CN116652181A - Silver-coated copper preparation method, silver-coated copper and electronic paste - Google Patents
Silver-coated copper preparation method, silver-coated copper and electronic paste Download PDFInfo
- Publication number
- CN116652181A CN116652181A CN202310563026.6A CN202310563026A CN116652181A CN 116652181 A CN116652181 A CN 116652181A CN 202310563026 A CN202310563026 A CN 202310563026A CN 116652181 A CN116652181 A CN 116652181A
- Authority
- CN
- China
- Prior art keywords
- silver
- coated copper
- copper
- preparation
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 91
- 239000004332 silver Substances 0.000 title claims abstract description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 238000005253 cladding Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009791 electrochemical migration reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a preparation method of silver-coated copper, which comprises the following steps: (1) Adding dilute sulfuric acid into copper powder, performing ultrasonic treatment, and cleaning; (2) Adding the copper powder obtained in the step (1) into water, stirring, adding a reducing agent, adjusting the pH value of the solution to 11+/-0.5, and then continuously stirring at 70+/-5 ℃; (3) And (3) dropwise adding an ammonia water solution of silver salt into the solution obtained in the step (2), and then reacting at 70+/-5 ℃ to obtain the silver-coated copper. The method has simple reaction steps, simple and convenient operation and easily controlled reaction conditions, and the prepared silver layer has good cladding compactness and uniformity and can effectively improve the oxidation resistance of silver-coated copper.
Description
Technical Field
The invention belongs to the technical field of electronic paste, and particularly relates to a preparation method of silver-coated copper, silver-coated copper and electronic paste.
Background
The electronic paste is a paste which is prepared by uniformly mixing solid powder and an organic solvent through three-roller rolling, is a base material for manufacturing thick film elements, and is widely applied to the fields of aviation, chemical industry, printing, construction and the like.
The conductive phase commonly used in traditional electronic paste is pure silver powder, but the conductive phase is expensive and is easy to electrochemically migrate. The metallic copper and the metallic silver have relatively similar conductivity, but the oxidation resistance and the conductivity of the copper are relatively poor; the introduction of the silver-coated copper can reduce the cost of a conductive phase in the slurry, has good oxidation resistance, conductivity and electrochemical migration resistance, and has important application value.
The traditional silver-coated copper preparation method is divided into a melting atomization method, a mechanical ball milling method, a displacement deposition method and a chemical reduction method, wherein the former two methods not only need an inert atmosphere, but also have complex process equipment; the displacement deposition method is that silver ions and copper undergo displacement reaction, and the reaction speed is difficult to control; the reduction method is usually to add a reducing agent such as ammonia water, ascorbic acid, formaldehyde, glucose, hydrazine hydrate and the like, and silver particles are generated by the reaction of silver coordination ions and the reducing agent to coat the surface of copper, but the reduction rate of silver is high, a uniformly distributed silver layer is difficult to obtain, and the problems of poor coating property, complex coating steps and the like exist.
Disclosure of Invention
Based on the above, the invention aims to provide the preparation method of the silver-coated copper, which has the advantages of simple operation, easily controlled reaction conditions, good compactness and uniformity of the prepared or silver coating, and can effectively improve the oxidation resistance of the silver-coated copper.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A method for preparing silver-coated copper, the method comprising the steps of: (1) Adding dilute sulfuric acid into copper powder, performing ultrasonic treatment, and cleaning; (2) Adding the copper powder obtained in the step (1) into water, stirring, adding a reducing agent, adjusting the pH value of the solution to 11+/-0.5, and then continuously stirring at 70+/-5 ℃; (3) And (3) dropwise adding an ammonia water solution of silver salt into the solution obtained in the step (2), and then reacting at 70+/-5 ℃ to obtain the silver-coated copper.
In some embodiments, the molar ratio of silver to copper powder in the silver salt is (0.15-1.1): 1; preferably, the molar ratio of silver to copper powder in the silver salt is (0.50-1): 1.
in some embodiments, the molar ratio of silver to reducing agent in the silver salt is (0.25-1.78): 1, a step of; and/or the molar ratio of silver to reducing agent in the silver salt is (0.45-1): 1.
in some embodiments, the dilute sulfuric acid of step (1) has a mass concentration of 5% to 10%.
