CN114905038B - Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof - Google Patents
Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof Download PDFInfo
- Publication number
- CN114905038B CN114905038B CN202210340655.8A CN202210340655A CN114905038B CN 114905038 B CN114905038 B CN 114905038B CN 202210340655 A CN202210340655 A CN 202210340655A CN 114905038 B CN114905038 B CN 114905038B
- Authority
- CN
- China
- Prior art keywords
- silver
- pes
- nano
- sphere structure
- composite powder
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 59
- 239000004332 silver Substances 0.000 title claims abstract description 59
- 239000010949 copper 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 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 36
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 16
- 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
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 45
- 229920006393 polyether sulfone Polymers 0.000 claims description 45
- 239000012528 membrane Substances 0.000 claims description 34
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000009467 reduction Effects 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
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 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
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 238000005232 molecular self-assembly Methods 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229940023462 paste product Drugs 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 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
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- DVGPWKIRAFDGCE-UHFFFAOYSA-N [C].[Cu].[Ag] Chemical compound [C].[Cu].[Ag] DVGPWKIRAFDGCE-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007772 electroless plating Methods 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000004806 packaging method and process 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
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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 nanometer polyhedral sphere structure and a preparation method thereof, wherein spherical copper powder is 100 percent coated by silver to form the silver-coated copper composite powder with the polyhedral sphere structure; the preparation method comprises the steps of S1, preparing Cu-PVP/PES film by utilizing copper sulfate and polyvinylpyrrolidone; s2, adding NaBH after preparing Cu-PVP/PES film 4 The aqueous solution is dried to obtain Cu/PES nano particles; s3, slowly adding AgNO 3 And (3) obtaining the bimetallic Cu-Ag nano particles by using the aqueous solution. According to the invention, through a chemical molecular self-assembly electroless deposition technology, the surface electronic structure of copper powder in the product is finely regulated and controlled, the aggregation and the falling of silver particles are improved, an optimization test is carried out, a simple and efficient method for preparing the high-quality silver-coated copper composite metal micro powder with a polyhedral sphere structure in a large scale is established, and the production cost is greatly reduced.
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 silver conductive paste manufacturing technology is silver powder preparation, and research shows that the morphology and the particle size of the silver powder play a key role in the properties of the silver paste such as electrical performance, fluidity, adhesiveness and the like, and the technical level and the production capacity of the silver conductive paste directly influence the development of the whole industry. The cost of silver paste has become an important factor affecting the price of the battery, and is an important means for reducing the cost of the photovoltaic battery.
Foreign electronic paste production enterprises have perfect high-level research and development systems, and are devoted to various silver powder preparation methods and technological researches for a long time. Different requirements of base materials, film forming conditions, film performances and reliability require different silver electronic pastes, and different silver electronic pastes require different silver powders. Research content is continuously refined, and each large development company has own characteristics and specialized content. In the case of continuous rising international silver prices, how to reduce and replace the use of silver is an urgent issue to be resolved. Under the premise that the existing silver powder silver paste product meets the performance requirements of users, developers try to replace silver with Cu, ni, al and the like, and the use amount of silver is continuously reduced. In recent years, foreign silver conductor slurry layers with high performance and high reliability are endless: such as: according to patent reports, non-noble metals (Cu, ni and Al) are adopted as base powder, and mixed powder or composite powder is prepared from the base powder and silver powder, so that the cost of slurry is greatly reduced; the ultra-fine thick film conductive paste was prepared by kawasaki corporation of japan using ultra-fine particles of copper and nickel having a particle size of 0.1-1 μm; according to the requirements of chip type component production, the Japan Beijing ceramic company develops that the resistance-capacitance component uses Ag-Pd composite slurry, pure silver slurry or even non-noble metal slurry; high conductivity, high adhesion strength, and high solderability noble metal conductor pastes for use in high end products as thick film conductors and multilayer wiring; high adhesion strength, low cure temperature polymer conductive paste, etc. used in related products such as membrane switches, flexible circuits, light emitting devices, etc.
