CN114905038A - Nano polyhedral sphere structure silver-coated copper composite powder and preparation method thereof - Google Patents
Nano polyhedral sphere structure silver-coated copper composite powder and preparation method thereof Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010949 copper Substances 0.000 title claims abstract description 54
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 50
- 239000004332 silver Substances 0.000 title claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000843 powder Substances 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 55
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 15
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 12
- 229910017770 Cu—Ag Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 42
- 229920006393 polyether sulfone Polymers 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 19
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 4
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- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- DVGPWKIRAFDGCE-UHFFFAOYSA-N [C].[Cu].[Ag] Chemical compound [C].[Cu].[Ag] DVGPWKIRAFDGCE-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229940023462 paste product Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a silver-coated copper composite powder with a nano polyhedral sphere structure and a preparation method thereof, wherein spherical copper powder is coated by 100% of silver to form the silver-coated copper composite powder with the polyhedral sphere structure; the preparation method comprises the steps of S1, preparing a Cu-PVP/PES membrane by using copper sulfate and polyvinylpyrrolidone; s2, adding NaBH after preparing a Cu-PVP/PES membrane 4 Water solution, and then drying to obtain Cu/PES nano particles; s3, slowly adding AgNO 3 And (5) obtaining the bimetallic Cu-Ag nano particles by using an aqueous solution. The invention finely regulates and controls the content of the product by a chemical molecule self-assembly electroless deposition technologyThe surface electronic structure of the copper powder improves the aggregation and the shedding of silver particles, carries out optimization tests, establishes a simple and efficient method for preparing the high-quality silver-coated copper composite metal micro powder with the polyhedral sphere structure on a large scale, and greatly reduces the production cost.
Description
Technical Field
The invention relates to the field of conductive paste electronic materials, in particular to silver-coated copper composite powder with a nano polyhedral sphere structure and a preparation method thereof.
Background
The core of the manufacturing technology of the silver conductive paste is the preparation of the silver powder, and researches show that the form and the particle size of the silver powder play a key role in the electrical property, the fluidity, the adhesion and other properties of the silver paste, and the technical level and the production capacity of the silver conductive paste directly influence the development of the whole industry. The cost of the silver paste becomes an important factor influencing the price of the cell, and is an important means for reducing the cost of the photovoltaic cell.
All foreign electronic paste production enterprises have perfect high-level research and development systems, and are dedicated to the research on various silver powder preparation methods and technologies for a long time. Different silver electronic pastes are required by different requirements on base materials, film forming conditions, film layer performance and reliability, and different silver electronic pastes require different silver powders. The research content is continuously refined, and each large development company has own characteristics and special attack content. With the continuous rise of international silver prices, how to reduce and replace the use of silver becomes an urgent problem to be solved. On the premise that the existing silver powder silver paste product meets the performance requirements of users, developers try to substitute silver with Cu, Ni, Al and the like, and the using amount of the silver is continuously reduced. In recent years, foreign high-performance and high-reliability silver conductor paste has been developed: such as: according to patent reports, non-noble metals (Cu, Ni and Al) are used as basic powder and are prepared into mixed powder or composite powder with silver powder, so that the cost of the slurry is greatly reduced; the Japanese Kawasaki company uses copper and nickel ultrafine particles with the particle size of 0.1-1 mu m to prepare ultrafine thick film conductive paste; in response to the requirements of chip-type device production, the company of Beijing pottery, Japan, developed Ag-Pd composite slurry, pure silver slurry and even non-noble metal slurry for resistance-capacitance devices; noble metal conductor pastes of high conductivity, high adhesion strength and high solderability for use in high end products as thick film conductors and multilayer wiring; high adhesion strength, low curing temperature polymer conductive paste used in related products such as membrane switches, flexible circuits, light emitting devices, etc.
