CN118080848A - Preparation method of superfine silver-coated copper powder for conductive paste - Google Patents
Preparation method of superfine silver-coated copper powder for conductive paste Download PDFInfo
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- CN118080848A CN118080848A CN202410196832.9A CN202410196832A CN118080848A CN 118080848 A CN118080848 A CN 118080848A CN 202410196832 A CN202410196832 A CN 202410196832A CN 118080848 A CN118080848 A CN 118080848A
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- conductive paste
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 53
- 239000004332 silver Substances 0.000 title claims abstract description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 238000004140 cleaning Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 44
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 36
- 239000003638 chemical reducing agent Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 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 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- -1 silver ions Chemical class 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 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 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 4
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 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 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 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
- 229960001031 glucose Drugs 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 3
- 239000010946 fine silver Substances 0.000 claims 3
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- 238000010405 reoxidation reaction Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical group [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000126 substance 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
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to the technical field of preparation methods of superfine silver-coated copper powder, in particular to a preparation method of superfine silver-coated copper powder for conductive paste. The method comprises the following steps: (1) alkali washing; (2) acid washing; (3) electroless silver plating. And cleaning and vacuum drying to obtain the silver-coated copper powder. Compared with the traditional silver plating under the air or inert gas atmosphere, the method adopts the hydrogen reducing atmosphere, can greatly reduce the possibility of reoxidation of the copper powder after pickling, and is favorable for the replacement reaction of copper and silver, so that active silver is uniformly distributed on the surface of the copper powder, the uniformity and compactness of the subsequent reduction silver plating are ensured, and the oxidation resistance of the silver-coated copper powder is improved.
Description
Technical Field
The invention relates to the technical field of preparation methods of superfine silver-coated copper powder, in particular to a preparation method of superfine silver-coated copper powder for conductive paste.
Background
The main electrode materials of the electronic components such as the printed circuit board, the capacitor, the filter, the carbon film potentiometer, the membrane switch and the like are silver powder conductive adhesive. With the increase of the amount of silver powder conductive paste, especially the demand for low-temperature paste for solar cells is rapidly increasing, in order to reduce the cost, the appearance of a new generation of conductive paste with high performance and low cost is expected. The silver-coated copper powder is used as a novel multifunctional powder material with a core-shell structure, combines the excellent characteristics of silver and copper, overcomes the defect of silver migration, and maintains the good conductivity, thermal stability and oxidation resistance of silver powder.
Most of the silver-coated copper powder is prepared by adopting a chemical replacement method and a chemical reduction method, but the prepared silver-coated copper powder has the problems of low oxidation resistance, loose plating layer, insufficient binding force and the like when being used in a high-temperature environment, and the technical problem that how to improve the oxidation resistance and the binding force of the silver-coated copper powder and control the cost is needed to be solved at present is urgent.
Chinese patent application No. 201710693443.7 is a preparation method of superfine copper-silver core-shell composite powder for medium-high temperature electronic paste, which is characterized in that copper powder is prepared by a liquid phase chemical reduction method, and silver-coated copper powder with good oxidation resistance is obtained by an electroless plating method after the copper powder is phosphated, but the process is complex, and the conductivity of the copper powder can be adversely affected after the copper powder is phosphated; the preparation method of the oxidation-resistant silver-coated copper powder disclosed in China patent application No. 201610721155.3 adopts a multi-plating process to obtain the silver-coated copper powder with excellent high-temperature oxidation resistance, and the preparation process is more complicated.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of superfine silver-coated copper powder for conductive paste.
The invention is realized by the following technical scheme: the preparation method of the superfine silver-coated copper powder for the conductive paste is characterized by comprising the following steps of:
(1) Alkali washing: ultrasonically cleaning organic matters on the surface of the copper powder by using an alkali solution with the concentration of 3% -10%, and then washing alkali solution remained on the surface of the copper powder by using deionized water to obtain clean copper powder;
(2) Acid washing: ultrasonically cleaning oxide on the surface of copper powder by using a dilute acid solution with the concentration of 3% -10%, and then washing off acid liquor remained on the surface of the copper powder by using deionized water to obtain cleaned copper powder;
(3) Electroless silver plating: placing the acid-washed copper powder into a mixed solution of a dispersing agent and a complexing agent, introducing hydrogen into a reaction container at the same time, enabling the whole reaction to be carried out in a reducing atmosphere, reducing the possibility of oxidation of the copper powder after acid washing, then starting to dropwise add a silver-ammonia solution for activation, then dropwise adding the silver-ammonia solution and a reducing agent at the same time until the reaction is complete, continuously dropwise adding the reducing agent after the dropwise adding of the silver-ammonia solution is finished, keeping stirring, filtering, cleaning, and vacuum drying to obtain the silver-coated copper powder when no residual silver ions exist in the solution.