The method is beneficial to the strong support of the national photovoltaic manufacturing, and the localization process of the silver paste is accelerated along with the rising of the domestic photovoltaic manufacturing capacity and the rapid increase of the market demand. However, the current state of the electronic paste industry in China is seriously lagged behind the development requirement of the electronic information industry, and various conventional silver powder and related silver paste can be produced, but the electronic paste industry is far behind advanced countries in the world no matter from the production technology, the product variety and quality and market share. In particular, in the high-end product field, the requirements of high-end electronic components on the quantity and quality of electronic paste varieties have to be met by means of a large number of foreign imports during a quite long period of time. Because the development of silver powder and silver paste covers metal powder technology, organic polymer material technology and inorganic nonmetallic material technology, belongs to the interdiscipline, and relates to a plurality of fields of powder metallurgy, chemical industry, electronics and the like, the technology has considerable difficulty, and the research, development and application in the aspect are not systematically accumulated, talent lack and invested funds are insufficient in China, so the quality management level and innovation capability are far less than those of developed countries such as the United states, japan and the like. The main expression is as follows: 1) The middle-low-end electronic paste product has been mostly realized in domestic, can basically meet the requirements of the middle-low grade field in China at present, and part of the products have certain strength and level, but compared with international level, the products have great gap, and the products have small scale, few varieties, single variety, unstable quality and performance, can not completely meet the requirements of users, and can not reach the scale benefit of industry; 2) The process technology and equipment level are low, and the production equipment is basically in a manual operation state after the production equipment is lagged; 3) The units with independent intellectual property rights and patents are less, most of them are imitation and repetitive production, and the special equipment production is separated from the process technology of slurry production; 4) The required raw materials and auxiliary materials are low in quality grade, and the consistency and stability of the performance are poor; 5) Neglecting long-term development, not paying attention to scientific research investment and technical development, and slowly improving the production level and the technology of the product. The current silver-coated copper composite powder has great market demands, and the main market demands are light Fu Zhengyin/back silver, 5G, semiconductor packaging, electric contacts, low-temperature touch screens, high heat conduction and high heat dissipation, silver-copper-carbon composite materials and the like.
Disclosure of Invention
The invention aims to solve the technical problems that: the silver-coated copper composite powder with the nano polyhedral sphere structure and the preparation method thereof have the characteristics of good compactness of a coating layer, high conductivity, low production cost and the like.
The technical scheme adopted for solving the technical problems is as follows: the silver-coated copper composite powder with the nanometer polyhedral sphere structure is prepared by coating spherical copper powder with 100% of silver to form the silver-coated copper composite powder with the polyhedral sphere structure, wherein the weight percentage of each element is Cu: ag=34 to 38:62 to 66.
Meanwhile, the invention also provides a preparation method of the silver-coated copper composite powder with the nanometer polyhedral sphere structure, which comprises the following steps,
s1, preparing a Cu-PVP/PES film by using copper sulfate and polyvinylpyrrolidone;
s2, adding NaBH after preparing Cu-PVP/PES film 4 The aqueous solution is dried to obtain Cu/PES nano particles;
s3, slowly adding AgNO 3 And (3) obtaining the bimetallic Cu-Ag nano particles by using the aqueous solution.
Further, in order to prevent oxidation of the Cu-Ag nanoparticles, the present invention further includes the steps of,
s4, adding the sodium citrate solution of the metal salt mixed solution into a conical flask of deionized water, and then heating the solution to boiling under inert gas flow and magnetic stirring and rapidly cooling to room temperature;
s5, adding 1mL of new NaBH 4 And rapidly adding the aqueous solution into the mixed solution, stirring and standing to obtain Cu-Ag nano particles.
In further detail, in the step S1 of the invention, the method for preparing the Cu-PVP/PES film comprises the following steps,
1) Putting a copper nitrate polyethersulfone PES membrane into a stainless steel filter, slowly penetrating a copper sulfate solution through the PES membrane under a certain nitrogen pressure, drying the PES membrane after penetration is finished, recrystallizing the copper sulfate, and separating out PES membrane holes;
2) The dry PES film fixed in the film hole is arranged in a stainless steel filter, and the polyvinylpyrrolidone water solution slowly permeates into the PES film under a certain nitrogen pressure; drying the PES film after the permeation is finished;
3) The above procedure was repeated four times to obtain the desired Cu-PVP/PES film with 80% loading.
Still further, in the above step 2), polyvinylpyrrolidone and copper sulfate coordinate and precipitate in the membrane pores during the permeation process.
