CN116197396A - Preparation method of submicron silver-coated copper powder - Google Patents
Preparation method of submicron silver-coated copper powder Download PDFInfo
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- CN116197396A CN116197396A CN202310091632.2A CN202310091632A CN116197396A CN 116197396 A CN116197396 A CN 116197396A CN 202310091632 A CN202310091632 A CN 202310091632A CN 116197396 A CN116197396 A CN 116197396A
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- 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
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- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- 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
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- 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
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a preparation method of submicron silver-coated copper powder, which comprises the following steps: s1, dissolving copper salt in a first solvent, and adding a complexing agent or chelating agent to complex or chelate copper ions; s2, adding a dispersing agent or a surfactant into the copper salt complexing solution prepared in the step S1, and then adding a reagent to adjust the pH value; s3, heating the copper salt complexing solution in the step S2, adding a first reducing agent, stirring for reaction, and performing post-treatment to obtain submicron copper powder; s4, mixing the second solvent and the second reducing agent with the copper powder prepared in the S3 to form turbid liquid, and adding silver salt solution or silver salt complexing solution to react to form silver shells on the copper surface; s5, post-treating the reaction solution of S4 to obtain silver-coated copper powder. The submicron silver-coated copper powder prepared by the preparation method has compact silver shell coating on the surface, good oxidation resistance, high vibration bulk density, small specific surface area and high conductivity, and the performance of the submicron silver-coated copper powder is higher than that of similar products on the market.
Description
Technical Field
The invention relates to a preparation method of silver-coated copper powder, in particular to a preparation method of submicron silver-coated copper powder.
Background
The silver-coated copper powder is used as a good high-conductivity filler, and can be added into paint (oil paint), adhesive (adhesive), printing ink, polymer slurry, plastic, rubber and the like to prepare various conductive and electromagnetic shielding products and the like, and the silver-coated copper powder can be widely applied to the fields of conductive and electromagnetic shielding of various industrial departments such as electronics, electromechanics, communication, printing, aerospace, weapons and the like.
The existing researches show that the morphology, stacking mode, vibration bulk density and the like of the conductive filler silver-coated copper powder have great influence on the conductivity of the material, and the higher the vibration bulk density is, the larger the mutual contact point surface is, the better the conductivity is; the normal distribution of the particle size of the powder is also beneficial to the accumulation of the powder, and the contact area and the high-temperature sintering performance are increased. The existing silver-coated copper powder cannot well and stably meet the requirements. The spherical conductive filler is in point contact, the contact area is increased due to the smooth surface, the conduction of charges is facilitated, and the conductivity is improved. The existing silver-coated copper powder cannot completely coat the copper surface, and has poor conductivity; after the exposed copper is oxidized for a long time, the conductivity is further reduced; however, to achieve better performance, the usage amount of silver must be increased, thereby leading to cost rise and limited economic benefit and losing production and use values. Expensive plating solutions and reagents are used for coating performance, which also increases the cost.
The general synthesis method of the silver-coated copper powder is physical deposition or chemical deposition, and the patent number CN102211185B is prepared by adopting a physical deposition method, but the silver content of the method is higher; the patent number CN113020587A is prepared by synthesis of liquid phase chemical reaction, and the particle size of the silver-coated copper powder prepared by the preparation method is larger.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a preparation method of submicron silver-coated copper powder. According to the method, when the copper powder is prepared, the complexing agent is added, so that the silver-coated copper powder is better in compactness on the premise of low silver content.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the submicron silver-coated copper powder comprises the following steps:
s1, preparing copper salt complexing solution: dissolving copper salt in a first solvent, and adding a complexing agent or chelating agent to complex or chelate copper ions;
s2, adjusting copper salt complexing solution: adding a dispersing agent or a surfactant into the copper salt complexing solution prepared in the step S1, and then adding a reagent to adjust the pH value;
s3, reduction of copper ions: heating the copper salt complexing solution in the step S2, adding a first reducing agent, stirring for reaction, and performing post-treatment to obtain submicron copper powder;
s4, silver plating of copper powder: mixing a second solvent, a second reducing agent and the copper powder prepared in the step S3 to form turbid liquid, adding silver salt solution or complexing solution of silver salt for reaction, and forming a silver shell on the surface of copper;
s5, silver coated copper powder treatment: and (5) post-treating the reaction solution of the step S4 to obtain silver-coated copper powder.