In some embodiments, the sonication time of step (1) is from 1min to 30min.
In some embodiments, the reducing agent is selected from at least one of ascorbic acid, glucose; and/or the silver salt is at least one selected from silver nitrate and silver sulfate.
In some embodiments, the reaction time of step (3) is from 10 minutes to 30 minutes.
The invention also provides the silver-coated copper prepared by the preparation method.
The invention also provides application of the silver-coated copper prepared by the preparation method in preparation of electronic slurry.
The invention also provides an electronic paste, and the preparation raw material of the electronic paste comprises the silver-coated copper prepared by the preparation method.
The invention discloses a method for synthesizing silver-coated copper by one-step chemical synthesis, which comprises the steps of firstly stirring copper powder and a reducing agent at a specific temperature (the temperature is too high, the reduction speed of silver ions is higher, free silver particles are more formed, the temperature is too low, the reaction speed is slower, only part of silver is coated on the surface of copper) and under the condition of pH value, and then adding ammonia water solution of silver salt for reaction, so that the problems of poor coating property and uneven silver layer distribution in the preparation of silver-coated copper by the existing reduction method can be effectively solved.
The method has simple reaction steps, simple and convenient operation and easily controlled reaction conditions, and the prepared silver layer has good cladding compactness and uniformity and can effectively improve the oxidation resistance of silver-coated copper.
Drawings
FIG. 1 is an electron microscope image of copper and silver coated copper in example 1 of the present invention.
FIG. 2 is an electron microscope image of the silver-coated copper in example 2 of the present invention.
FIG. 3 is an electron microscope image of the silver-coated copper in example 3 of the present invention.
Fig. 4 is an electron microscopic view of the silver-coated copper of comparative example 1.
FIG. 5 is a TGA graph of silver-coated copper and copper samples prepared in examples and comparative examples of the present invention.
Detailed Description
The experimental methods of the present invention, in which specific conditions are not specified in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The various chemicals commonly used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
In the present invention, the term "plurality" means two or more. "and/or", describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate: a exists alone, A and B exist together, and B exists alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
The following description is made with reference to specific embodiments.
Example 1
The embodiment provides a preparation method of silver-coated copper, which comprises the following steps:
1. removing an oxide layer on the surface of copper powder: 1g of copper powder is weighed, 50mL of 10wt% dilute sulfuric acid is added, ultrasonic stirring is carried out for 10min, and oxide on the surface is washed by deionized water to be neutral;
2. copper powder suspension preparation: placing the pretreated copper powder into a beaker, adding 50mL of water, magnetically stirring for 10min at a stirring speed of 200r/min, simultaneously adding 50mL of ascorbic acid solution (containing 1.76g of ascorbic acid), adjusting the pH of the solution to be 11 by using 1M sodium hydroxide, and stirring for 10min at 70 ℃;
3. coating reaction: adding 20mL of ammonia water solution of silver nitrate (the silver nitrate content is 1.70 g), the dropping speed is 2mL/min, the reaction temperature is 70 ℃, and the reaction time is 20min, so as to obtain silver-coated copper powder;
4. cleaning silver-coated copper powder: washing the silver-coated copper for 6 times by using a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:4;
5. and (3) drying: and drying the cleaned silver-coated copper at 60 ℃ for 3 hours to obtain the silver-coated copper with the average particle size of 0.54 mu m.
FIG. 1 is an electron microscope image of copper and silver coated copper in example 1 of the present invention. As shown in fig. 2, TGA shows that the oxidation temperature of copper is 128 ℃, the oxidation temperature of silver-coated copper is 168 ℃, and the oxidation resistance of the prepared silver-coated copper is improved.
The structure of the silver-coated copper prepared in this example is shown in fig. 1.