Further, the method for preparing the Cu-PVP/PES film further comprises the steps of,
4) And (3) putting the Cu-PVP/PES film into a baking oven for baking, and removing the superfluous ligand and the unstable Cu-PVP coordination compound on the surface of the film by ultrasonic cleaning.
Still more particularly, the step S2 of the present invention includes the steps of,
A. putting the prepared Cu-PVP/PES membrane into a stainless steel filter, pouring NaBH4 aqueous solution into the stainless steel filter, and slowly flowing through the membrane pores at room temperature;
B. cu nanoparticles are obtained in the membrane pores through in-situ reduction of Cu-PVP;
C. and (5) drying, washing and drying to obtain the Cu/PES nano-particles.
In still further detail, in step S3 of the present invention, an aqueous AgNO3 solution is poured into a stainless steel filter containing dry Cu/PES nanoparticles, and slowly flows through the membrane pores at room temperature; in this process, cu nanoparticles and Ag + And (3) carrying out spontaneous displacement reaction in the membrane hole to obtain the bimetallic Cu-Ag nano particle.
Further, the molar ratio of the copper sulfate to the polyvinylpyrrolidone is 1:4-5; the copper sulfate and AgNO 3 The molar ratio of (2) is 1-2:1, a step of; the NaBH 4 The concentration of the aqueous solution was in the range of 50-100mM,250mL.
The method has the beneficial effects that the defects in the background technology are overcome, the problems of poor compactness and uneven surface of a coating layer in a product by an electroless plating method in the production of the silver-coated copper composite powder at present are solved, the surface electronic structure of copper powder in the product is finely regulated and controlled by a chemical molecular self-assembly electroless deposition technology, the aggregation and the falling of silver particles are improved, an optimization test is carried out, and a simple and efficient method for preparing the high-quality silver-coated copper composite metal micro powder with a polyhedral sphere structure in a large scale is established, so that the production cost is greatly reduced.
Drawings
FIG. 1 is a schematic diagram of a silver-coated copper composite powder with a polyhedral sphere structure;
FIG. 2 is an energy spectrum diagram of a silver-coated copper composite powder with a polyhedral sphere structure of example 1;
FIG. 3 is a graph showing the specific surface area of the silver-coated copper composite powder with the polyhedral sphere structure of example 1;
fig. 4 is a particle size diagram of the silver-coated copper composite powder with the polyhedral sphere structure of example 1.
In the figure: 1. copper; 2. silver.
Detailed Description
The invention will now be described in further detail with reference to the drawings and a preferred embodiment. The drawings are simplified schematic representations which merely illustrate the basic structure of the invention and therefore show only the structures which are relevant to the invention.
The silver-coated copper composite powder with the nano polyhedral sphere structure is shown in the figure 1, 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 percentage and the atomic percentage of each element are shown in the following table:
preparing spherical copper powder into silver-coated copper powder with a polyhedral sphere structure, wherein 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 method for preparing the silver-coated copper composite powder with the polyhedral sphere structure is described in detail below.
Example 1
First, a copper nitrate polyethersulfone membrane (PES) was placed in a stainless steel filter, 0.3M 50ml of a copper sulfate solution was slowly permeated through the PES membrane under a certain nitrogen pressure, and after permeation was completed, the PES membrane was dried at 60℃for 30 minutes. After drying, the copper sulfate recrystallized and PES membrane pores were precipitated. Then, the dried PES film fixed in the film holes was mounted in a stainless steel filter, and 1.2M, 50mL of an aqueous solution of polyvinylpyrrolidone (PVP, 55000 molecular weight) was slowly permeated into the PES film under a certain nitrogen pressure. Polyvinylpyrrolidone and copper sulfate coordinate and precipitate in the membrane pores during the permeation process. After the permeation was completed, the PES film was dried at 60℃for 30 minutes. The above procedure was repeated four times to obtain the desired Cu-PVP/PES membrane with 80% load (based on an electronic balance). Finally, the Cu-PVP/PES film is put into a 60 ℃ oven for drying. The superfluous ligand and the unstable Cu-PVP coordination compound on the surface of the membrane are removed by ultrasonic cleaning.