Further, in S1, the copper salt comprises one or more of copper nitrate, copper sulfate pentahydrate, copper acetate, copper chloride, basic copper carbonate, basic copper sulfate and copper carbonate, and the mass volume ratio of the copper salt to the first solvent is (70-250) g: (500-1000 ml).
Further, in S1, the complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylenepolyamine, N, N ' -dibenzylethylenediamine diacetic acid and esters thereof, and N, N, N ', N ' -tetra (2-hydroxypropyl) ethylenediamine, and the mass-volume ratio of the complexing agent or chelating agent to the first solvent is (10-250) g: (500-1000 ml);
the first solvent comprises one or more of water, methanol, ethanol, ethylene glycol, DMF, petroleum ether, n-butanol and n-hexane.
Further, in S2, the dispersant or surfactant includes one or more of polyvinyl alcohol, β -cyclodextrin, OP-10, oleic acid, linoleic acid, ricinoleic acid, polyvinylpyrrolidone, palmitic acid, stearic acid, polyethylene glycol, methyl oleate, dodecenyl succinic anhydride, lauric acid, and esters thereof; the mass volume ratio of the dispersant or the surfactant to the first solvent is (10-150) g: (500-1000 ml).
Further, in S2, the pH value is 2-10, and the reagent comprises one or more of potassium hydroxide, sodium citrate, ammonia water, concentrated sulfuric acid, concentrated nitric acid, acetic acid and concentrated hydrochloric acid.
Further, in S3, the reaction temperature is 20-100 ℃ and the reaction time is 10-60 min;
the first reducing agent comprises one or more of hydrazine hydrate, glyoxal, hydrazine sulfate, oxalic acid, ascorbic acid, sodium ascorbate, sodium hypophosphite, sodium borohydride, salicylic acid and VC ethyl ether, and the mass volume ratio of the reducing agent to the first solvent is (30-120) g: (500-1000 ml).
Further, in S4, the copper powder is subjected to pretreatment by a pretreatment liquid before silver plating of the copper powder, wherein the pretreatment liquid is an aqueous solution of a pretreatment reagent, and the pretreatment reagent comprises one or more of concentrated sulfuric acid, concentrated nitric acid, ammonia water, sodium hydroxide, ethylenediamine tetraacetic acid and salts thereof; the concentration of the aqueous solution of the pretreatment agent is 10-150 g/L; the pretreatment stirring time is 5-60 minutes.
Further, in S4, the reaction temperature is 0-60 ℃ and the reaction time is 10-120 minutes;
further, in S4, the second solvent comprises one or more of water, methanol, ethanol, glycol, isopropanol, DMF, petroleum ether, n-butanol and n-hexane, and the ratio of the mass of the copper powder to the volume of the second solvent is (10-250) g: (500-1000 ml).
The second reducing agent comprises one or more of sodium borohydride, hydrazine hydrate, hydrazine sulfate, oxalic acid, formaldehyde, glyoxal, ascorbic acid, sodium ascorbate, sodium hypophosphite and salicylic acid, and the mass volume ratio of the second reducing agent to the second solvent is (20-120 g): (500-1000 ml);
the silver salt solution is an aqueous solution of silver nitrate, and the mass concentration is 20-150 g/L;
the silver salt complexing solution is a solution obtained by adding a complexing agent or chelating agent into 20-150 g/L silver nitrate aqueous solution, wherein the used complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, N, N ' -dibenzylethylenediamine diacetic acid and esters thereof, and N, N, N ', N ' -tetra (2-hydroxypropyl) ethylenediamine, and the mol ratio of the complexing agent or chelating agent to the silver nitrate is 1-7:1.