Further, the copper powder has a particle size of 0.5 to 10 μm, and is spherical or irregularly shaped.
Further, the alkali solution adopts one or more of sodium hydroxide, potassium hydroxide, mixed solution of ammonia water and ammonium sulfate and mixed solution of sodium carbonate and sodium hydroxide.
Further, the acid solution adopts one or more of sulfuric acid and hydrochloric acid.
Further, the dispersing agent adopts one or more of polyvinylpyrrolidone, gum arabic, polyethylene glycol and polyvinyl alcohol, and the dosage of the dispersing agent is 0.5-5% of the mass of the copper powder.
Further, the complexing agent adopts one or more of disodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate and ethylenediamine tetraacetic acid, and the dosage of the complexing agent is 1-10% of the mass of the copper powder.
Further, the reducing agent adopts one or more of glucose, potassium sodium tartrate, formaldehyde, ascorbic acid, sodium hypophosphite and hydrazine hydrate, the concentration of the reducing agent is 10-100g/L, the dosage of the reducing agent is 20-50% of the mass of copper powder, and the titration speed of the reducing agent is 15-30ml/min.
Further, the concentration of the silver-ammonia solution is 10-50g/L, the addition amount of the silver-ammonia solution alkali is 1-20% of the mass of silver nitrate, and the titration speed of the silver-ammonia solution is 10-50ml/min.
The beneficial effects of the invention are as follows: compared with the traditional silver plating under the air or inert gas atmosphere, the method adopts the hydrogen reducing atmosphere, can greatly reduce the possibility of reoxidation of the copper powder after pickling, and is favorable for the replacement reaction of copper and silver, so that active silver is uniformly distributed on the surface of the copper powder, the uniformity and compactness of the subsequent reduction silver plating are ensured, and the oxidation resistance of the silver-coated copper powder is improved.
Detailed Description
In order to better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The invention provides a preparation method of superfine silver-coated copper powder for conductive paste, which comprises the following steps:
(1) Alkali washing: ultrasonically cleaning organic matters on the surface of the copper powder by using an alkali solution with the concentration of 3% -10%, and then washing alkali solution remained on the surface of the copper powder by using deionized water to obtain clean copper powder;
(2) Acid washing: ultrasonically cleaning oxide on the surface of copper powder by using a dilute acid solution with the concentration of 3% -10%, and then washing off acid liquor remained on the surface of the copper powder by using deionized water to obtain cleaned copper powder;
(3) Electroless silver plating: placing the acid-washed copper powder into a mixed solution of a dispersing agent and a complexing agent, introducing hydrogen into a reaction container at the same time, enabling the whole reaction to be carried out in a reducing atmosphere, reducing the possibility of oxidation of the copper powder after acid washing, then starting to dropwise add a silver-ammonia solution for activation, then dropwise adding the silver-ammonia solution and a reducing agent at the same time until the reaction is complete, continuously dropwise adding the reducing agent after the dropwise adding of the silver-ammonia solution is finished, keeping stirring, filtering, cleaning, and vacuum drying to obtain the silver-coated copper powder when no residual silver ions exist in the solution.
The alkali solution in the step (1) adopts one or more of sodium hydroxide, potassium hydroxide, mixed solution of ammonia water and ammonium sulfate and mixed solution of sodium carbonate and sodium hydroxide.
The acid solution in the step (2) adopts one or more of sulfuric acid and hydrochloric acid.
The dispersing agent in the step (3) adopts one or more of polyvinylpyrrolidone, gum arabic, polyethylene glycol and polyvinyl alcohol, and the dosage of the dispersing agent is 0.5-5% of the mass of the copper powder.
The complexing agent in the step (3) adopts one or more of disodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate and ethylenediamine tetraacetic acid, and the dosage of the complexing agent is 1-10% of the mass of the copper powder.
The reducing agent in the step (3) adopts one or more of glucose, potassium sodium tartrate, formaldehyde, ascorbic acid, sodium hypophosphite and hydrazine hydrate, the concentration of the reducing agent is 10-100g/L, the dosage of the reducing agent is 20-50% of the mass of copper powder, and the titration speed of the reducing agent is 15-30ml/min.
The concentration of the silver-ammonia solution in the step (3) is 10-50g/L, the alkali addition amount of the silver-ammonia solution is 1-20% of the mass of silver nitrate, and the titration speed of the silver-ammonia solution is 10-50ml/min.
The invention is further illustrated below with reference to specific examples.
Example 1
(1) Alkali washing: taking 50g of spherical copper powder with the average particle size of 3 microns, ultrasonically stirring the spherical copper powder in 200mL of sodium hydroxide solution with the concentration of 5% at room temperature for 30min, and washing the spherical copper powder with deionized water to be neutral;
(2) Acid washing: ultrasonically stirring the copper powder in 200mL sulfuric acid solution with the concentration of 3% at room temperature for 30min, and cleaning the copper powder with deionized water to be neutral;
(3) Preparing a reducing agent: taking 10 glucose, 25g of potassium sodium tartrate and 0.5L of deionized water, boiling for 5min, and cooling to room temperature for standby;
preparing silver ammonia solution: taking 20g of silver nitrate, adding 1g of sodium hydroxide, and then adding ammonia water until precipitation disappears to prepare a silver ammonia solution with the concentration of 25 g/L;
preparing a base solution: taking 1g of polyvinylpyrrolidone, 2g of disodium ethylenediamine tetraacetate and 0.6L of deionized water to prepare a base solution;
electroless silver plating: adding the copper powder subjected to acid washing into a base solution, simultaneously introducing hydrogen, stirring for 5min by ultrasonic, starting to titrate a silver-ammonia solution for 10min, then starting to dropwise add the silver-ammonia solution and a reducing agent solution simultaneously, wherein the dropwise adding speed of the silver-ammonia solution is 20ml/min, the dropwise adding speed of the reducing agent is 15 ml/min, continuing to dropwise add the reducing agent after the dropwise adding of the silver-ammonia solution is finished, keeping stirring, and carrying out suction filtration and cleaning until no silver ions remain in the solution;
(1) And (3) putting the cleaned solution into a vacuum drying oven for drying to obtain silver-coated copper powder, wherein the drying temperature is 80 ℃ and the drying time is 6 hours.
Example two
(1) Alkali washing: taking 50g of spherical copper powder with the average particle size of 2.5 microns, ultrasonically stirring the spherical copper powder in 200mL of sodium hydroxide solution with the concentration of 3% at room temperature for 30min, and washing the spherical copper powder with deionized water to be neutral;
(2) Acid washing: ultrasonically stirring the copper powder in 200mL sulfuric acid solution with the concentration of 5% at room temperature for 30min, and washing the copper powder with deionized water to be neutral;
(3) Preparing silver ammonia solution: taking 10g of silver nitrate, adding 1g of sodium hydroxide, and then adding ammonia water until precipitation disappears to prepare a silver ammonia solution with the concentration of 50 g/L;
preparing a base solution: taking 2g of polyvinylpyrrolidone, 5g of disodium ethylenediamine tetraacetate and 0.6L of deionized water to prepare a base solution;
Electroless silver plating: adding the copper powder subjected to acid washing into a base solution, simultaneously introducing hydrogen, stirring for 5min by ultrasonic, starting to titrate a silver-ammonia solution for 10min, then starting to dropwise add the silver-ammonia solution and a reducing agent solution simultaneously, wherein the dropwise adding speed of the silver-ammonia solution is 25ml/min, the dropwise adding speed of the reducing agent formaldehyde is 15 ml/min, continuing dropwise adding the reducing agent after the dropwise adding of the silver-ammonia solution is finished, keeping stirring, and carrying out suction filtration and cleaning until no silver ions remain in the solution;
(2) And (3) putting the cleaned solution into a vacuum drying oven for drying to obtain silver-coated copper powder, wherein the drying temperature is 100 ℃ and the drying time is 5 hours.