The prepared Cu-PVP/PES film was put into a stainless steel filter. Then NaBH is applied 4 The aqueous solution (50 mM,250 mL) was poured into a stainless steel filter and slowly flowed through the membrane pores at room temperature. Cu nanoparticles can be obtained in membrane pores through in-situ reduction of Cu-PVP, and finally the Cu nanoparticles are dried at 60 ℃, washed with deionized water for several times and dried to obtain the Cu/PES nanoparticles. Subsequently, 0.06M, 250mL of AgNO3 aqueous solution was poured into the solution containing the dried Cu/PES nanoparticlesIn the stainless steel filter of the seed, the membrane pores were slowly flowed through at room temperature. In this process, cu nanoparticles and Ag + A spontaneous displacement reaction was performed in the membrane pores to obtain bimetallic Cu-Ag nanoparticles, and a metal salt mixed solution and 10mL sodium citrate (Na 3C6H5 O7.2H2O) solution (1 wt%, serving as a cap reagent) were added to a 100mL Erlenmeyer flask. The solution was then heated to boiling under inert gas flow and magnetic stirring and rapidly cooled to room temperature to prevent possible oxidation of the Cu-Ag nanoparticles. 1mL of fresh excess NaBH4 in water was added quickly to the mixed solution. Stirring and maintaining for a few minutes, and then standing for a few minutes to obtain the Cu-Ag nano-particles.
Repeating the experiment on the obtained silver-coated copper composite powder with the polyhedral sphere structure for three times, wherein the obtained bulk density and tap density are 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-coated copper composite powder with the polyhedral sphere structure obtained by the embodiment is shown in figure 2; the specific surface area diagram of the silver-coated copper composite powder with the polyhedral sphere structure obtained by the embodiment is shown in fig. 3; the particle size diagram of the silver-coated copper composite powder with the polyhedral sphere structure obtained in the embodiment is shown in fig. 4.
Example 2
The concentration of the polyvinylpyrrolidone aqueous solution in example 1 was changed to 1.5M and 50mL, and the other conditions were unchanged.
Example 3
AgNO in example 1 3 The concentration of the aqueous solution was 0.03M and 250mL, and the other conditions were unchanged.
The foregoing description is merely illustrative of specific embodiments of the invention, and the invention is not limited to the details shown, since modifications and variations of the foregoing embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (6)
1. A preparation method of silver-coated copper composite powder with a nano polyhedral sphere structure is characterized by comprising the following steps: comprises the steps of,
s1, preparing a Cu-PVP/PES film by using copper sulfate and polyvinylpyrrolidone:
1) Putting a polyether sulfone membrane (PES) into a stainless steel filter, slowly penetrating a copper sulfate solution into the PES membrane under certain nitrogen pressure, drying the PES membrane after penetration is finished, recrystallizing the copper sulfate, and separating out PES membrane holes;
2) The dry PES film fixed in the film hole is arranged in a stainless steel filter, and the polyvinylpyrrolidone water solution slowly permeates into the PES film under a certain nitrogen pressure; drying the PES film after the permeation is finished;
3) Repeating the steps four times to obtain the required Cu-PVP/PES film with 80% load;
s2, adding NaBH after preparing Cu-PVP/PES film 4 Aqueous solution, thenDrying to obtain Cu/PES nano particles;
s3, slowly adding AgNO 3 Obtaining a bimetallic Cu-Ag nano particle by using the aqueous solution;
s4, adding the mixed solution in the step S3 and the sodium citrate solution into a conical flask of deionized water, and then heating the solution to boiling under inert gas flow and magnetic stirring and rapidly cooling to room temperature;
s5, adding 1mL of new NaBH 4 Adding the aqueous solution into the mixed solution rapidly, stirring and standing to obtain Cu-Ag nano particles, namely the silver-coated copper composite powder with the nano polyhedral sphere structure;
the silver-coated copper composite powder with the nanometer polyhedral sphere structure is formed by coating spherical copper powder with 100% of silver to form the silver-coated copper composite powder with the polyhedral sphere structure, wherein the weight percentage of each element is Cu: ag=34 to 38: 62-66.
2. The method for preparing the silver-coated copper composite powder with the nano-polyhedral sphere structure, as claimed in claim 1, is characterized in that: in the step 2) of the S1, polyvinylpyrrolidone and copper sulfate coordinate and precipitate in the membrane pores in the infiltration process.
3. The method for preparing the silver-coated copper composite powder with the nano-polyhedral sphere structure, as claimed in claim 1, is characterized in that: in S1, the method further comprises the step of,
4) And (3) after removing the superfluous ligand and the unstable Cu-PVP coordination compound on the surface of the membrane by ultrasonic cleaning, putting the Cu-PVP/PES membrane into an oven for drying.