Further, in S5, the post-treatment includes precipitation, filtration, washing, and drying of the reaction solution of S4, and the washing solvent includes one or more of water, methanol, ethanol, acetone, dichloromethane, and ethyl acetate.
The beneficial effects of the invention are as follows:
1) The preparation method comprises the steps of complexing the complexing agent and copper ions, reducing to obtain submicron copper powder, and replacing the copper powder with a silver ion complexing solution to obtain submicron silver-coated copper powder. The submicron silver-coated copper powder has compact silver shell coated on the surface, good oxidation resistance, high vibration bulk density, small specific surface area and high conductivity, and the performance of the submicron silver-coated copper powder is higher than that of similar products on the market.
2) The preparation method has the advantages of high reaction concentration, simple preparation route, mild synthesis condition, strong operability and lower cost, and is suitable for industrial mass production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of copper powder prepared in step S3 of example 1 of the present invention;
FIG. 2 is an XRD pattern of copper powder prepared in step S3 of example 1 of the present invention;
fig. 3 is an SEM image of the silver-coated copper powder prepared in example 1 of the present invention;
fig. 4 is an SEM image of the copper powder prepared in step S3 of example 2 of the present invention;
fig. 5 is an SEM image of the silver-coated copper powder prepared in example 2 of the present invention;
fig. 6 is an SEM image of the copper powder prepared in step S3 of example 3 of the present invention;
fig. 7 is an SEM image of the silver-coated copper powder prepared in example 3 of the present invention;
fig. 8 is an SEM image of the copper powder prepared in step S3 of example 4 of the present invention;
fig. 9 is an SEM image of the silver-coated copper powder prepared in example 4 of the present invention;
fig. 10 is a TEM image of the silver-coated copper powder prepared in example 4 of the present invention;
FIG. 11 is an SEM image of a commercially available silver-coated copper powder according to the present invention;
fig. 12 is another SEM image of commercially available silver-coated copper powder of the present invention;
fig. 13 is a flow chart of a method of preparing submicron silver-coated copper powder according to the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
The applicant finds that although reports of preparing submicron silver-coated copper by a chemical reduction method at home and abroad are not rare, most of the current products still have defects such as unstable thermodynamic properties, easy agglomeration, difficult opening by a mechanical method after the agglomeration, low tap density and unstable quality of amplified products, and the physical properties, functions and related applications of the submicron silver-coated copper powder are seriously influenced.
Aiming at the problems in the prior art, referring to fig. 5, the invention provides a preparation method of submicron silver-coated copper powder, which comprises the following steps:
s1, preparing copper salt complexing solution: copper salt is dissolved in a first solvent, and complexing agent or chelating agent is added to complex or chelate copper ions.
The copper salt comprises one or more of copper nitrate, copper sulfate pentahydrate, copper acetate, copper chloride, basic copper carbonate, basic copper sulfate and copper carbonate, and the mass volume ratio of the copper salt to the first solvent is (70-250) g: (500-1000 ml). Illustratively, the mass to volume ratio of copper salt to first solvent is 70g:1000ml;250g:500ml;100g:700ml;200g:900ml.
The complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, N, N ' -dibenzylethylenediamine diacetic acid and esters thereof, and N, N, N ', N ' -tetra (2-hydroxypropyl) ethylenediamine, and the mass volume ratio of the complexing agent or chelating agent to the first solvent is (10-250) g: (500-1000 ml); illustratively, the mass to volume ratio of complexing or chelating agent to first solvent is 10g:500ml;100g:500ml;200g:800ml;250g:1000ml.
The first solvent comprises one or more of water, methanol, ethanol, ethylene glycol, DMF, petroleum ether, n-butanol and n-hexane.