Example III
(1) Alkali washing: taking 100g of copper powder with an average particle size of 1 micron and in an irregular shape, ultrasonically stirring the copper powder in 200mL of sodium hydroxide solution with a concentration of 10% at room temperature for 30min, and washing the copper powder with deionized water to be neutral;
(2) Acid washing: ultrasonically stirring the copper powder in 200mL sulfuric acid solution with the concentration of 8% at room temperature for 30min, and washing the copper powder with deionized water to be neutral;
(3) Preparing silver ammonia solution: taking 30g of silver nitrate, adding 3g of sodium hydroxide, and then adding ammonia water until precipitation disappears to prepare a silver ammonia solution with the concentration of 35 g/L;
Preparing a base solution: taking 1g of polyvinylpyrrolidone, 8g of disodium ethylenediamine tetraacetate and 0.6L of deionized water to prepare a base solution;
Electroless silver plating: adding the copper powder subjected to acid washing into a base solution, simultaneously introducing hydrogen, stirring for 5min by ultrasonic, starting to titrate a silver-ammonia solution for 10min, then starting to dropwise add the silver-ammonia solution and a reducing agent solution simultaneously, wherein the dropping speed of the silver-ammonia solution is 40ml/min, the concentration of ascorbic acid of the reducing agent is 50g/L, the dropping speed is 25 ml/min, continuing to dropwise add the reducing agent after the dropping of the silver-ammonia solution is finished, keeping stirring, and carrying out suction filtration and cleaning until no silver ions remain in the solution;
(3) And (3) putting the cleaned solution into a vacuum drying oven for drying to obtain silver-coated copper powder, wherein the drying temperature is 80 ℃ and the drying time is 6 hours.
The technical features are known to those skilled in the art except the technical features described in the specification.
Claims (8)
1. The preparation method of the superfine silver-coated copper powder for the conductive paste is characterized by comprising the following steps of:
alkali washing: ultrasonically cleaning organic matters on the surface of the copper powder by using an alkali solution with the concentration of 3% -10%, and then washing alkali solution remained on the surface of the copper powder by using deionized water to obtain clean copper powder;
Acid washing: ultrasonically cleaning oxide on the surface of copper powder by using a dilute acid solution with the concentration of 3% -10%, and then washing off acid liquor remained on the surface of the copper powder by using deionized water to obtain cleaned copper powder;
Electroless silver plating: placing the acid-washed copper powder into a mixed solution of a dispersing agent and a complexing agent, introducing hydrogen into a reaction container at the same time, enabling the whole reaction to be carried out in a reducing atmosphere, then starting to dropwise add a silver-ammonia solution for activation, then dropwise adding the silver-ammonia solution and a reducing agent at the same time until the reaction is complete, continuing dropwise adding the reducing agent and keeping stirring after the dropwise adding of the silver-ammonia solution is completed, and obtaining the silver-coated copper powder after the solution is free of residual silver ions, carrying out suction filtration, cleaning and vacuum drying.
2. The method for preparing ultra-fine silver-coated copper powder for conductive paste according to claim 1, wherein the alkali solution is one or more of sodium hydroxide, potassium hydroxide, a mixed solution of ammonia water and ammonium sulfate, and a mixed solution of sodium carbonate and sodium hydroxide.
3. The method for preparing ultra-fine silver-coated copper powder for conductive paste according to claim 1, wherein the acid solution is one or more of sulfuric acid and hydrochloric acid.
4. The method for preparing the superfine silver-coated copper powder for the conductive paste according to claim 1, wherein the dispersing agent is one or more of polyvinylpyrrolidone, gum arabic, polyethylene glycol and polyvinyl alcohol, and the amount of the dispersing agent is 0.5-5% of the mass of the copper powder.
5. The preparation method of the superfine silver-coated copper powder for the conductive paste according to claim 1, wherein the complexing agent is one or more of disodium ethylenediamine tetraacetate, tetrasodium ethylenediamine tetraacetate and ethylenediamine tetraacetic acid, and the amount of the complexing agent is 1-10% of the mass of the copper powder.
6. The preparation method of the superfine silver-coated copper powder for the conductive paste according to claim 1, wherein the reducing agent is one or more of glucose, potassium sodium tartrate, formaldehyde, ascorbic acid, sodium hypophosphite and hydrazine hydrate, the concentration of the reducing agent is 10-100g/L, the consumption of the reducing agent is 20-50% of the mass of the copper powder, and the titration speed of the reducing agent is 15-30ml/min.
7. The method for preparing ultrafine silver-coated copper powder for conductive paste according to claim 1, wherein the concentration of the silver-ammonia solution is 10-50g/L, the alkali addition amount of the silver-ammonia solution is 1-20% of the mass of silver nitrate, and the titration speed of the silver-ammonia solution is 10-50ml/min.
8. The method for preparing ultra-fine silver-coated copper powder for conductive paste according to claim 1, wherein the particle size of the copper powder is 0.5 to 10 μm, spherical or irregularly shaped.
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