Example 2
The embodiment provides a preparation method of silver-coated copper, which comprises the following steps:
1. removing an oxide layer on the surface of copper powder: 1.28g of copper powder is weighed, 50mL of 10wt% dilute sulfuric acid is added, ultrasonic stirring is carried out for 20min, and oxide on the surface is washed by deionized water until the solution is neutral;
2. copper powder suspension preparation: placing the pretreated copper powder in a beaker, adding 50mL of water, magnetically stirring for 10min at a stirring speed of 200r/min, simultaneously adding 50mL of ascorbic acid solution (containing 2.2g of ascorbic acid), adjusting the pH of the solution to be 11.5 by using 1M sodium hydroxide, and stirring for 10min at 75 ℃;
3. coating reaction: adding 20mL of ammonia water solution of silver nitrate (the silver nitrate content is 1.70 g), the dropping speed is 2mL/min, the reaction temperature is 75 ℃, and the reaction time is 25min, so as to obtain silver-coated copper powder;
4. cleaning silver-coated copper powder: washing the silver-coated copper for 6 times by using a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:4;
5. and (3) drying: and drying the cleaned silver-coated copper at 60 ℃ for 3 hours to obtain the silver-coated copper.
The structure of the silver-coated copper prepared in this example is shown in fig. 2.
Example 3
The embodiment provides a preparation method of silver-coated copper, which comprises the following steps:
1. removing an oxide layer on the surface of copper powder: weighing 0.73g of copper powder, adding 50mL of 10wt% dilute sulfuric acid, ultrasonically stirring for 30min, and washing oxide on the surface by deionized water to neutrality;
2. copper powder suspension preparation: placing the pretreated copper powder in a beaker, adding 50mL of water, magnetically stirring for 10min at a stirring speed of 200r/min, simultaneously adding 50mL of ascorbic acid solution (containing 3.91g of ascorbic acid), adjusting the pH of the solution to be 10.5 by using 1M sodium hydroxide, and stirring for 15min at 72 ℃;
3. coating reaction: adding 20mL of ammonia water solution of silver nitrate (the silver nitrate content is 1.70 g), the dropping speed is 2mL/min, the reaction temperature is 72 ℃, and the reaction time is 30min, so as to obtain silver-coated copper powder;
4. cleaning silver-coated copper powder: washing the silver-coated copper for 6 times by using a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:4;
5. and (3) drying: and drying the cleaned silver-coated copper at 60 ℃ for 3 hours to obtain the silver-coated copper.
The structure of the silver-coated copper prepared in this example is shown in fig. 3.
Comparative example 1
The comparative example provides a preparation method of silver-coated copper, which comprises the following steps:
1. 3.52g of ascorbic acid was weighed, 150mL of water was added, and after stirring to dissolve, the solution ph=11 was adjusted with 1M sodium hydroxide;
2. 15mL of copper ammonia solution (containing 2.49g of copper sulfate pentahydrate) is added into the solution at the speed of 2mL/min, the mixture is stirred for 20min at the temperature of 70 ℃, and then 20mL of ammonia water solution of silver nitrate (the silver nitrate content is 1.70 g) is added into the mixture at the same speed, and the reaction time is 30min, so that silver-coated copper powder is obtained;
3. cleaning silver-coated copper powder: washing the silver-coated copper for 6 times by using a mixed solution of ethanol and water, wherein the volume ratio of the ethanol to the water is 1:4;
4. and (3) drying: and drying the cleaned silver-coated copper at 60 ℃ for 3 hours to obtain the silver-coated copper.
The structure of the silver-coated copper obtained in this comparative example is shown in fig. 4.
The silver-coated copper prepared in the above examples and comparative examples was tested for silver-coated compactibility, dispersibility and oxidation temperature as follows:
(1) Silver coating compactness: and (5) SEM.
(2) Dispersibility: and (5) SEM.
(3) Oxidation temperature: TGA.
The test results are shown in table 1:
TABLE 1
The results show that the silver layer coating compactness and uniformity obtained by the preparation method disclosed by the invention (examples 1-3) are better than those of comparative example 1, and the oxidation resistance of the silver-coated copper can be correspondingly improved.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the silver-coated copper is characterized by comprising the following steps of: (1) Adding dilute sulfuric acid into copper powder, performing ultrasonic treatment, and cleaning; (2) Adding the copper powder obtained in the step (1) into water, stirring, adding a reducing agent, adjusting the pH value of the solution to 11+/-0.5, and then continuously stirring at 70+/-5 ℃; (3) And (3) dropwise adding an ammonia water solution of silver salt into the solution obtained in the step (2), and then reacting at 70+/-5 ℃ to obtain the silver-coated copper.