S2, adjusting copper salt complexing solution: adding a dispersing agent or a surfactant into the copper salt complexing solution prepared in the step S1, and adding a reagent to adjust the pH value to 2-10, wherein the reagent comprises one or more of potassium hydroxide, sodium citrate, ammonia water, concentrated sulfuric acid, concentrated nitric acid, acetic acid and concentrated hydrochloric acid. Illustratively, the pH is 2, 4, 6, 8, 10.
The dispersing agent or surfactant comprises one or more of polyvinyl alcohol, beta-cyclodextrin, OP-10, oleic acid, linoleic acid, ricinoleic acid, polyvinylpyrrolidone, palmitic acid, stearic acid, polyethylene glycol, methyl oleate, dodecenyl succinic anhydride, lauric acid and esters thereof; the mass volume ratio of the dispersant or the surfactant to the first solvent is (10-150) g: (500-1000 ml). Illustratively, the mass to volume ratio of dispersant or surfactant to first solvent is 10g:500ml;100g:500ml;150g:500ml;10g:1000ml;100g:750ml;150g:1000ml.
S3, reduction of copper ions: heating the copper salt complexing solution in the step S2, adding a first reducing agent, stirring and reacting at 20-100 ℃ for 10-60 min; post-processing to obtain submicron copper powder;
the first reducing agent comprises one or more of hydrazine hydrate, glyoxal, hydrazine sulfate, oxalic acid, ascorbic acid, sodium ascorbate, sodium hypophosphite, sodium borohydride, salicylic acid and VC ethyl ether, and the mass volume ratio of the first reducing agent to the first solvent is (30-120) g: (500-1000 ml). Illustratively, the mass to volume ratio of the first reducing agent to the first solvent is 30g:500ml;80g:500ml;120g:500ml;30g:1000ml;100g:750ml;120g:1000ml.
S4, silver plating of copper powder: pretreatment is carried out on copper powder by using pretreatment liquid before silver plating of the copper powder, wherein the pretreatment liquid is aqueous solution of pretreatment reagent, and the pretreatment reagent comprises one or more of concentrated sulfuric acid, concentrated nitric acid, ammonia water, sodium hydroxide, ethylenediamine tetraacetic acid and salts thereof; the concentration of the aqueous solution of the pretreatment agent is 10-150 g/L; the pretreatment stirring time is 5-60 minutes. Illustratively, the aqueous solution of the pretreatment agent has a concentration of 10g/L, 50g/L, 100g/L, 150g/L.
Mixing the second solvent, the second reducing agent and the copper powder prepared in the step S3 to form turbid liquid, and adding silver salt solution or silver salt complexing solution for reduction reaction at the temperature of 0-60 ℃ for 10-120 minutes. Illustratively, the reaction temperature is 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃; the reaction time was 10 minutes, 30 minutes, 50 minutes, 80 minutes, 100 minutes, 120 minutes.
The second solvent comprises one or more of water, methanol, ethanol, glycol, isopropanol, DMF, petroleum ether, n-butanol and n-hexane, and the ratio of the mass of the copper powder to the volume of the second solvent is (10-250) g: (500-1000 ml). Illustratively, the ratio of copper powder mass to second solvent volume is 10g:500ml;100g:500ml;250g:500ml;10g:750ml;10g:1000ml.
The second reducing agent comprises one or more of sodium borohydride, hydrazine hydrate, hydrazine sulfate, oxalic acid, formaldehyde, glyoxal, ascorbic acid, sodium ascorbate, sodium hypophosphite and salicylic acid, and the mass volume ratio of the second reducing agent to the second solvent is (20-120 g): (500-1000 ml). Illustratively, the mass to volume ratio of the second reducing agent to the second solvent is 20g:500ml;80g:500ml;120g:500ml;120g:750ml;120g:1000ml.
The silver salt solution is an aqueous solution of silver nitrate, and the mass concentration is 20-150 g/L. Exemplary silver salt solutions have a mass concentration of 20g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L.