The method benefits from the vigorous support of the state on photovoltaic manufacturing, and with the rise of the domestic photovoltaic manufacturing capacity and the rapid increase of the market demand, the localization process of the silver paste is accelerated. However, the current situation of the electronic paste industry in China is seriously lagged behind the development demand of the electronic information industry, and although various conventional silver powders and related silver pastes can be produced, the electronic paste industry is far behind the advanced countries in the world from the aspects of production technology, product varieties, quality and market share. Especially in the high-end product field, the demand of high-end electronic components for the quantity and quality of the electronic paste varieties has to be satisfied by a large number of foreign imports for a long period of time. The development of silver powder and silver paste covers metal powder technology, organic polymer material technology and inorganic non-metal material technology, belongs to the interdisciplinary department, relates to a plurality of fields of powder metallurgy, chemical industry, electronics and the like, and has considerable technical difficulty. The main points are as follows: 1) most of middle-and-low-end electronic paste products are made domestically, and can basically meet the requirements of the current middle-and-low-grade fields in China, and some products have certain strength and level, but have great difference compared with the international level, and the products have small scale, less variety, single variety, unstable quality and performance, can not completely meet the requirements of users, and can not reach the industrial scale benefit; 2) the process technology and equipment level is low, the production equipment is backward and basically in a manual operation state; 3) the units with independent intellectual property rights and patents are few, the copying and repeated production is mostly carried out, and the process technology of special equipment production and slurry production is separated; 4) the required raw and auxiliary materials have low quality grade, and poor performance consistency and stability; 5) long-term development is ignored, scientific research investment and technical development are not paid attention, and the production level and the technology of the product are slowly improved. At present, silver-coated copper composite powder has huge market demands, and main market demands are photovoltaic front silver/back silver, 5G, semiconductor packaging, electric contacts, low-temperature touch screens, high heat conduction and heat dissipation, silver-copper-carbon composite materials and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the silver-coated copper composite powder with the nano polyhedral sphere structure and the preparation method thereof have the characteristics of good coating compactness, high conductivity, low production cost and the like.
The technical scheme adopted by the invention for solving the technical problem is as follows: the spherical copper powder is 100% coated by silver to form the silver-coated copper composite powder with the polyhedral sphere structure, wherein the weight percentages of Cu of all elements are as follows: ag is 34-38: 62 to 66.
Meanwhile, the invention also provides a preparation method of the silver-coated copper composite powder with the nano polyhedral sphere structure, which comprises the following steps,
s1, preparing a Cu-PVP/PES membrane by using copper sulfate and polyvinylpyrrolidone;
s2, adding NaBH after preparing a Cu-PVP/PES membrane 4 Water solution, and then drying to obtain Cu/PES nano particles;
s3, slowly adding AgNO 3 And (5) obtaining the bimetallic Cu-Ag nano particles by using an aqueous solution.
Further, in order to prevent the Cu-Ag nanoparticles from being oxidized, the present invention further comprises the steps of,
s4, adding the sodium citrate solution of the metal salt mixed solution into a conical flask of deionized water, then heating the solution to boiling under inert gas flow and magnetic stirring, and rapidly cooling to room temperature;
s5, 1mL of fresh NaBH 4 And quickly adding the aqueous solution into the mixed solution, stirring and standing to obtain the Cu-Ag nano particles.
More specifically, in step S1 of the present invention, the method for preparing a Cu-PVP/PES membrane comprises the following steps,
1) putting a copper nitrate polyether sulfone (PES) membrane into a stainless steel filter, slowly permeating a copper sulfate solution through the PES membrane under certain nitrogen pressure, drying the PES membrane after permeation is finished, and recrystallizing copper sulfate and separating out PES membrane pores;
2) installing the dried PES membrane fixed in the membrane hole in a stainless steel filter, and slowly permeating the aqueous solution of polyvinylpyrrolidone into the PES membrane under a certain nitrogen pressure; after permeation, drying the PES film;
3) the above procedure was repeated four times to obtain the desired Cu-PVP/PES membrane with 80% loading.
Still further, in the step 2), the polyvinylpyrrolidone and the copper sulfate are coordinated and precipitated in the pores of the membrane during the permeation process.
Furthermore, the method for preparing the Cu-PVP/PES film also comprises the steps of,
4) and (3) putting the Cu-PVP/PES membrane into an oven for drying, and ultrasonically cleaning and removing redundant ligand and unstable Cu-PVP coordination compound on the surface of the membrane.
Still more specifically, step S2 of the present invention includes the following steps,
A. putting the prepared Cu-PVP/PES membrane into a stainless steel filter, pouring the NaBH4 aqueous solution into the stainless steel filter, and slowly flowing through membrane pores at room temperature;
B. obtaining Cu nano particles in the pores of the membrane by in-situ reduction of Cu-PVP;
C. drying, washing and drying to obtain the Cu/PES nano particles.
More specifically, in step S3, the AgNO3 aqueous solution is poured into a stainless steel filter containing dried Cu/PES nanoparticles, and slowly flows through the pores at room temperature; in the process, Cu nanoparticles and Ag + And carrying out spontaneous displacement reaction in the membrane pores to obtain the bimetallic Cu-Ag nano particles.
Furthermore, the molar ratio of the copper sulfate to the polyvinylpyrrolidone is 1: 4-5; the copper sulfate and AgNO 3 In a molar ratio of 1-2: 1; the NaBH 4 The concentration of the aqueous solution ranges from 50 to 100mM, 250 mL.
The method has the beneficial effects that the defects in the background technology are overcome, the problems of poor compactness of the cladding layer and uneven surface of the product in the chemical plating method in the existing silver-clad copper composite powder production are solved, the surface electronic structure of the copper powder in the product is finely regulated and controlled through the chemical molecular self-assembly electroless deposition technology, the aggregation and the falling of silver particles are improved, the optimization test is carried out, the method for simply and efficiently preparing the high-quality silver-clad copper composite metal micro powder with the polyhedral sphere structure on a large scale is established, and the production cost is greatly reduced.
Drawings
FIG. 1 is a schematic structural view of a silver-clad copper composite powder with a polyhedral sphere structure according to the present invention;
FIG. 2 is an energy spectrum of the silver-clad copper composite powder with a polyhedral spherical structure of example 1;
FIG. 3 is a diagram showing the specific surface area of the silver-clad copper composite powder of the polyhedral sphere structure of example 1;
fig. 4 is a particle size diagram of the silver-clad copper composite powder having the polygonal spherical structure of example 1.
In the figure: 1. copper; 2. silver.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings and preferred embodiments. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
As shown in fig. 1, the spherical copper powder is 100% coated with silver to form the silver-coated copper composite powder with a polyhedral nano-sphere structure, wherein the weight percentages and atom percentages of the elements are as follows:
the spherical copper powder is made into silver-coated copper powder with a polyhedral sphere structure, and the particle size is 500-700 nanometers, 1-3 microns and 3-5 microns; the contact area of the powder in the slurry can be increased, and the conductivity of the slurry is improved;
the following describes in detail the preparation method of the silver-clad copper composite powder with the polyhedral sphere structure.
Example 1
Firstly, a copper nitrate polyether sulfone (PES) membrane is placed in a stainless steel filter, 0.3M 50ml of copper sulfate solution slowly permeates through the PES membrane under certain nitrogen pressure, and after permeation is finished, the PES membrane is dried for 30 minutes at 60 ℃. After drying, the copper sulfate recrystallizes and precipitates PES membrane pores. Then, the dried PES membrane fixed in the membrane pores was mounted on a stainless steel filter, and 1.2M 50mL of an aqueous solution of polyvinylpyrrolidone (PVP, 55000 molecular weight) was slowly permeated into the PES membrane under a certain nitrogen pressure. The polyvinylpyrrolidone and the copper sulfate are coordinated and precipitated in the membrane pores during the permeation process. After the permeation, the PES membrane was dried at 60 ℃ for 30 minutes. The above procedure was repeated four times to obtain the desired Cu-PVP/PES membrane with 80% loading (based on electronic balance). And finally, putting the Cu-PVP/PES film into a 60 ℃ drying oven for drying. Redundant ligand and unstable Cu-PVP coordination compound on the surface of the membrane are removed by ultrasonic cleaning.
The prepared Cu-PVP/PES membrane was placed in a stainless steel filter. Then, NaBH is added 4 The aqueous solution (50mM, 250mL) was poured into a stainless steel filter and allowed to flow slowly through the membrane pores at room temperature. Cu nanoparticles can be obtained in membrane pores by in-situ reduction of Cu-PVP, and finally, drying is carried out at 60 ℃, then deionized water is used for washing for several times, and drying is carried out, thus obtaining the Cu/PES nanoparticles. Subsequently, 0.06M, 250mL of AgNO3 in water was poured into a stainless steel filter containing dried Cu/PES nanoparticles and slowly flowed through the membrane pores at room temperature. In the process, Cu nanoparticles and Ag + Spontaneous displacement reactions occurred within the pores of the membrane to give bimetallic Cu-Ag nanoparticles, and the metal salt mixed solution and 10mL sodium citrate (Na3C6H5O 7.2H 2O) solution (1 wt%, used as a capping reagent) were added to a 100mL conical flask in deionized water. The solution was then heated to boiling and rapidly cooled to room temperature under inert gas flow and magnetic stirring to prevent possible oxidation of the Cu-Ag nanoparticles. 1mL of fresh excess aqueous NaBH4 solution was added quickly to the mixed solution. Stirring is kept for several minutes, and then standing is carried out for several minutes to obtain the Cu-Ag nano particles.
The obtained multi-surface sphere structure silver-coated copper composite powder was subjected to three times of experiments, and the obtained bulk density and tap density were as shown in the following table:
| a | b | c | |
| bulk density g/cm 3 | 2.248 | 2.233 | 2.237 |
| Tap density g/cm 3 | 4.284 | 4.282 | 4.283 |
Meanwhile, the energy spectrum of the silver-clad copper composite powder with the polyhedral spherical structure obtained by the embodiment is shown in fig. 2; the specific surface area diagram of the silver-clad copper composite powder with the polyhedral spherical structure obtained in the present example is shown in fig. 3; the particle size diagram of the silver-clad copper composite powder having a polyhedral spherical structure obtained in this example is shown in fig. 4.
Example 2
The concentration of the aqueous polyvinylpyrrolidone solution in example 1 was changed to 1.5M and 50mL, and the remaining conditions were not changed.
Example 3
AgNO as in example 1 3 The concentration of the aqueous solution was changed to 0.03M and 250mL, and the remaining conditions were not changed.
While particular embodiments of the present invention have been described in the foregoing specification, various modifications and alterations to the previously described embodiments will become apparent to those skilled in the art from this description without departing from the spirit and scope of the invention.
Claims (9)
1. The silver-coated copper composite powder with the nano polyhedral sphere structure is characterized in that: coating 100% of spherical copper powder with silver to form the silver-coated copper composite powder with a polyhedral spherical structure, wherein the weight percentages of Cu of the elements are as follows: ag is 34-38: 62 to 66.
2. A preparation method of silver-coated copper composite powder with a nano polyhedral sphere structure is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing a Cu-PVP/PES membrane by using copper sulfate and polyvinylpyrrolidone;
s2, adding NaBH after preparing a Cu-PVP/PES membrane 4 Water solution, and then drying to obtain Cu/PES nano particles;
s3, slowly adding AgNO 3 And (5) obtaining the bimetallic Cu-Ag nano particles by using an aqueous solution.
3. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure as claimed in claim 2, wherein the method comprises the following steps: the method also comprises the step of carrying out the following steps,
s4, adding the sodium citrate solution of the metal salt mixed solution into a conical flask of deionized water, then heating the solution to boiling under inert gas flow and magnetic stirring, and rapidly cooling to room temperature;
s5, 1mL of new NaBH 4 And quickly adding the aqueous solution into the mixed solution, stirring and standing to obtain the Cu-Ag nano particles.
4. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure according to claim 3, which is characterized by comprising the following steps of: in step S1, the method for preparing Cu-PVP/PES film comprises the following steps,
1) putting a copper nitrate polyether sulfone (PES) membrane into a stainless steel filter, slowly permeating a copper sulfate solution through the PES membrane under certain nitrogen pressure, drying the PES membrane after permeation is finished, and recrystallizing copper sulfate and separating out PES membrane pores;
2) installing the dried PES membrane fixed in the membrane hole in a stainless steel filter, and slowly permeating the aqueous solution of polyvinylpyrrolidone into the PES membrane under a certain nitrogen pressure; after permeation, drying the PES film;
3) the above procedure was repeated four times to obtain the desired Cu-PVP/PES membrane with 80% loading.
5. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure as claimed in claim 4, wherein the method comprises the following steps: in the step 2), polyvinylpyrrolidone and copper sulfate are coordinated and precipitated in the membrane pores in the permeation process.
6. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure as claimed in claim 4, wherein the method comprises the following steps: the method also comprises the step of carrying out the following steps,
4) and (3) putting the Cu-PVP/PES membrane into an oven for drying, and ultrasonically cleaning and removing redundant ligand and unstable Cu-PVP coordination compound on the surface of the membrane.
7. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure according to claim 5, which is characterized by comprising the following steps: the step S2 includes the following steps,
A. putting the prepared Cu-PVP/PES membrane into a stainless steel filter, pouring an aqueous solution of NaBH4 into the stainless steel filter, and slowly flowing through membrane pores at room temperature;
B. obtaining Cu nano particles in the pores of the membrane by in-situ reduction of Cu-PVP;
C. and drying, washing and drying to obtain the Cu/PES nano particles.
8. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure according to claim 5, which is characterized by comprising the following steps: in the step S3, pouring AgNO3 aqueous solution into a stainless steel filter containing dried Cu/PES nano particles, and slowly flowing through membrane pores at room temperature; in the process, Cu nanoparticles and Ag + And carrying out spontaneous displacement reaction in the membrane pores to obtain the bimetallic Cu-Ag nano particles.
9. The method for preparing the silver-coated copper composite powder with the nano polyhedral sphere structure as claimed in claim 2, wherein the method comprises the following steps: said sulfurThe molar ratio of the acid copper to the polyvinylpyrrolidone is 1: 4-5; the copper sulfate and AgNO 3 In a molar ratio of 1-2: 1; the NaBH 4 The concentration of the aqueous solution ranges from 50 to 100mM, 250 mL.
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| KR20110047911A (en) * | 2009-10-31 | 2011-05-09 | 주식회사 지오션 | Copper powder for silver coated and manufacturing method |
| CN102161104A (en) * | 2011-04-02 | 2011-08-24 | 东南大学 | Preparation method of copper-silver composite powder |
| CN103128308A (en) * | 2013-03-06 | 2013-06-05 | 东南大学 | Method for preparing compact silver-coated copper powder by using one pot method |
| CN104999076A (en) * | 2015-06-01 | 2015-10-28 | 浙江亚通焊材有限公司 | One-pot prepared silver covered copper nanometer powder with controllable shell thickness and preparation method of silver covered copper nanometer powder |
| CN105598468A (en) * | 2016-03-17 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of silver coated copper nanoparticles capable of being used for conductive ink |
| WO2020143273A1 (en) * | 2019-01-08 | 2020-07-16 | 南京邮电大学 | Core-shell structured ag@cu nanoparticle conductive ink, preparation method therefor and use thereof |
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| KR20110047911A (en) * | 2009-10-31 | 2011-05-09 | 주식회사 지오션 | Copper powder for silver coated and manufacturing method |
| CN102161104A (en) * | 2011-04-02 | 2011-08-24 | 东南大学 | Preparation method of copper-silver composite powder |
| CN103128308A (en) * | 2013-03-06 | 2013-06-05 | 东南大学 | Method for preparing compact silver-coated copper powder by using one pot method |
| CN104999076A (en) * | 2015-06-01 | 2015-10-28 | 浙江亚通焊材有限公司 | One-pot prepared silver covered copper nanometer powder with controllable shell thickness and preparation method of silver covered copper nanometer powder |
| CN105598468A (en) * | 2016-03-17 | 2016-05-25 | 中国科学院深圳先进技术研究院 | Preparation method of silver coated copper nanoparticles capable of being used for conductive ink |
| WO2020143273A1 (en) * | 2019-01-08 | 2020-07-16 | 南京邮电大学 | Core-shell structured ag@cu nanoparticle conductive ink, preparation method therefor and use thereof |
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