CN102950283A - Preparation method for superfine silver plating copper powder used for electronic paste - Google Patents
Preparation method for superfine silver plating copper powder used for electronic paste Download PDFInfo
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- CN102950283A CN102950283A CN2012104378161A CN201210437816A CN102950283A CN 102950283 A CN102950283 A CN 102950283A CN 2012104378161 A CN2012104378161 A CN 2012104378161A CN 201210437816 A CN201210437816 A CN 201210437816A CN 102950283 A CN102950283 A CN 102950283A
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Abstract
The invention discloses a preparation method for superfine silver plating copper powder used for electronic paste, and belongs to the technical field of functional powder. The preparation method solves the problem that the silver plating copper powder used for the electronic paste can not be prepared in the prior art. The preparation method comprises the following steps of: (1) after superfine copper powder is subjected to surface treatment, preparing copper powder to be plated; (2) adding dispersing agent, additive and reducing agent into deionized water, adding the copper powder to be plated, and regulating a pH (potential of hydrogen) value to 12-14 to obtain mixture to be plated; (3) adding silver nitrate into the deionized water and amine complexing agent to obtain silver amide solution; (4) adding the silver amide solution into the mixture to be plated to obtain the silver plating copper powder; (5) washing the silver plating copper powder with the deionized water to serve as the copper powder to be plated, entering steps (2) to (4) for silver plating circulation to obtain secondary silver plating copper powder; and (6) putting the secondary silver plating copper powder into organic solution, carrying out suction filtration, dewatering and drying to obtain the superfine silver plating copper powder. The preparation method has the advantages of simple technology, stable technology and high silver plating efficiency, and the product can be used as electronic slurry.
Description
Technical field
The invention belongs to the function powder material preparing technical field, relate to a kind of preparation method of superfine cupper powder.
Background technology
Develop rapidly along with science and technology, electronic product more and more is tending towards miniaturization, highly integrated, the application of electric slurry is more and more extensive, and silver powder is as the optimal conductive filler of electric slurry, its consumption also increases thereupon, but under the effect of DC voltage, transport phenomena easily occurs and causes short circuit in silver, this just becomes electronic product march toward miniaturization, highly integrated a great problem, and silver-colored price is higher, especially nearly 2 years, silver-colored valency was advanced by leaps and bounds, is remained high, and this makes the substitute of a kind of silver of a lot of field active demands.And copper powder low price (only be silver-colored price 1/100), ability of resisting to migration is much higher than silver, and (specific insulation is close with silver: ρ to have good electric conductivity
ν (Cu)=1.75 * 10
-8Ω m, ρ
ν (Ag)=1.60 * 10
-8Ω m), thereby be used widely, superfine cupper powder makes it be widely used in the fields such as electronics, catalyst because its larger specific area, higher apparent activation energy have more excellent properties.But copper powder is easily oxidized in preparation and application process, and superfine cupper powder is easier to be oxidized.So at superfine cupper powder plated surface last layer silver, can improve like this oxidation resistance of copper powder, the premium properties that can keep again superfine cupper powder, the excellent properties of comprehensive two kinds of metal materials, form a kind of new composite, its each performance and silver are more approaching, even can be fully alternative in certain fields, thereby Silver Coated Copper Powders will have very vast potential for future development.
Patent of invention [US19910731313] has proposed a kind of substep and has added the method that complexing agent prepares silver-plated copper powder, and the silver-plated copper powder of preparation has good non-oxidizability, stability and good electric conductivity.Application for a patent for invention [CN101709461A] proposes to utilize at the strong simple substance palladium of Copper Powder Surface pre-value catalytic activity and forms catalytic center, in silver plating liquid, promote the silver ion reduction deposition, hinder cuprammonium and cooperate ion in the effect of copper adsorption, thereby obtain the continuously silver coating of covering.Patent of invention [CN101294281B] discloses a kind of preparation method of silver-plated copper powder for low-temperature slurry, proposes to add polynary complexing agent complexed acidic Ag-containing solution in copper powder solution and carries out preparing silver-plated copper powder without the silver-plated method of cyaniding.Document [electroless plating method prepares silver-colored Coated copper powder reaction process research] is introduced the strong reductant hydrazine hydrate, suppress displacement reaction by control, make silver ammino solution that Liquid reduction reaction process preferentially occur, prepared the bimetal Cu-Ag powder roughly the same with former copper powder size and pattern.Application for a patent for invention [CN101214547A] discloses a kind of silver powder with micron-scale, silver-coated copper powder or silver-copper mixing split for supporting matrix, make silver salt be reduced to nano-silver powder with the reproducibility compound, and be deposited on the described stromal surface that supports, thereby obtain containing the preparation method of the micrometer silver-copper granule of nano level surface structure.