The silver salt complexing solution is a solution obtained by adding complexing agent or chelating agent into 20-150 g/L silver nitrate aqueous solution, wherein the used complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, N, N ' -dibenzylethylenediamine diacetic acid and esters thereof, and N, N, N ', N ' -tetra (2-hydroxypropyl) ethylenediamine, and the mol ratio of the complexing agent or chelating agent to the silver nitrate is 1-7:1. Illustratively, the molar ratio of complexing or chelating agent to silver nitrate is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1.
S5, silver coated copper powder treatment: and (5) post-treating the reaction solution of the step S4 to obtain silver-coated copper powder.
The post-treatment comprises the steps of precipitating, filtering and cleaning the reaction solution of the S4, and drying, wherein the cleaning solvent comprises one or more of water, methanol, ethanol, acetone, methylene dichloride and ethyl acetate.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1
S1, preparing copper salt complexing solution: 200g of copper nitrate is taken and dissolved in 750ml of deionized water, 20g of ethylenediamine is added into the solution, and the mixture is fully mixed;
s2, adjusting copper salt complexing solution: 50g of polyvinyl alcohol was added to the prepared copper salt complex solution, and stirred to be sufficiently dissolved, and then the pH of the solution was adjusted to 9 using potassium hydroxide and dilute sulfuric acid, where the dilute sulfuric acid was obtained by diluting concentrated sulfuric acid with water.
S3, reduction of copper ions: heating and maintaining the adjusted copper salt complexing solution at 50 ℃, adding 40g of hydrazine hydrate while stirring by a stirring paddle, stopping heating and stirring after reacting for 20min, and obtaining about 65g of copper powder after precipitation, filtration, washing by deionized water and drying;
s4, copper powder pretreatment: dissolving 15g of concentrated sulfuric acid in 500ml of deionized water, preparing to obtain a pretreatment solution, ultrasonically stirring 65g of copper powder obtained in the step S3 in the pretreatment solution for 30 minutes, removing a surface oxide layer, and then filtering to remove the pretreatment solution;
silver plating of copper powder: dispersing the pretreated activated copper powder in 1L of deionized water, adding 60g of sodium borohydride while stirring, keeping stirring to form a uniform suspension, then adding 100mL of 130g/L silver nitrate aqueous solution into the suspension, keeping stirring, and reacting for 120 minutes at 25 ℃;
6. silver coated copper powder treatment: after the silver plating reaction is finished, the reaction solution is removed by precipitation and filtration, the precipitate is washed by deionized water, and the precipitate is dried in a 60 ℃ oven for 12 hours, so that about 70g of dried silver-coated copper powder is obtained.
Example 2
S1, preparing copper salt complexing solution: 2.5kg of copper sulfate pentahydrate is taken and dissolved in 10L of deionized water, 200g of trisodium ethylenediamine tetraacetate is added into the solution, and the solution is fully mixed;
s2, adjusting copper salt complexing solution: 600g of polyvinylpyrrolidone K30 was added to the prepared copper salt complex solution, stirred to be sufficiently dissolved, and then the pH of the solution was adjusted to 8 using sodium hydroxide and dilute sulfuric acid, where the dilute sulfuric acid was obtained by diluting concentrated sulfuric acid with water.
