CN114433839B - Method for preparing silver-coated copper powder by electroplating - Google Patents
Method for preparing silver-coated copper powder by electroplating Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000009713 electroplating Methods 0.000 title claims abstract description 70
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 52
- 239000004332 silver Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 4
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 53
- 238000005406 washing Methods 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229940093932 potassium hydroxide Drugs 0.000 claims description 6
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000011664 nicotinic acid Substances 0.000 claims description 4
- 229960003512 nicotinic acid Drugs 0.000 claims description 4
- 235000001968 nicotinic acid Nutrition 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000005202 decontamination Methods 0.000 claims description 2
- 230000003588 decontaminative effect Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940093956 potassium carbonate Drugs 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- -1 silver ions Chemical class 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 230000005684 electric field Effects 0.000 abstract 1
- 239000013589 supplement Substances 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/20—Electroplating using ultrasonics, vibrations
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the field of composite materials, and particularly relates to a method for preparing silver-coated copper powder by electroplating, which comprises the following steps: s1, decontaminating and activating copper powder; s2, preparing an electroplating auxiliary agent and an electroplating solution; s3, flatly paving the activated copper powder at the bottom of the electroplating device, adding an electroplating auxiliary agent, electrifying, adding an electroplating solution, and starting electroplating; and S4, after electroplating is completed, filtering and cleaning to obtain silver-coated copper powder. Copper powder is uniformly dispersed on a conductive bearing sheet during electroplating, the conductive bearing sheet is connected with the negative electrode of a power supply, and meanwhile, an anode silver sheet is connected with the positive electrode of the power supply. And (3) slowly adding the electroplating solution and the silver-ammonia solution along the inner wall of the electroplating bath sequentially through a liquid adding pipeline. Because silver ions in the electroplating solution move to the copper powder under the action of an external electric field force, electrons are obtained on the surface of the copper powder and reduced into silver simple substances so as to be plated on the surface of the copper powder, and the anode silver sheet can continuously dissolve and supplement silver ions in the solution along with the deposition of the silver ions.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a method for preparing silver-coated copper powder by electroplating.
Background
With the continued development of electronic information technology and industry, the packaging of integrated circuits and the coupling of microelectronic devices has become an important issue to be addressed. In addition, due to the widespread use of computers, communication devices and network systems, problems such as electromagnetic interference and electromagnetic pollution are also increasing, and thus electromagnetic shielding technology has become one of the key technologies. While metal powder materials are essential functional materials in integrated circuit packaging, microelectronic device bonding and electromagnetic shielding technologies, powder materials are also becoming increasingly important to researchers.
Among common metal powder materials, silver powder is the most popular preparation material because of good electric conductivity and oxidation resistance, but the silver powder has high price, high manufacturing cost and silver migration problems to restrict the application of the silver powder. The conductivity of copper powder is close to that of silver powder, but copper powder is easily oxidized, and the conductivity of copper powder is reduced along with the easy oxidation. Thus, the preparation process and method of silver-coated copper powder are developed.
The electroless plating method is the most common method in the preparation of silver-coated copper powder, and the common method for preparing coated powder by using electroless plating is a direct replacement method. The direct replacement method is to directly utilize silver nitrate solution or silver ammonia solution to contact copper powder for reaction, and because the metal activity sequence of copper is in front of silver, the copper powder can directly reduce silver ions in the solution.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing silver-coated copper powder by electroplating, and the prepared silver-coated copper powder has good coating property, high conductivity and good oxidation resistance.
The invention provides the following technical scheme:
a method for preparing silver-coated copper powder by electroplating comprises the following steps:
s1, decontaminating and activating copper powder;
s2, preparing an electroplating auxiliary agent and an electroplating solution;
s3, flatly paving the activated copper powder at the bottom of the electroplating device, adding an electroplating auxiliary agent, electrifying, adding an electroplating solution, and starting electroplating;
and S4, after electroplating is completed, filtering and cleaning to obtain silver-coated copper powder.
Preferably, the decontamination activation adopts alkali washing or alkali washing followed by acid washing.
Preferably, the alkali in the alkali washing is at least one selected from sodium hydroxide, potassium hydroxide, ammonia water and sodium carbonate, and the acid in the acid washing is at least one selected from hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
Preferably, the electroplating auxiliary agent is an aqueous solution containing potassium carbonate, potassium hydroxide, nicotinic acid and ammonium acetate.
Preferably, the plating solution is a silver ammonia solution.
Preferably, in the step S3, before the energizing, a step of adding a dispersant is further included.
Preferably, the dispersing agent comprises an aqueous solution of at least one of polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol.
