating by using deionized water and absolute ethyl alcohol, drying for 5-6h at 45-60 ℃, and grinding to obtain the micron copper powder;
wherein the average grain diameter of the micron copper powder is 1-10 μm.
In a second aspect, the invention provides the application of the preparation method of the micron copper powder in preparing silver-coated copper slurry.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the ethylene glycol and the water as the mixed solvent, which not only can greatly improve the reaction concentration of the system and increase the yield in the large-scale production process, but also can reduce the dosage of the ethylene glycol and reduce the production cost;
(2) The preparation method provided by the invention is simple in preparation route and strong in operability, and the prepared copper powder is low in resistivity and adjustable in particle size, so that a universal preparation strategy is provided for high-concentration and low-conductivity micron copper powder in a liquid phase system, and the preparation method is suitable for popularization and application.
Drawings
FIG. 1 is an SEM image of micron copper powder prepared by the method at different reaction system concentrations of 0.4-2.0M.
FIG. 2 is a graph showing the particle size of copper powder as a function of the concentration of the reaction system.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
The embodiment provides a preparation method of 0.4M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 120g (0.48 mol) of copper sulfate pentahydrate, 144g of polyvinylpyrrolidone K30, 14.4g of beta-cyclodextrin and 800mL of solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(2) Mixing 42.2g of sodium hypophosphite, 4.22g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The 0.4M reaction concentration micron copper powder prepared in this example had an average particle size of 3.93 μ M.
Example 2
The embodiment provides a preparation method of 0.6M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 180g (0.72 mol) of copper sulfate pentahydrate, 216g of polyvinylpyrrolidone K30, 21.6g of beta-cyclodextrin and 800mL of solvent (the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1;
(2) Mixing 63.3g of sodium hypophosphite, 6.33g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 1.9 hours at 105 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 5 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 48 ℃ for 5.1 hours, taking out, and grinding to obtain the micron copper powder.
The 0.6M reaction concentration micron copper powder prepared in this example had an average particle size of 8.57 μ M.
Example 3
The embodiment provides a preparation method of 0.8M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 240g (0.96 mol) of copper sulfate pentahydrate, 288g of polyvinylpyrrolidone K30, 28.8g of beta-cyclodextrin and 800mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(2) Mixing 84.4g of sodium hypophosphite, 8.44g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2.3 hours at 95 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 55 ℃ for 5.2 hours, taking out, and grinding to obtain the micron copper powder.
The 0.8M reaction concentration micron copper powder prepared in this example had an average particle size of 4.83 μ M.
Example 4
The embodiment provides a preparation method of 1.0M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 300g (1.2 mol) of copper sulfate pentahydrate, 360g of polyvinylpyrrolidone K30, 36.0g of beta-cyclodextrin and 800mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(2) Mixing 105.5g of sodium hypophosphite, 10.55g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 1.0M reaction concentration micron copper powder prepared in this example was 1.83. Mu.m.
Example 5
The embodiment provides a preparation method of 1.2M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 360g (1.44 mol) of copper sulfate pentahydrate, 432g of polyvinylpyrrolidone K30, 43.2g of beta-cyclodextrin and 800mL of solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(2) Mixing 126.6g of sodium hypophosphite, 12.66g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 1.2M reaction concentration micron copper powder prepared in this example was 6.6. Mu.m.
Example 6
The embodiment provides a preparation method of 1.4M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 420g (1.68 mol) of copper sulfate pentahydrate, 504g of polyvinylpyrrolidone K30, 50.4g of beta-cyclodextrin and 800mL of solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(2) Mixing 147.7g of sodium hypophosphite, 14.77g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 1.4M reaction concentration micron copper powder prepared in this example was 7.44. Mu.m.