S3, reduction of copper ions: heating and maintaining the adjusted copper salt complexing solution at 50 ℃, adding 600g of glyoxal while stirring by a stirring paddle, stopping heating and stirring after reacting for 30min, precipitating, filtering, washing by deionized water, and drying to obtain about 630g of copper powder;
s4, copper powder pretreatment: dissolving 150g of concentrated sulfuric acid in 5L of deionized water, preparing to obtain a pretreatment solution, ultrasonically stirring 630g of copper powder obtained in the step 3 in the pretreatment solution for 30 minutes, removing a surface oxide layer, and then filtering to remove the pretreatment solution;
silver plating of copper powder: dispersing activated copper powder after pretreatment in 4L of deionized water, adding 500g of sodium ascorbate while stirring, keeping stirring to form a uniform suspension, then adding 1L of silver nitrate complexing aqueous solution with the concentration of 125g/L into the suspension, using ammonia water as a complexing agent, wherein the molar ratio of the ammonia content in the ammonia water to the silver nitrate in the solution is 1-1.2:1, keeping stirring, and reacting for 60 minutes at 25 ℃;
s5, silver coated copper powder treatment: after the silver plating reaction is finished, the reaction solution is removed by precipitation and filtration, the precipitate is washed by deionized water, and the precipitate is dried in a 60 ℃ oven for 3 hours, so that about 700g of dried silver-coated copper powder is obtained.
Example 3
S1, preparing copper salt complexing solution: 2.5kg of copper sulfate pentahydrate is taken and dissolved in 10L of deionized water, 200g of trisodium ethylenediamine tetraacetate is added into the solution, and the solution is fully mixed;
s2, adjusting copper salt complexing solution: adding 600g of polyvinylpyrrolidone K30 into the prepared copper salt complexing solution, stirring for full dissolution, and adjusting the pH value of the solution to 11 by using sodium hydroxide solution
S3, reduction of copper ions: heating and maintaining the adjusted copper salt complexing solution at 50 ℃, adding 600g of glyoxal while stirring by a stirring paddle, stopping heating and stirring after reacting for 30min, precipitating, filtering, washing by deionized water, and drying to obtain about 630g of copper powder;
s4, copper powder pretreatment: weighing 150g of ammonia water in 5L of deionized water, preparing a pretreatment solution, ultrasonically stirring 630g of copper powder obtained in the step 3 in the pretreatment solution for 30 minutes, removing a surface oxide layer, and filtering to remove the pretreatment solution;
silver plating of copper powder: dispersing activated copper powder after pretreatment in 4L of deisopropanol, adding 500g of sodium ascorbate while stirring, keeping stirring to form a uniform suspension, then adding 1L of silver ammonia water solution with the concentration of 125g/L into the suspension, wherein the complexing agent is ethylenediamine, the molar ratio of the ammonia content in the solution to the silver nitrate in the solution is 1-1.2:1, keeping stirring, and reacting for 60 minutes at 25 ℃;
s5, silver coated copper powder treatment: after the silver plating reaction is finished, the reaction solution is removed by precipitation and filtration, the precipitate is washed by deionized water, and the precipitate is dried in a 60 ℃ oven for 6 hours, so that about 700g of dried silver-coated copper powder is obtained.
Example 4
S1, preparing copper salt complexing solution: 2.5kg of copper sulfate pentahydrate is taken and dissolved in 10L of deionized water, 900g of sodium citrate is added into the solution, and the solution is fully mixed;
s2, adjusting copper salt complexing solution: 600g of polyvinylpyrrolidone K30 is added into the prepared copper salt complexing solution, and the mixture is stirred and fully dissolved;
s3, reduction of copper ions: heating and maintaining the adjusted copper salt complexing solution at 70 ℃, adding 1.2kg of sodium hypophosphite while stirring by a stirring paddle, stopping heating and stirring after reacting for 30min, and obtaining about 630g of copper powder after precipitation, filtration, washing by deionized water and drying;
s4, copper powder pretreatment: 300g of sodium hydroxide is weighed and dissolved in 5L of deionized water, a pretreatment solution is prepared, 630g of copper powder obtained in the step S3 is ultrasonically stirred in the pretreatment solution for 30 minutes, a surface oxide layer is removed, and then the pretreatment solution is filtered and removed;
silver plating of copper powder: dispersing activated copper powder after pretreatment in 4L of n-butanol, adding 500g of sodium ascorbate while stirring, keeping stirring to form a uniform suspension, then adding 1L of aqueous silver-amine solution with the concentration of 125g/L into the suspension, using ammonia water as a complexing agent, wherein the molar ratio of the ammonia content in the ammonia water to the silver nitrate in the solution is 1-1.2:1, keeping stirring, and reacting for 60 minutes at 25 ℃;
s5, silver coated copper powder treatment: after the silver plating reaction is finished, the reaction solution is removed by precipitation and filtration, the precipitate is washed by deionized water, and the precipitate is dried in a 60 ℃ oven for 9 hours, so that about 700g of dried silver-coated copper powder is obtained.