Preferably, in step S3, the electroplating device includes an electroplating tank and a power supply, a conductive carrier is arranged at the bottom of the electroplating tank, an anode silver sheet is further arranged in the electroplating tank, the power supply, the anode silver sheet and the conductive carrier form a closed loop, and the silver powder is tiled and covered on the conductive carrier.
Preferably, the conductive carrier sheet is selected from any one of graphite, silver and platinum.
Preferably, the plating bath is provided with ultrasonic equipment for carrying out ultrasonic treatment on the plating solution and the copper powder, and the power density of the ultrasonic equipment is 0.1-0.3W/cm 2 。
Preferably, the side wall of the electroplating bath is provided with a liquid adding port, and the liquid adding port is in a bent pipe shape, so that the impact on copper powder at the bottom of the electroplating bath can be effectively reduced, and other structures or methods capable of achieving similar effects can be adopted.
The beneficial effects of the invention are as follows:
1. because the grain size of copper powder is smaller, it is difficult to directly plate by adopting the conventional copper product plating method, and the copper metal activity sequence is in front of silver, and can directly reduce silver ions in the solution, so that the silver coated copper is generally plated by chemical plating.
2. The invention applies ultrasonic wave to copper powder to make copper powder particles slightly vibrate, thereby avoiding the generation of unplated areas due to the accumulation between copper powder.
3. The liquid feeding port is an elbow, so that the flow rate of the solution can be reduced, and the impact on copper powder at the bottom of the electroplating tank is reduced.
4. The invention adopts the cyanide-free electroplating solution, is more environment-friendly than cyanide-containing silver plating solution, and has no pollution to the environment.
5. The silver-coated copper powder obtained by the method does not agglomerate among particles, and is beneficial to adding in different systems.
Drawings
Fig. 1 is a surface SEM image of raw copper powder;
fig. 2 is a surface SEM image of the raw copper powder;
FIG. 3 is an SEM image of the silver-coated copper powder obtained in example 3;
FIG. 4 is an SEM image of the silver-coated copper powder obtained in example 3;
FIG. 5 is an XRD pattern of the silver-coated copper powder prepared in examples 1-9;
FIG. 6 is an EDS chart of the silver-coated copper powder prepared in example 3;
fig. 7 is a conductivity test chart of examples 1, 3 and comparative examples 1, 2, 3;
FIG. 8 is a thermogravimetric plot of example 3 and comparative example 1;
FIG. 9 is a schematic view of the structure of the electroplating apparatus.
The meaning of the labels in fig. 9 is as follows:
1-plating bath 2-power supply 3-conductive carrier 4-anode silver piece 5-ultrasonic equipment 6-liquid adding port 7-tiled copper powder 8-plating solution
Detailed Description
The present invention will be specifically described with reference to the following examples.
Example 1
(1) The surface of the anode silver flake was cleaned with absolute ethanol.
(2) Alkali washing: 1g of sodium hydroxide is weighed and dissolved in 500ml of deionized water to prepare a solution of 0.05mol/L, 3g of copper powder is weighed and poured into the solution, meanwhile, the solution is mechanically stirred for 10min, the supernatant is poured out after standing, and the activated copper powder is obtained after washing for a plurality of times by using the deionized water.
(3) The preparation of the dispersing agent solution, namely polyvinylpyrrolidone (PVP) is a common dispersing agent, and has high molecular water solubility, easy water compatibility, strong film forming property and dispersibility, and can prevent tiny particles from mutually aggregating to form a precipitate. 0.8g PVP was weighed and dissolved in 50ml deionized water at a concentration of 16g/L for use.
(4) Configuration of electroplating auxiliary agent: firstly, 8g of anhydrous potassium carbonate and 1.5g of potassium hydroxide are weighed and dissolved in a proper amount of deionized water, and then 10g of nicotinic acid and 6g of ammonium acetate are weighed and dissolved in the deionized water.
Preparing a plating solution: in order to reduce the displacement reaction of copper and silver ions, 4.5g of silver nitrate is weighed again, dissolved in a small amount of deionized water, and then ammonia water is slowly added dropwise, and the solution becomes turbid first and then becomes clear, and is added dropwise until the solution becomes clear.
The total amount of plating aid and plating solution was about 100ml, plating solution temperature 18.4 ℃, ph=8.89.
(5) Transferring the treated copper powder into an electroplating device, spreading the copper powder on a conductive carrier sheet (silver sheet), slowly pouring 50ml of PVP solution, slowly pouring an electroplating auxiliary agent, and pouring the electroplating solution after the copper powder is electrified. The voltage set point was 3.200V, the actual output value was 3.198V, and the plating time was 20 minutes.
(6) After the electroplating is finished, transferring the sample into a beaker, carrying out suction filtration, washing for a plurality of times by deionized water, and finally placing the sample into a vacuum drying oven for drying at the temperature of 80 ℃ for 12 hours. And (5) after drying, sieving by using a 300-mesh standard inspection sieve.
Example 2
(1) The surface of the anode silver flake was cleaned with absolute ethanol.
(2) Alkali washing: 1g of sodium hydroxide is weighed and dissolved in 500ml of deionized water to prepare a solution of 0.05mol/L, 3g of copper powder is weighed and poured into the solution, meanwhile, the solution is mechanically stirred for 10min, the supernatant is removed after standing, and the activated copper powder suspension is obtained after washing for a plurality of times by using the deionized water.
(3) Acid washing: preparing sulfuric acid solution with the mass fraction of 5%, pouring the copper powder subjected to alkaline washing treatment into 500ml of sulfuric acid solution, mechanically stirring for 10min, standing the solution, and washing the solution with deionized water for several times to obtain copper powder for later use.
(4) Preparation of dispersant solution 0.8g of polyvinyl alcohol (PVA) was weighed and dissolved in 50ml of deionized water at a concentration of 16g/L for use.
(5) Configuration of electroplating auxiliary agent: firstly, 8g of anhydrous potassium carbonate and 1.5g of potassium hydroxide are weighed and dissolved in a proper amount of deionized water, and then 10g of nicotinic acid and 6g of ammonium acetate are weighed and dissolved in the deionized water.
Preparing a plating solution: in order to reduce the displacement reaction of copper and silver ions, 4.5g of silver nitrate is weighed again, dissolved in a small amount of deionized water, and then ammonia water is slowly added dropwise, and the solution becomes turbid first and then becomes clear, and is added dropwise until the solution becomes clear.
The total amount of plating aid and plating solution was about 100ml, plating solution temperature 18.4 ℃, ph=8.89.
(6) Transferring the treated copper powder into an electroplating device, spreading the copper powder on a conductive carrier sheet (silver sheet), slowly pouring 50ml of PVA solution, slowly pouring an electroplating auxiliary agent, and pouring the electroplating solution after the copper powder is electrified. The voltage set point was 1.600V, the actual output value was 1.599V, and the plating time was 20 minutes.
(7) After the electroplating is finished, transferring the sample into a beaker, carrying out suction filtration, washing for a plurality of times by deionized water, and finally placing the sample into a vacuum drying oven for drying at the temperature of 80 ℃ for 12 hours. And (5) after drying, sieving by using a 300-mesh standard inspection sieve.
Example 3
The difference between this example and example 2 is that "the voltage set point in step (6) is 3.200V, the actual output value is 3.198V, and the plating time is 20 minutes. "
Example 4
The difference between this example and example 2 is that "the voltage set point in step (6) was 4.800V, the actual output value was 4.797V, and the plating time was 20 minutes. "
Example 5
This example differs from example 2 in that "the mass of silver nitrate weighed in step (5) is 3.5g; the voltage set value in the step (6) is 3.200V, the actual output value is 3.198V, and the electroplating time is 20 minutes. "
Example 6
This example differs from example 2 in that "the mass of silver nitrate weighed in step (5) is 5.5g; the voltage set value in the step (6) is 3.200V, the actual output value is 3.198V, and the electroplating time is 20 minutes. "
Example 7
The difference between this example and example 2 is that "the voltage set point in step (6) is 3.200V, the actual output value is 3.198V, and the plating time is 30 minutes. "
Example 8
The difference between this example and example 2 is that "the voltage set point in step (6) is 3.200V, the actual output value is 3.198V, and the plating time is 40 minutes. "
Example 9
This example differs from example 2 in that "the voltage set point in step (6) is 3.200V, the actual output value is 3.198V, the plating time is 20 minutes, and the ultrasonic apparatus with the frequency of 40kHz is turned on with the power density of 0.1-0.3W/cm 2 。”
Comparative example 1
(1) Taking 3g of raw copper powder without any treatment.
Comparative example 2
(1) 3g of raw copper powder was weighed.
(2) Alkali washing: 1g of sodium hydroxide is weighed and dissolved in 500ml of deionized water to prepare a solution with the concentration of 0.05mol/L, copper powder is poured into the solution, the solution is mechanically stirred for 10min, the supernatant is poured out after standing, and the solution is washed with deionized water for a plurality of times.
Comparative example 3
(1) 3g of raw copper powder was weighed.
(2) Alkali washing: 1g of sodium hydroxide is weighed and dissolved in 500ml of deionized water to prepare a solution with the concentration of 0.05mol/L, copper powder is poured into the solution, the solution is mechanically stirred for 10min, the supernatant is poured out after standing, and the solution is washed with deionized water for a plurality of times.
(3) Acid washing: preparing sulfuric acid solution with the mass fraction of 5%, pouring the copper powder subjected to alkaline washing treatment into 500ml of sulfuric acid solution, mechanically stirring for 10min, standing the solution, and washing the solution with deionized water for several times to obtain copper powder for later use.
Fig. 5 is the XRD analysis patterns of examples 1, 2, 3, 4, 5, 6, 7, 8, 9, which show that the characteristic peaks of the crystal planes of copper and silver are consistent, and no impurity peaks are generated.
Fig. 6 is an EDS spectrum analysis chart of example 3, wherein the oxygen element is caused by the upper surface of the conductive adhesive on the sample stage, the silver element is not seen on the surface of the copper powder, and the silver layer is almost completely coated.
The invention uses an intelligent powder resistivity tester, which is model FT-301B of the Ruiko Wei instruments Co., ltd. A cylinder in a sample state, the mass of the sample is 1.0g, the automatic pressure is 180KG, the constant pressure time is 5s, the diameter is 10mm,
the conductivity was measured as shown in fig. 7. a comparative example 1, b comparative example 2, c comparative example 3, d example 1, e example 3. As can be seen from comparison of b, d or c and e, the conductivity of the plating solution can be increased after the plating; the comparison of a, b and c shows that the conductivity of the raw copper powder can be improved by dilute acid treatment after alkali washing, the metal greasy dirt on the surface of the copper powder can be removed by alkali washing, and the surface oxide layer can be removed by acid washing, so that the acid-base treatment is used for electroplating at the same time, and the conductivity is optimal. The conductivities of the examples and comparative examples are shown in table 1.
TABLE 1
The oxidation resistance of the material is analyzed by a thermogravimetric analyzer, the air atmosphere, the flow rate of 100ml/min, the heating rate of 10 ℃/min and the test temperature of 30-700 ℃. As a result, as shown in FIG. 8, the raw copper powder was oxidized from about 180℃and the weight was increased, whereas the silver-coated copper powder prepared in example 3 was oxidized from 380℃and the oxidation resistance was improved.
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The method for preparing the silver-coated copper powder by electroplating is characterized by comprising the following steps of:
s1, decontaminating and activating copper powder;
s2, preparing an electroplating auxiliary agent and an electroplating solution;
s3, flatly paving the activated copper powder at the bottom of the electroplating device, adding an electroplating auxiliary agent, electrifying, adding an electroplating solution, and starting electroplating;
s4, after electroplating is completed, filtering and cleaning to obtain silver-coated copper powder;
in the step S3, the electroplating device comprises an electroplating bath (1) and a power supply (2), wherein a conductive carrier sheet (3) is arranged at the bottom of the electroplating bath, an anode silver sheet (4) is further arranged in the electroplating bath (1), the power supply (2), the anode silver sheet (4) and the conductive carrier sheet (3) form a closed loop, and copper powder is flatly paved and covered on the conductive carrier sheet (3);
an ultrasonic device (5) for carrying out ultrasonic treatment on the electroplating liquid and the copper powder is arranged on the electroplating bath (1);
the power density of the ultrasonic equipment (5) is 0.1-0.3W/cm 2 ；
The electroplating solution is silver ammonia solution.
2. The method for preparing silver-coated copper powder by electroplating according to claim 1, wherein the decontamination activation is alkali washing or alkali washing followed by acid washing.
3. The method for preparing silver-coated copper powder by electroplating according to claim 2, wherein the alkali in the alkaline washing is at least one of sodium hydroxide, potassium hydroxide, ammonia water and sodium carbonate, and the acid in the acid washing is at least one of hydrochloric acid, sulfuric acid, nitric acid and acetic acid.
4. The method for preparing silver-coated copper powder by electroplating according to claim 1, wherein the electroplating auxiliary agent is an aqueous solution containing potassium carbonate, potassium hydroxide, nicotinic acid and ammonium acetate.
5. The method for preparing silver-coated copper powder according to claim 1, wherein in the step S3, a step of adding a dispersing agent is further included before the energizing.
6. The method for preparing copper-clad silver powder by electroplating according to claim 5, wherein the dispersing agent comprises an aqueous solution of at least one of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol.
7. A method for preparing silver-coated copper powder by electroplating according to claim 1, wherein the conductive carrier sheet (3) is selected from any one of graphite, silver and platinum.
8. The method for preparing silver-coated copper powder by electroplating according to claim 1, wherein a liquid filling opening (6) is arranged on the side wall of the electroplating tank (1), and the liquid filling opening is in a bent pipe shape.
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