Example 7
The embodiment provides a preparation method of 1.6M reaction concentration micron copper powder, which comprises the following steps:
(1) 480g (1.92 mol) of copper sulfate pentahydrate, 576g of polyvinylpyrrolidone K30, 57.6g of beta-cyclodextrin and 800mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1;
(2) Mixing 168.8g of sodium hypophosphite, 16.88g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 1.6M reaction concentration micron copper powder prepared in this example was 6.72. Mu.m.
Example 8
The embodiment provides a preparation method of 1.8M reaction concentration micron copper powder, which comprises the following steps:
(1) 540g (2.16 mol) of copper sulfate pentahydrate, 648g of polyvinylpyrrolidone K30, 64.8g of beta-cyclodextrin and 800mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1;
(2) Mixing 189.9g of sodium hypophosphite, 18.99g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 1.8M reaction concentration micron copper powder prepared in this example was 4.67. Mu.m.
Example 9
The embodiment provides a preparation method of micron copper powder with a reaction concentration of 2.0M, and the preparation method of the micron copper powder comprises the following steps:
(1) Mixing 600g (2.4 mol) of copper sulfate pentahydrate, 720g of polyvinylpyrrolidone K30, 72.0g of beta-cyclodextrin and 800mL of a solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(2) 211g of sodium hypophosphite, 21.1g of ascorbic acid and 400mL of a solvent (the solvent is a combination of ethylene glycol and deionized water with the mass ratio of 1;
(3) Uniformly mixing the solution I and the solution II, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(4) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
The average particle size of the 2.0M reaction concentration micron copper powder prepared in this example was 3.43. Mu.m.
Example 10
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which is different from example 1 only in that in step (1), polyvinylpyrrolidone K30 is replaced by polyvinylpyrrolidone K60 of the same mass, and the other steps are the same as example 1.
Example 11
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which is different from example 1 only in that in step (1), no beta-cyclodextrin is contained, the amount of polyvinylpyrrolidone K30 is increased to 160 g, and other steps are the same as example 1.
Example 12
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which is different from example 1 only in that polyvinylpyrrolidone K30 is not contained in step (1), the amount of beta-cyclodextrin is increased to 75g, and the other steps are the same as example 1.
Example 13
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which differs from example 1 only in that, in step (1) and step (2), the solvent is 800mL, the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1.
Example 14
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which differs from example 1 only in that, in step (1) and step (2), the solvent is 800mL, the solvent is a combination of ethylene glycol and deionized water with a mass ratio of 1.
Example 15
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which differs from example 1 only in that sodium hypophosphite is not included in step (2) and the mass of ascorbic acid is increased to 180g, and the other steps are the same as example 1.
Example 16
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which is different from example 1 only in that ascorbic acid is not contained in step (2), the mass of sodium hypophosphite is increased to 45g, and other steps are the same as example 1.
Example 17
This example provides a method for preparing 0.4M reaction concentration micron copper powder, which differs from example 1 only in that 120g (0.48 mol) of copper sulfate pentahydrate is replaced by 0.48mol of copper nitrate hexahydrate in step (1), and the other steps are the same as example 1.
Comparative example 1
The comparative example provides a method for preparing 0.4M reaction concentration micron copper powder, which comprises the following steps:
(1) Mixing 120g (0.48 mol) of copper sulfate pentahydrate, 144g of polyvinylpyrrolidone K30, 14.4g of beta-cyclodextrin and 1200mL of solvent (the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1;
(2) Uniformly mixing 42.2g of sodium hypophosphite, 4.22g of ascorbic acid and the solution I, and reacting for 2 hours at 100 ℃ to obtain a solution III;
(3) And transferring the solution III to a beaker, cooling to room temperature, naturally settling, removing supernatant, washing the bottom precipitate with deionized water for 6 times, washing with absolute ethyl alcohol for 3 times, drying in a vacuum drying oven at 50 ℃ for 5 hours, taking out, and grinding to obtain the micron copper powder.
Comparative example 2
This comparative example provides a method for preparing 0.4M reaction concentration micron copper powder, which differs from example 1 only in that the solvent in step (1) and step (2) is 800mL of ethylene glycol, and no deionized water is contained, and the other steps are the same as example 1.