2. The method for producing silver-coated copper according to claim 1, wherein the molar ratio of silver to copper powder in the silver salt is (0.15 to 1.1): 1; preferably, the molar ratio of silver to copper powder in the silver salt is (0.50-1): 1.
3. the method of producing a silver-coated copper according to claim 1, wherein the molar ratio of silver to the reducing agent in the silver salt is (0.25 to 1.78): 1, a step of; and/or the molar ratio of silver to reducing agent in the silver salt is (0.45-1): 1.
4. the method for preparing silver-coated copper according to claim 1, wherein the mass concentration of the dilute sulfuric acid in the step (1) is 5% -10%.
5. The method of claim 1, wherein the ultrasonic treatment time in step (1) is 1 to 30 minutes.
6. The method according to claim 1, wherein the reducing agent is at least one selected from the group consisting of ascorbic acid and glucose; and/or the silver salt is at least one selected from silver nitrate and silver sulfate.
7. The method of claim 1, wherein the reaction time in step (3) is 10 to 30 minutes.
8. The silver-coated copper produced by the production method according to any one of claims 1 to 7.
9. Use of silver-coated copper prepared by the preparation method according to any one of claims 1 to 7 in the preparation of electronic paste.
10. An electronic paste, wherein the raw material for preparing the electronic paste comprises silver-coated copper prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310563026.6A CN116652181A (en) | 2023-05-18 | 2023-05-18 | Silver-coated copper preparation method, silver-coated copper and electronic paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310563026.6A CN116652181A (en) | 2023-05-18 | 2023-05-18 | Silver-coated copper preparation method, silver-coated copper and electronic paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116652181A true CN116652181A (en) | 2023-08-29 |
Family
ID=87719888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310563026.6A Pending CN116652181A (en) | 2023-05-18 | 2023-05-18 | Silver-coated copper preparation method, silver-coated copper and electronic paste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116652181A (en) |
-
2023
- 2023-05-18 CN CN202310563026.6A patent/CN116652181A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101789213B1 (en) | Method of Manufacturing Silver-Coated Copper Nano Wire Having Core-Shell Structure by Chemical Reduction Method | |
| WO2015194850A1 (en) | Silver-coated copper nanowire and preparation method therefor | |
| US5945158A (en) | Process for the production of silver coated particles | |
| CN113020587B (en) | Preparation method of silver-coated copper powder | |
| CN112570728A (en) | Flaky silver powder and preparation method and application thereof | |
| CN108326293B (en) | Method for producing silver-coated nickel powder | |
| CN110899722B (en) | Thin single crystal flake silver powder synthesized by chemical method and preparation method thereof | |
| CN112501598B (en) | Chemical nickel plating solution for aluminum substrate PCB circuit board and preparation method thereof | |
| CN109423637A (en) | A kind of preparation method of high conductive material | |
| CN111360246A (en) | Silver-coated copper powder with high coating rate and excellent quality and preparation method thereof | |
| CN115805318B (en) | High-index crystal face exposure type silver powder and preparation method and application thereof | |
| TWI583802B (en) | Conductive particles, a method for producing the same, a conductive resin composition containing the same, and a conductive coating | |
| JP2002180110A (en) | Method for manufacturing metallic colloidal solution | |
| CN114029499A (en) | Preparation method of ultralong nano silver wire material | |
| US7338686B2 (en) | Method for producing conductive particles | |
| JP2001011502A (en) | Copper powder, its manufacture, and electrical conductive paste using the same | |
| CN116652181A (en) | Silver-coated copper preparation method, silver-coated copper and electronic paste | |
| JP2003342621A (en) | Method for manufacturing copper powder and copper powder obtained thereby | |
| CN108213415B (en) | Production method of corrosion-resistant high-temperature-resistant silver-copper coated powder | |
| CN115233200A (en) | Antenna surface metallization plating solution and metallization method thereof | |
| JP2602495B2 (en) | Manufacturing method of nickel plating material | |
| KR20160099513A (en) | Method of Preapring Silver Coated Copper Nanowire | |
| WO2016112081A1 (en) | Silver coated copper flakes and methods of their manufacture | |
| CN112010572A (en) | Conductive glass fiber and preparation method thereof | |
| JP3858971B2 (en) | Electroless plating method for fine particles |
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 |