The silver-plated copper powder majority of said method preparation is only applicable to the electromagnetic shielding field, the requirement that does not reach the used conductive filler in electric slurry field at aspects such as granularity, color, glossiness, electric conductivity, tap densities, and technological operation remains further to be optimized, and has that silver-plated efficient is low, has the thickness of deposition of silver, silvering to be difficult to the shortcomings such as control on the coating bath.
Summary of the invention
The problem that can't prepare the used silver-plated copper powder conductive filler in electric slurry field for solving prior art the invention provides the preparation method that a kind of electric slurry is used Silver Coated Copper Powders, and its technical scheme is as follows:
A kind of electric slurry preparation method of Silver Coated Copper Powders comprises following sequential steps:
(1) gets the spherical or ultrafine flake copper powder that micro-granularity is 200 ~ 400nm, through alkali cleaning, pickling, remove greasy dirt and the oxide layer impurity of Copper Powder Surface;
Above-mentioned superfine cupper powder after surface treatment as copper powder to be plated, is entered following steps (2) to the silver-plated circulation of step (4);
(2) get the dispersant of 1 ~ 2 ‰ weight portion, the additive of 20 ~ 40% weight portions, the reducing agent of 30 ~ 60% weight portions, join in the deionized water of 20 weight portions, be mixed with reducing solution, the copper powder to be plated that in this reducing solution, adds 1 weight portion, stir, then add the pH value to 12 of NaOH or ammoniacal liquor regulator solution ~ 14, be prepared into mixture to be plated;
Described additive is one or more the mixture in tartaric acid, sodium tartrate, sodium potassium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, the natrium citricum;
(3) silver nitrate of getting 0.6 ~ 1.6 weight portion adds in the deionized water of 40 weight portions, adds the amine complexing agent of 0.6 ~ 2.4 weight portion, is prepared into argentamine liquid;
(4) under stirring or ultrasound condition, and under the condition of normal temperature, the argentamine liquid that step (3) is prepared is added dropwise in the mixture to be plated of step (2) preparation continuously, reacts 15 minutes, obtains silver-plated copper powder;
(5) above-mentioned silver-plated copper powder is cleaned up with deionized water after, as copper powder to be plated, again enter above-mentioned steps (2) to the silver-plated circulation of step (4), obtain the secondary silver-plated copper powder, the secondary silver-plated copper powder is behind vacuum filtration, extremely neutral with washed with de-ionized water;
(6) under the condition that stirs, the secondary silver-plated copper powder of above-mentioned neutrality is put into (quantity of the ethanol that please remark additionally) ethanolic solution of (3) weight portion of the surface modifier that is dissolved with 1 ~ 2% weight portion, stirred 10 minutes, through suction filtration, clean up after, dewater with acetone, after 60 ℃ of vacuum drying, obtain Silver Coated Copper Powders again.
As the priority scheme of the inventive method, such scheme also can be done following design:
Dispersant in the described step (2) is any one in BTA, polyvinylpyrrolidone, APES or the terpinol.
Further priority scheme as the inventive method:
Reducing agent in the described step (2) is one or more the mixture in formaldehyde, hydrazine hydrate or the glucose.
Further priority scheme as the inventive method:
Amine complexing agent in the described step (3) is ethylenediamine or diethylenetriamine or polyhydric alcohol amine.
Further priority scheme as the inventive method:
Surface modifier in the described step (6) is one or more the mixture in silane coupler, titanate coupling agent, fatty acid ester, polyvinylpyrrolidone or the oleic acid.