Comparative example 3
This comparative example provides a method for preparing 0.4M reaction concentration micron copper powder, which is different from example 1 only in that the solvent is 800mL of deionized water and no ethylene glycol is contained in step (1) and step (2), and the other steps are the same as example 1.
Test example 1
Particle size measurement
Testing a sample: copper powder obtained by the preparation method provided in examples 1 to 9
As shown in FIG. 1, SEM images of micron copper powder prepared by the method at different reaction system concentrations of 0.4-2.0M are shown. The method provided by the invention can realize the preparation of the micron copper powder from low concentration to high concentration. In addition, the system concentration is 0.4-2.0M, the copper powder has small shape difference and is small in granular intermingled copper flakes, and the average grain size of the copper powder is about 2 mu M when 1.0M is the smallest; at other concentrations, the average particle size of the copper powder varied, but was 10 μm or less.
FIG. 2 is a graph showing the variation of the particle size of copper powder depending on the concentration of the reaction system, and it can be seen that the average particle size of copper powder is the smallest at 1.0M, and the average particle size of copper powder fluctuates at other concentrations, but they are all 10 μ M or less.
Test example 2
Average resistivity test
Testing a sample: copper powder obtained by the production methods provided in examples 1 to 17 and comparative examples 1 to 3
The test method comprises the following steps: average resistivity test for testing copper powder under 30MPa test pressure
The test results are shown in table 1 below:
TABLE 1
As can be seen from the data in Table 1, the copper powder prepared by the preparation method provided by the invention has lower resistivity, and the average resistivity is 0.00008-0.0007 ohm cm.
As can be seen by comparing example 1 with examples 10-12, the choice of dispersant affects the resistivity of the copper powder.
As can be seen from a comparison of examples 1, 13 to 14 and comparative examples 2 to 3, the resistivity of the copper powder prepared was low only when the mixed solvent of ethylene glycol and deionized water was used in a mass ratio of 1 (0.5 to 2).
It is clear from a comparison of example 1 and examples 15-16 that the choice of reducing agent affects the resistivity of the copper powder.
As can be seen from a comparison of example 1 and example 17, the substitution of copper sulfate pentahydrate with an equimolar amount of copper nitrate hexahydrate affected the resistivity of the copper powder.
It is understood from a comparison between example 1 and comparative example 1 that the resistivity of the copper powder is affected by directly adding the reducing agent to the reaction system.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it is not meant to imply that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (13)
1. The preparation method of the micron copper powder is characterized by comprising the following steps of:
(1) Mixing a copper source, a dispersant and a solvent, and stirring to obtain a solution I;
(2) Mixing a reducing agent and a solvent, and stirring to obtain a solution II;
(3) Mixing the solution I and the solution II, and reacting to obtain a solution III;
(4) Naturally settling, drying and grinding the solution III to obtain the micron copper powder with the average particle size of 0.5-10 microns;
in the step (1) and the step (2), the solvent respectively and independently comprises a combination of ethylene glycol and deionized water, and the mass ratio of the ethylene glycol to the deionized water is 1 (0.5-2); the copper source is copper sulfate pentahydrate; the dispersing agent is a combination of polyvinylpyrrolidone K30 and beta-cyclodextrin; the reducing agent is a combination of sodium hypophosphite and ascorbic acid; in the step (3), the reaction temperature is 90-110 ℃, the reaction time is 1.5-2.5h, and the molar concentration of the copper source in the solution III is 0.4-2 mol/L.
2. The method for preparing micron copper powder according to claim 1, wherein in step (1) and step (2), the stirring temperature is 70-90 ℃ and the stirring time is 0.5-1 h.
3. The method for preparing micron copper powder as defined in claim 1, wherein in step (1), the mass ratio of the copper source, the dispersant and the solvent is 1 (0.8-1.5) to (1.5-7.3).