4. The method for preparing the silver-coated copper composite powder with the nano-polyhedral sphere structure according to claim 2, which is characterized in that: the step S2 includes the following steps,
A. putting the prepared Cu-PVP/PES membrane into a stainless steel filter, pouring NaBH4 aqueous solution into the stainless steel filter, and slowly flowing through the membrane pores at room temperature;
B. cu nanoparticles are obtained in the membrane pores through in-situ reduction of Cu-PVP;
C. and (5) drying, washing and drying to obtain the Cu/PES nano-particles.
5. The method for preparing the silver-coated copper composite powder with the nano-polyhedral sphere structure according to claim 2, which is characterized in that: in the step S3, the AgNO3 aqueous solution is poured into a stainless steel filter containing dry Cu/PES nano particles, and slowly flows through the membrane pores at room temperature; in this process, cu nanoparticles and Ag + And (3) carrying out spontaneous displacement reaction in the membrane hole to obtain the bimetallic Cu-Ag nano particle.
6. The method for preparing the silver-coated copper composite powder with the nano-polyhedral sphere structure, as claimed in claim 1, is characterized in that: the molar ratio of the copper sulfate to the polyvinylpyrrolidone is 1:4-5; the copper sulfate and AgNO 3 The molar ratio of (2) is 1-2:1, a step of; the NaBH 4 The concentration of the aqueous solution ranges from 50 to 100 mM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210340655.8A CN114905038B (en) | 2022-04-02 | 2022-04-02 | Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210340655.8A CN114905038B (en) | 2022-04-02 | 2022-04-02 | Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114905038A CN114905038A (en) | 2022-08-16 |
| CN114905038B true CN114905038B (en) | 2024-01-05 |
Family
ID=82762584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210340655.8A Active CN114905038B (en) | 2022-04-02 | 2022-04-02 | Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114905038B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-04-02 CN CN202210340655.8A patent/CN114905038B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114905038A (en) | 2022-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102176337B (en) | Composite conductive particles for anisotropic conductive film and preparation method | |
| US20040115340A1 (en) | Coated and magnetic particles and applications thereof | |
| Kao et al. | Electroless copper plating onto printed lines of nanosized silver seeds | |
| CN102328076A (en) | Preparation method of silver coated copper powder for electronic slurry | |
| CN103476199B (en) | Based on the printed circuit addition preparation method of copper self-catalysis and electroless copper | |
| CN107498064A (en) | A kind of preparation method of high temperature electric slurry ultra-fine copper galactic nucleus shell composite powder | |
| TWI423930B (en) | Nano metal solution, nanometal complex grains and manufacturing method of metal film | |
| CN110029382A (en) | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated | |
| CN102672168B (en) | Preparation method for core-shell structural nickel-silver bimetallic powder | |
| CN105063580A (en) | Preparation method of nickel-coated graphite powder for electroconductive rubber of electromagnetic shielding material | |
| CN104801709A (en) | Nickel-coated copper clad metal powder and preparation method and application thereof | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same | |
| CN104143385A (en) | Electroconductive copper slurry for grid electrodes of silicon solar cells and preparation method thereof | |
| CN114905038B (en) | Silver-coated copper composite powder with nano polyhedral sphere structure and preparation method thereof | |
| CN101320642B (en) | Production method of electric contact point | |
| Wang et al. | Functional metal powders: Design, properties, applications, and prospects | |
| CN113020587B (en) | Preparation method of silver-coated copper powder | |
| Liu et al. | Effects of Ag shell on electrical, thermal and mechanical properties of Cu@ Ag composite solder preforms by electromagnetic compaction for power electronics | |
| CN111570822A (en) | Nano silver powder and preparation method thereof | |
| CN114914011B (en) | Repairing type silver-coated copper powder and preparation method thereof, electronic paste and preparation method thereof | |
| CN111560192A (en) | Preparation method of high-dispersion stable conductive ink material | |
| CN113523649A (en) | Preparation method of composite soldering paste | |
| CN103894603A (en) | Method for preparing tinned copper through chemical reduction | |
| CN113814396A (en) | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof | |
| TWI653307B (en) | Method of fabricating conductive thick-film paste of base metal for achieving high conductivity |
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 |