The silver plating process that the present invention relates to carries out under normal temperature, alkali condition, technological operation is simple, stable process conditions, silver-plated efficient are high, adopt the method for displacement-reduction Composite Coatings to improve silver-plated efficient, through twice silver-plated, increase thickness and the density of coating, and the coating bath surface does not have the silver layer of deposition, can obtain granularity is 400 ~ 500nm, and coating is even, thickness is controlled, density is high, and antioxygenic property is good, good conductivity, apparent density are 1.4 ~ 1.6g/cm
3, tap density is 3.5 ~ 4.0g/cm
3, color is silvery white, near-spherical Silver Coated Copper Powders.The Silver Coated Copper Powders that adopts this method to prepare can be used as the conductive filler of the electric slurry in the fields such as thin film switch, flexible circuitry, touch-screen, solar cell, its dispersed fine in electric slurry, electric conductivity is also fine, its amount of filling can be the user and saves 10 ~ 20% silver nearly, can replace wholly or in part silver powder, greatly reduce user's production cost.
The specific embodiment
Below in conjunction with example, the technical scheme that the present invention is proposed is described further:
Embodiment one:
(1) gets the near-spherical superfine cupper powder that micro-granularity is 200nm, through alkali cleaning, pickling, remove the impurity such as the greasy dirt of Copper Powder Surface and oxide layer;
(2) 1 ‰ BTA, 20% tartaric acid, 30% formaldehyde of copper powder weight is added in the deionized water consist of reducing solution, the mass ratio of deionized water and copper powder to be plated is: 20:1, add copper powder to be plated and stir, the pH value that then adds sodium hydrate regulator solution is 12;
(3) getting weight ratio with superfine cupper powder is that 0.6 silver nitrate adds deionized water, and adding with the silver nitrate mass ratio is the ethylenediamine of 1:1, obtains argentamine liquid;
(4) under the condition that stirs, the argentamine liquid with step 3 under the normal temperature is added dropwise in the reducing solution of step 2 continuously, reacts 15 minutes, obtains once silver-plated copper powder;
Will be through the silver-plated copper powder washed with de-ionized water that obtains once, after cleaning up, repeat step (2) preparation and obtain reducing solution, then add a silver-plated copper powder is stirred, the pH value that adds sodium hydrate regulator solution is 12, then repeats above-mentioned steps (3)-(4), obtains the secondary silver-plated copper powder, the secondary silver-plated copper powder is carried out vacuum filtration, extremely neutral with washed with de-ionized water;
(5) under the condition that stirs, the Silver Coated Copper Powders that finally obtains is placed the organic solution that contains 1% silane coupler, stirred 10 minutes, suction filtration after cleaning up, with the acetone dehydration, obtains Silver Coated Copper Powders after 60 ℃ of vacuum drying.The granularity D50 of this Silver Coated Copper Powders is about 1.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 20m Ω/ /mil.
Embodiment two:
(1) gets the near-spherical superfine cupper powder that micro-granularity is 400nm, through alkali cleaning, pickling, remove the impurity such as the greasy dirt of Copper Powder Surface and oxide layer;
(2) 2 ‰ BTA, 40% tartaric acid, 60% formaldehyde of copper powder weight is added in the deionized water consist of reducing solution, add copper powder and stir, the pH value that then adds sodium hydrate regulator solution is 14;
(3) getting weight ratio with superfine cupper powder is that 1.6 silver nitrate adds deionized water, and adding with the silver nitrate mass ratio is the ethylenediamine of 1:1.5, obtains argentamine liquid;
(4) under the condition that stirs, the argentamine liquid with step 3 under the normal temperature is added dropwise in the reducing solution of step 2 continuously, reacts 15 minutes, obtains once silver-plated copper powder;
(5) will be through the silver-plated copper powder washed with de-ionized water that obtains once, after cleaning up, repeat compound silver-plated step, namely repeat step (2) preparation and obtain reducing solution, then add a silver-plated copper powder is stirred, the pH value that adds sodium hydrate regulator solution is 12, then repeat above-mentioned steps (3)-(4), obtain the secondary silver-plated copper powder, the secondary silver-plated copper powder is carried out vacuum filtration, extremely neutral with washed with de-ionized water;
(6) under the condition that stirs, the Silver Coated Copper Powders that obtains is placed the organic solution of 2% silane coupler, stirred 10 minutes, suction filtration after cleaning up, with the acetone dehydration, obtains Silver Coated Copper Powders after 60 ℃ of vacuum drying.The granularity D50 of this Silver Coated Copper Powders is about 1.5 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10m Ω/ /mil.