4. The method for preparing micron copper powder according to claim 1, wherein the mass ratio of polyvinylpyrrolidone K30 to beta-cyclodextrin is (10-1): 1.
5. The method for preparing micron copper powder according to claim 1, wherein in the step (2), the mass ratio of the reducing agent to the solvent is 1 (2.1-10.4).
6. The method for preparing micron copper powder according to claim 1, wherein the mass ratio of the sodium hypophosphite to the ascorbic acid is (10-1): 1.
7. The method for preparing micron copper powder as defined in claim 1, wherein in step (3), the mass ratio of the copper source, the dispersant and the reducing agent in the solution III is (2.5-3.0): (3.0-3.5): 1.
8. The method for preparing micron copper powder as claimed in claim 1, wherein in the step (3), the mass concentration of the dispersing agent in the solution III is 132-660 g/L.
9. The method for preparing micron copper powder according to claim 1, wherein in the step (3), the mass concentration of the reducing agent in the solution III is 38-194 g/L.
10. The method for preparing micron copper powder according to claim 1, wherein in the step (4), the drying temperature is 45-60 ℃ and the drying time is 5-6 h.
11. The method for preparing micron copper powder as claimed in claim 1, wherein in step (4), before the drying, the precipitate obtained by natural sedimentation of the solution III is sequentially washed by deionized water and absolute ethyl alcohol.
12. Method for the preparation of copper micro-powder according to claim 1, characterized in that it comprises the following steps:
(1) Mixing a copper source, a dispersant and a solvent, and stirring to obtain a solution I;
wherein the copper source is copper sulfate pentahydrate, the dispersant is the combination of polyvinylpyrrolidone K30 and beta-cyclodextrin in a mass ratio of (10-1): 1, and the solvent is the combination of ethylene glycol and deionized water in a mass ratio of 1: (0.5-2);
(2) Mixing a reducing agent and a solvent, and stirring to obtain a solution II;
the reducing agent is a combination of sodium hypophosphite and ascorbic acid in a mass ratio of (10-1): 1, and the solvent is a combination of ethylene glycol and deionized water in a mass ratio of 1: (0.5-2);
(3) Mixing the solution I and the solution II, and reacting to obtain a solution III;
wherein the molar concentration of the copper source in the solution III is 0.4-2mol/L, the reaction temperature is 90-110 ℃, and the reaction time is 1.5-2.5h;
(4) Naturally settling the solution III, removing supernatant, sequentially cleaning and precipitating by using deionized water and absolute ethyl alcohol, drying for 5-6h at 45-60 ℃, and grinding to obtain the micron copper powder;
wherein the average grain diameter of the micron copper powder is 1-10 μm.
13. Use of a method for the preparation of micro copper powder according to any one of claims 1 to 12 for the preparation of a silver-coated copper slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210450054.2A CN114749677B (en) | 2022-04-26 | 2022-04-26 | Preparation method and application of micron copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210450054.2A CN114749677B (en) | 2022-04-26 | 2022-04-26 | Preparation method and application of micron copper powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114749677A CN114749677A (en) | 2022-07-15 |
| CN114749677B true CN114749677B (en) | 2023-04-11 |
Family
ID=82332596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210450054.2A Active CN114749677B (en) | 2022-04-26 | 2022-04-26 | Preparation method and application of micron copper powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114749677B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474678A (en) * | 2008-11-28 | 2009-07-08 | 中国兵器工业第五二研究所 | Method for preparing antioxidated superfine copper powder |
| TW201608032A (en) * | 2014-08-27 | 2016-03-01 | 永源化工原料股份有限公司 | Method of manufacturing micro or submicron copper powder |
| JP2020029611A (en) * | 2018-08-24 | 2020-02-27 | 住友電気工業株式会社 | Production method of copper nanoparticle |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102240813A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院过程工程研究所 | Preparing method for cubic crystallized copper micro powder |