Example 5
Examples 1-4 and commercial silver-coated copper powder were tested, wherein the commercial silver-coated copper powder was similar in morphology and higher in silver content to the silver-coated copper powder prepared in examples 1-4, and the test performance data were as follows:
according to the comparison of the electric conductivity of the powder after high-temperature oxidation, the compactness of the self-made silver-coated copper is superior to that of the commercial silver-coated copper powder, wherein the commercial silver-coated copper powder is purchased from Suzhou crystal silver new material Co., ltd, and the data in the table and the attached figures 1-4 show that: the submicron silver-coated copper powder obtained by the method has compact surface-coated silver shell, good oxidation resistance, high vibration bulk density which is up to 5.1g/cm < 3 >, low resistivity and high conductivity, and the performances of the submicron silver-coated copper powder are higher than those of similar products on the market.
Wherein:
the conductivity of the powder at normal temperature is detected by an ST 2742B-type automatic powder resistivity tester;
the conductivity of the powder after high-temperature oxidation is that firstly, the powder is heated in a drying oven at 180 ℃ for 1h, then the conductivity of the powder after high-temperature oxidation is detected and then cooled down, and the powder is detected by an ST2742B type automatic powder resistivity tester;
the vibrating tap density is detected by a tap density tester with the model BT-313;
silver content detection data were as follows:
the detecting instrument is as follows: ICP-OES Aglient 5110
Wherein:
m: when analyzing the sample, the mass of the sample taken, in g, is recorded by an analytical balance, corresponding to column B data in the following table
V 0 : after digestion of the sample, the volume of the constant volume, in mL, corresponds to the data in column C of the following table;
f, dilution times, corresponding to the data of the column F in the following table;
C o : testing the concentration of the solution element in mg/L, wherein the data are obtained by instrument testing;
C 1 : element concentration of the stock solution of the sample digestion solution, wherein the unit is mg/L, and C1 (mg/L) =CO (mg/L) f corresponds to the data in the column G in the following table;
cx, final test results of the measured elements, unit mg/kg. Calculated from the above equation 1, corresponds to the H column data in the following table;
w (%) the final test results of the measured elements, expressed in percent, were calculated from the above equation 2 and correspond to the data in column I of the following table.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the submicron silver-coated copper powder is characterized by comprising the following steps of:
s1, preparing copper salt complexing solution: dissolving copper salt in a first solvent, and adding a complexing agent or chelating agent to complex or chelate copper ions;
s2, adjusting copper salt complexing solution: adding a dispersing agent or a surfactant into the copper salt complexing solution prepared in the step S1, and then adding a reagent to adjust the pH value;
s3, reduction of copper ions: heating the copper salt complexing solution in the step S2, adding a first reducing agent, stirring for reaction, and performing post-treatment on the reaction solution to obtain submicron copper powder;
s4, silver plating of copper powder: mixing a second solvent, a second reducing agent and the copper powder prepared in the step S3 to form turbid liquid, adding silver salt solution or complexing solution of silver salt for reaction, and forming a silver shell on the surface of copper;
s5, silver coated copper powder treatment: and (5) post-treating the reaction solution of the step S4 to obtain silver-coated copper powder.
2. The preparation method of submicron silver-coated copper powder according to claim 1, wherein in S1, the copper salt comprises one or more of copper nitrate, copper sulfate pentahydrate, copper acetate, copper chloride, basic copper carbonate, basic copper sulfate and copper carbonate, and the mass-volume ratio of the copper salt to the first solvent is (70-250) g: (500-1000 ml).
3. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S1, the complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, N '-dibenzylethylenediamine diacetic acid and esters thereof, and N, N' -tetra (2-hydroxypropyl) ethylene, and the mass-volume ratio of the complexing agent or chelating agent to the first solvent is (10-250) g: (500-1000 ml);
the first solvent comprises one or more of water, methanol, ethanol, ethylene glycol, DMF, petroleum ether, n-butanol and n-hexane.
4. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S2, the dispersant or the surfactant comprises one or more of polyvinyl alcohol, β -cyclodextrin, OP-10, oleic acid, linoleic acid, ricinoleic acid, polyvinylpyrrolidone, palmitic acid, stearic acid, polyethylene glycol, methyl oleate, dodecenyl succinic anhydride, lauric acid and esters thereof; the mass volume ratio of the dispersant or the surfactant to the first solvent is (10-150) g: (500-1000 ml).
5. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S2, the pH value is 2-10, and the reagent comprises one or more of potassium hydroxide, sodium citrate, ammonia water, concentrated sulfuric acid, concentrated nitric acid, acetic acid, and concentrated hydrochloric acid.
6. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S3, the reaction temperature is 20-100 ℃ and the reaction time is 10-60 min;
the first reducing agent comprises one or more of hydrazine hydrate, glyoxal, hydrazine sulfate, oxalic acid, ascorbic acid, sodium ascorbate, sodium hypophosphite, sodium borohydride, salicylic acid and VC ethyl ether, and the mass volume ratio of the reducing agent to the first solvent is (30-120) g: (500-1000 ml).
7. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S4, the copper powder prepared in S3 is pretreated with a pretreatment liquid before silver plating of the copper powder, the pretreatment liquid is an aqueous solution of a pretreatment reagent, and the pretreatment reagent comprises one or more of concentrated sulfuric acid, concentrated nitric acid, ammonia water, sodium hydroxide, ethylenediamine tetraacetic acid and salts thereof; the concentration of the aqueous solution of the pretreatment agent is 10-150 g/L; the pretreatment stirring time is 5-60 minutes.
8. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S4, the reaction temperature is 0-60 ℃ and the reaction time is 10-120 minutes.
9. The preparation method of submicron silver-coated copper powder according to claim 1, wherein in S4, the second solvent comprises one or more of water, methanol, ethanol, ethylene glycol, isopropanol, DMF, petroleum ether, n-butanol and n-hexane, and the ratio of the mass of copper powder to the volume of the second solvent is (10-250) g: (500-1000 ml);
the second reducing agent comprises one or more of sodium borohydride, hydrazine hydrate, hydrazine sulfate, oxalic acid, formaldehyde, glyoxal, ascorbic acid, sodium ascorbate, sodium hypophosphite and salicylic acid, and the mass volume ratio of the second reducing agent to the second solvent is (20-120 g): (500-1000 ml);
the silver salt solution is an aqueous solution of silver nitrate, and the mass concentration is 20-150 g/L;
the silver salt complexing solution is a solution obtained by adding a complexing agent or chelating agent into 20-150 g/L silver nitrate aqueous solution, wherein the used complexing agent or chelating agent comprises one or more of ethylenediamine, ammonia water, citric acid and salts thereof, tartaric acid and salts thereof, ethylenediamine tetraacetic acid and salts thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine, N, N ' -dibenzylethylenediamine diacetic acid and esters thereof, and N, N, N ', N ' -tetra (2-hydroxypropyl) ethylenediamine, and the mol ratio of the complexing agent or chelating agent to the silver nitrate is 1-7:1.
10. The method for preparing submicron silver-coated copper powder according to claim 1, wherein in S5, the post-treatment comprises the steps of precipitating, filtering, cleaning and drying the reaction solution of S4, and the cleaning solvent comprises one or more of water, methanol, ethanol, acetone, methylene dichloride and ethyl acetate.
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