Embodiment three:
(1) gets the near-spherical superfine cupper powder that micro-granularity is 300nm, through alkali cleaning, pickling, remove the impurity such as the greasy dirt of Copper Powder Surface and oxide layer;
(2) 1.5 ‰ BTA, 30% tartaric acid, 50% formaldehyde of copper powder weight is added in the deionized water consist of reducing solution, add copper powder and stir, the pH value that then adds sodium hydrate regulator solution is 13;
(3) getting weight ratio with superfine cupper powder is that 1.1 silver nitrate adds deionized water, and adding with the silver nitrate mass ratio is the ethylenediamine of 1:1.25, obtains argentamine liquid;
(4) under the condition that stirs, the argentamine liquid with step 3 under the normal temperature is added dropwise in the reducing solution of step 2 continuously, reacts 15 minutes, obtains once silver-plated copper powder;
(5) will be through the silver-plated copper powder washed with de-ionized water that obtains once, after cleaning up, repeat compound silver-plated step, namely repeat step (2) preparation and obtain reducing solution, then add a silver-plated copper powder is stirred, the pH value that adds sodium hydrate regulator solution is 12, then repeat above-mentioned steps (3)-(4), obtain the secondary silver-plated copper powder, the secondary silver-plated copper powder is carried out vacuum filtration, extremely neutral with washed with de-ionized water;
(6) under the condition that stirs, the Silver Coated Copper Powders that obtains is placed the organic solution of 1.5% silane coupler, stirred 10 minutes, suction filtration after cleaning up, with the acetone dehydration, obtains Silver Coated Copper Powders after 60 ℃ of vacuum drying.The granularity D50 of this Silver Coated Copper Powders is about 1.3 μ m, is mixed with the cryotronics slurry, and sheet resistance is 15m Ω/ /mil.
Embodiment four:
BTA in the step (2) replaces with polyvinylpyrrolidone, and other are respectively with embodiment 1-3.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.2 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 12m Ω/ /mil.
Embodiment five:
Polyvinylpyrrolidone in the step (2) replaces with APES, and other are respectively with embodiment 1-3.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.4 μ m, is mixed with the cryotronics slurry, and sheet resistance is 13 ~ 16m Ω/ /mil.
Embodiment six:
APES in the step (2) replaces with terpinol, and other are respectively with embodiment 1-3.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.2 ~ 1.6 μ m, is mixed with the cryotronics slurry, and sheet resistance is 15 ~ 20m Ω/ /mil.
Embodiment seven:
Tartaric acid in the step (2) replaces with sodium tartrate, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.6 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment eight:
Sodium potassium tartrate tetrahydrate in the step (2) replaces with sodium ethylene diamine tetracetate, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.5 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment nine:
Sodium ethylene diamine tetracetate in the step (2) replaces with natrium citricum, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.6 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment ten:
Natrium citricum in the step (2) replaces with sodium potassium tartrate tetrahydrate and sodium ethylene diamine tetracetate additive package, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.4 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 11:
Sodium potassium tartrate tetrahydrate in the step (2) and sodium ethylene diamine tetracetate additive package replace with the additive package of sodium potassium tartrate tetrahydrate and natrium citricum, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.6 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 12:
Sodium potassium tartrate tetrahydrate in the step (2) and the additive package of natrium citricum replace with the additive package of sodium ethylene diamine tetracetate and natrium citricum, and other are respectively with embodiment 1-6.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.4 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 13:
Reducing agent formaldehyde in the step (2) replaces with hydrazine hydrate, and other are respectively with embodiment 1-12.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.6 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 14:
Reducing agent hydrazine hydrate in the step (2) replaces with glucose, and other are respectively with embodiment 1-12.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.8 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 16m Ω/ /mil.
Embodiment 15:
Reducing agent glucose in the step (2) replaces with the mixing reducing agent of formaldehyde and hydrazine hydrate, and other are respectively with embodiment 1-12.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.4 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 13m Ω/ /mil.
Embodiment 16:
Formaldehyde in the step (2) replaces with the reducing agent that mixes of glucose with formaldehyde with the reducing agent that mixes of hydrazine hydrate, and other are respectively with embodiment 1-12.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.7 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 17:
Formaldehyde in the step (2) replaces with the reducing agent that mixes of glucose with hydrazine hydrate with the reducing agent that mixes of glucose, and other are respectively with embodiment 1-12.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.7 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 18:
The NaOH aqueous ammonia to replace of the regulator solution pH value in the step (2), other are respectively with embodiment 1-17.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 19:
Ethylenediamine in the step (3) replaces with diethylenetriamine, and other are respectively with embodiment 1-18.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.5 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 20:
Diethylenetriamine in the step (3) substitutes with polyhydric alcohol amine, and other are respectively with embodiment 1-18.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.4 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 21:
Silane coupler in the step (6) replaces with titanate coupling agent, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 22:
Titanate coupling agent in the step (6) replaces with fatty acid ester, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 23:
Fatty acid ester in the step (6) replaces with polyvinylpyrrolidone, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.8 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 14m Ω/ /mil.
Embodiment 24:
Polyvinylpyrrolidone in the step (6) replaces with oleic acid, and other are respectively with embodiment 1-19.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 25:
Oleic acid in the step (6) replaces with the blending surface modifier of silane coupler and fatty acid ester, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.5 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 26:
Silane coupler in the step (6) and the blending surface modifier of fatty acid ester replace with the blending surface modifier of silane coupler and polyvinylpyrrolidone, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 27:
Silane coupler in the step (6) and the blending surface modifier of polyvinylpyrrolidone replace with the blending surface modifier of silane coupler and oleic acid, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 28:
The blending surface modifier of the silane coupler in the step (6) and the blending surface modifier of polyvinylpyrrolidone usefulness silane coupler and fatty acid ester, polyvinylpyrrolidone replaces, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 1.5 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 15m Ω/ /mil.
Embodiment 29:
The blending surface modifier of the silane coupler in the step (6) and the blending surface modifier of polyvinylpyrrolidone usefulness silane coupler and fatty acid ester, oleic acid replaces, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 20m Ω/ /mil.
Embodiment 30:
Silane coupler among the embodiment 26-29 replaces with titanate coupling agent, and other are respectively with embodiment 1-20.The granularity D50 of the Silver Coated Copper Powders that makes is about 1.0 ~ 2.0 μ m, is mixed with the cryotronics slurry, and sheet resistance is 10 ~ 22m Ω/ /mil.
Claims (5)
1. the preparation method of an electric slurry usefulness Silver Coated Copper Powders is characterized in that, comprises following sequential steps:
(1) gets the spherical or ultrafine flake copper powder that micro-granularity is 200 ~ 400nm, through alkali cleaning, pickling, remove greasy dirt and the oxide layer impurity of Copper Powder Surface;
Above-mentioned superfine cupper powder after surface treatment as copper powder to be plated, is entered following steps (2) to the silver-plated circulation of step (4);
(2) get the dispersant of 1 ~ 2 ‰ weight portion, the additive of 20 ~ 40% weight portions, the reducing agent of 30 ~ 60% weight portions, join in the deionized water of 20 weight portions, be mixed with reducing solution, the copper powder to be plated that in this reducing solution, adds 1 weight portion, stir, then add the pH value to 12 of NaOH or ammoniacal liquor regulator solution ~ 14, be prepared into mixture to be plated;
Described additive is one or more the mixture in tartaric acid, sodium tartrate, sodium potassium tartrate tetrahydrate, disodium ethylene diamine tetraacetate, the natrium citricum;
(3) silver nitrate of getting 0.6 ~ 1.6 weight portion adds in the deionized water of 40 weight portions, adds the amine complexing agent of 0.6 ~ 2.4 weight portion, is prepared into argentamine liquid;
(4) under stirring or ultrasound condition, and under the condition of normal temperature, the argentamine liquid that step (3) is prepared is added dropwise in the mixture to be plated of step (2) preparation continuously, reacts 15 minutes, obtains silver-plated copper powder;
(5) above-mentioned silver-plated copper powder is cleaned up with deionized water after, as copper powder to be plated, again enter above-mentioned steps (2) to the silver-plated circulation of step (4), obtain the secondary silver-plated copper powder, the secondary silver-plated copper powder is behind vacuum filtration, extremely neutral with washed with de-ionized water;
(6) under the condition that stirs, the secondary silver-plated copper powder of above-mentioned neutrality is put into (quantity of the ethanol that please remark additionally) ethanolic solution of (3) weight portion of the surface modifier that is dissolved with 1 ~ 2% weight portion, stirred 10 minutes, through suction filtration, clean up after, dewater with acetone, after 60 ℃ of vacuum drying, obtain Silver Coated Copper Powders again.
2. electric slurry according to claim 1 is characterized in that with the preparation method of Silver Coated Copper Powders:
Dispersant in the described step (2) is any one in BTA, polyvinylpyrrolidone, APES or the terpinol.
3. electric slurry according to claim 1 and 2 is characterized in that with the preparation method of Silver Coated Copper Powders:
Reducing agent in the described step (2) is one or more the mixture in formaldehyde, hydrazine hydrate or the glucose.
4. electric slurry according to claim 3 is characterized in that with the preparation method of Silver Coated Copper Powders:
Amine complexing agent in the described step (3) is ethylenediamine or diethylenetriamine or polyhydric alcohol amine.
5. electric slurry according to claim 4 is characterized in that with the preparation method of Silver Coated Copper Powders:
Surface modifier in the described step (6) is one or more the mixture in silane coupler, titanate coupling agent, fatty acid ester, polyvinylpyrrolidone or the oleic acid.
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| CN111304640A (en) * | 2020-03-10 | 2020-06-19 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Silver-coated copper powder, preparation method thereof and electronic paste |
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| CN113020587A (en) * | 2021-02-09 | 2021-06-25 | 哈尔滨工业大学（深圳） | Preparation method of silver-coated copper powder |
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| CN113770348A (en) * | 2021-09-09 | 2021-12-10 | 清华大学 | Preparation method and application of ultrahigh-conductivity material |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
| CN114378299A (en) * | 2021-12-30 | 2022-04-22 | 安徽壹石通材料科学研究院有限公司 | Preparation method of core-shell structure metal composite material |
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| CN103752842A (en) * | 2013-11-11 | 2014-04-30 | 南京工业大学 | Substitution and chemistry deposition compound preparation method for nano silver coated copper powder |
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| CN106148926B (en) * | 2015-04-23 | 2019-08-02 | 广州北峻工业材料有限公司 | Silver-coated copper powder and preparation method thereof |
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| CN112974827A (en) * | 2019-12-12 | 2021-06-18 | 长沙理工大学 | Preparation method of spherical silver powder with high tap density and surface wrinkles |
| CN111304640A (en) * | 2020-03-10 | 2020-06-19 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Silver-coated copper powder, preparation method thereof and electronic paste |
| WO2021180029A1 (en) * | 2020-03-10 | 2021-09-16 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Silver-coated copper powder, preparation method therefor, and electronic paste |
| CN111304640B (en) * | 2020-03-10 | 2022-03-18 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Silver-coated copper powder, preparation method thereof and electronic paste |
| CN113020587A (en) * | 2021-02-09 | 2021-06-25 | 哈尔滨工业大学（深圳） | Preparation method of silver-coated copper powder |
| CN113053561A (en) * | 2021-03-27 | 2021-06-29 | 苏州卡睿杰新材料科技有限公司 | Low-temperature slurry for heterojunction solar cell with silver-plated copper powder as conductive particles and preparation method thereof |
| CN113770348A (en) * | 2021-09-09 | 2021-12-10 | 清华大学 | Preparation method and application of ultrahigh-conductivity material |
| CN113814396A (en) * | 2021-10-18 | 2021-12-21 | 苏州卡睿杰新材料科技有限公司 | Submicron silver-plated copper powder for heterojunction solar cell low-temperature slurry and preparation method thereof |
| CN114378299A (en) * | 2021-12-30 | 2022-04-22 | 安徽壹石通材料科学研究院有限公司 | Preparation method of core-shell structure metal composite material |
| CN114378299B (en) * | 2021-12-30 | 2023-09-05 | 安徽壹石通材料科学研究院有限公司 | Preparation method of core-shell structure metal composite material |
| CN114464343A (en) * | 2022-01-20 | 2022-05-10 | 无锡晶睿光电新材料有限公司 | High-wear-resistance high-conductivity low-temperature curing silver paste and preparation method thereof |
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