| CN102601383A (en) * | 2012-03-30 | 2012-07-25 | 电子科技大学 | Method for preparing ultrafine copper powder at room temperature |
| JP2014152395A (en) * | 2013-02-14 | 2014-08-25 | Kansai Univ | Method for producing copper nanoparticle suitable for copper nanoink |
| CN104028778B (en) * | 2014-06-25 | 2016-05-25 | 东北大学 | A kind of method of preparing fast nanometer copper particle |
| CN108436096A (en) * | 2018-03-12 | 2018-08-24 | 西南科技大学 | A kind of method that Nanometer Copper microballoon is prepared under low temperature |
| CN109940169B (en) * | 2019-04-19 | 2022-03-29 | 陕西科技大学 | Nano copper and preparation method thereof |
-
2022
- 2022-04-26 CN CN202210450054.2A patent/CN114749677B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101474678A (en) * | 2008-11-28 | 2009-07-08 | 中国兵器工业第五二研究所 | Method for preparing antioxidated superfine copper powder |
| TW201608032A (en) * | 2014-08-27 | 2016-03-01 | 永源化工原料股份有限公司 | Method of manufacturing micro or submicron copper powder |
| JP2020029611A (en) * | 2018-08-24 | 2020-02-27 | 住友電気工業株式会社 | Production method of copper nanoparticle |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114749677A (en) | 2022-07-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110355380A (en) | A kind of preparation method of hexagonal flake micron crystalline substance silver powder | |
| CN107545941A (en) | A kind of method for preparing solar cell front side silver paste slurry | |
| CN106602081B (en) | A kind of palladium oxide catalyst and preparation method thereof for direct methanoic acid fuel cell | |
| CN104668572A (en) | Silver powder and silver paste for back electrode of solar cell and solar cell | |
| CN1857833A (en) | Preparing process of silver powder for printing slurry of electrode in solar cell | |
| CN112186107B (en) | Tin-based perovskite solar cell with hole transport layer and preparation method thereof | |
| CN108161024B (en) | Preparation method of linear micro-nano metal copper | |
| CN111525033B (en) | Reverse mesoporous perovskite solar cell structure and preparation method thereof | |
| CN114749677B (en) | Preparation method and application of micron copper powder | |
| CN114700490A (en) | Preparation method of nickel-coated graphite composite particles and application of nickel-coated graphite composite particles in electromagnetic shielding field | |
| CN114050226B (en) | Negative electrode material, preparation method thereof, negative electrode plate and lithium ion battery | |
| CN102103895B (en) | Silver paste used for positive electrodes of solar batteries and grid lines, preparation method thereof and solar battery containing same | |
| CN109920998B (en) | Application of ionic liquid in preparation of silicon-doped carbon quantum dots, and preparation method and application of silicon-doped carbon quantum dots | |
| CN113593772B (en) | Nano silver-copper solid solution and preparation method and application thereof | |
| CN114530278A (en) | Conductive slurry for HJT battery and production process thereof | |
| CN112108162B (en) | 0D/2D composite nano material and preparation method and application thereof | |
| CN114260461A (en) | Multi-fold spherical silver powder and preparation method and application thereof | |
| CN116532656B (en) | High-conductivity high-dispersion flaky silver adhesive and preparation method thereof | |
| CN102956282A (en) | Conductive composition, solar cell unit, and solar cell module | |
| CN108817413B (en) | Preparation of CoSnO3Method for @ Au amorphous nano cube | |
| CN108455655B (en) | ZnO/C hollow microsphere and preparation method thereof | |
| CN111313044A (en) | Bimetallic atom hollow carbon nanosphere catalyst and preparation method thereof | |
| CN114242991B (en) | Tin micron particle composite graphene high-performance lithium and sodium storage material and application thereof | |
| CN113257944B (en) | Heterojunction photoelectric detector and preparation method thereof | |
| CN108807988B (en) | Preparation method of spherical lithium ferrous silicate cathode material for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |