CN103128308B - Method for preparing compact silver-coated copper powder by using one pot method - Google Patents
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Abstract
The invention relates to a method for preparing compact silver-coated copper powder by using the one-pot method. The silver-coated copper powder is in a coated core-shell structure, a core layer is made of copper, and a shell layer is made of silver. The preparation method includes: adding ammoniacal copper solution prepared by copper sulfate into aqueous solution containing reducing agent and dispersing agent to obtain copper powder suspension; adding water-soluble organic chelating agent into the suspension containing copper powder; adding ammoniacal silver solution prepared by silver nitrate into the suspension containing the copper powder to enable silver ions and the copper powder to be in a displacement reaction; after the displacement reaction finishes, additionally adding a certain amount of weak reducing agent to restore residual silver ions into silver; and filtering, washing and drying to obtain silver-coated copper powder with different grain diameters of 0.8-5 micrometers. The obtained silver-coated copper powder is uniform in silver coating of the shell layer, compact, good in conductivity, high in high-temperature oxidation resistance, and capable of being used for preparation of various electrode slurry sintered in the air.
Description
Technical field
The present invention relates to a kind of preparation method of silver-coated copper powder, specifically, relate to a kind of method that one kettle way is prepared fine and close silver-coated copper powder.
Background technology
The fast development of electronic information industry has driven take the development of submicron particle as the electric slurry of major function phase, and along with the development of electronic component to aspects such as miniaturization, precise treatment, multifunctions, also more and more higher to the technical requirement of electric slurry.Common submicron particle has silver powder, bronze, palladium powder, nickel powder, aluminium powder, copper powder etc., and wherein silver powder is widely used in electronic component because having extremely good combination property.The low price of copper, and there is the specific insulation close with silver, oxidized but copper powder is easy in preparation and use procedure, the electric conductivity of material is reduced.And use silver-coated copper powder can take into account both advantages, and both can reduce costs, can improve again the non-oxidizability of powder, thereby there is development prospect widely.
The preparation method of silver-coated copper powder has a variety of, and what the most generally adopt is chemical replacement reducing process, by displacement reaction, replaces the copper of copper particle surface with silver, thereby obtains the silver-plated copper powder of surface cladding type structure.But first this method needs copper powder to be carried out to the pretreatment such as surface cleaning, activation, sensitization, and in preprocessing process, copper is easy to again oxidized.In addition displacement reaction is slower, the copper ion displacing is better than silver ion and is adsorbed on copper particle surface, hinder silver ion in the further displacement of copper particle surface, be difficult to form uniform coating, cause coated imprecision, and surface coated silver layer is thinner, in air, be easy to during high temperature sintering oxidizedly, be difficult to form uniform conductive layer.Sometimes method that also adopt to introduce reducing agent promotes the reduction of silver ion, to obtain, there is the silver coating of certain thickness even compact, but add reducing agent easily to cause silver-colored homogeneous nucleation, be not easy to control, and the less stable of silver plating liquid, has reduced silver-colored service efficiency and covered effect.
Notification number is the preparation method that the patent of CN1130553A discloses a kind of copper silver powder for electromagnetic-shielding conductive coating, this method be take copper powder as raw material, select edta and its sodium salt as copper ion chelating agent, oxalic acid or tartaric acid are as reducing agent, the high silver content in copper silver powder surface of preparation only has 5%, does not possess high-temperature oxidation resistance.
Notification number is that the patent of CN101244459B discloses a kind of preparation method who adopts rare earth modified chemical silvering copper powder, adopts clean, activation, sensitization before this method copper powder plating and adopts ultrasonic wave auxiliary, and technique more complicated, cost is higher.
Notification number is that the patent of CN1300381C discloses a kind of preparation method of conducting electricity compound copper powder and compound copper conductor slurry, the method adopts introduces reducing agent being reduced to silver and being deposited on Copper Powder Surface formation cladded type structure silver ion, the strong reductants such as the formaldehyde adopting, hydrazine hydrate make reaction speed fast, be not easy to reduce silver-colored spontaneous nucleation growth, reduced silver-colored service efficiency.
Publication number is that the patent of CN101214547A changes the surface topography layout of micron order copper silver particle by electronation, make it contain nanoscale structures surface, although reduced surperficial sintering or melt temperature, but when high temperature sintering, oxygen is easy to make copper oxidation through top layer, and this system is not used surfactant or ultrasonic dispersion to assist in addition, and the dispersiveness of system is poor, in preparation process, between particle, collision is easily reunited, and particle size were is distributed wide.
Summary of the invention
Technical problem: the object of this invention is to provide a kind of with low cost, simple to operate, easy control of reaction, reproducible one kettle way is prepared the method for fine and close silver-coated copper powder, and this silver-coated copper powder is spherical, between 0.8～5 micron of average grain diameter, conduct electricity very well, high-temperature oxidation resistance is strong, is applicable to making the electrode slurry of sintering in air.
Technical scheme: the invention provides a kind of preparation method of silver-coated copper powder, the method comprises the following steps:
The ammoniacal liquor that is 28% by copper sulphate and weight concentration preparation concentration of copper sulfate is that 50～200 grams per liters and ammonium hydroxide concentration are the cuprammonium aqueous solution of 22～86 grams per liters; Preparation reductant concentration is that 55～232 grams per liters and dispersant concentration are the mixed aqueous solution of 8～15 grams per liters, two kinds of aqueous solution that are 1:1.05 by copper sulphate and reducing agent mol ratio under the mixing speed of 160 revs/min, temperature is controlled at 30～90 ℃, under stirring, react 0.5～2 hour, obtain the suspension containing copper powder.The ammoniacal liquor that is 28% by silver nitrate and weight concentration preparation silver nitrate concentration is that 30～300 grams per liters and ammonium hydroxide concentration are the silver-colored ammonia spirit of 13～124 grams per liters, under stirring, the copper ion chelating agent of 0.5～3 times of silver nitrate mole dosage is added in the suspension that contains copper powder, then under agitation in silver in silver-coated copper powder: copper mass is than being the ratio of 35:65～65:35, silver-colored ammonia spirit is joined in described suspension, temperature is controlled at 30～80 ℃, continue reaction 1～2 hour, add again 10%～50% the weak reductant reaction 30 minutes of silver nitrate mole dosage, make residual silver ion reduction for silver, through standing, filter, washing, after dry processing, obtain granularity and be the silver-coated copper powder of 0.8～5 micron.
Reducing agent used is ascorbic acid, and particle diameter is easily controlled, the powder globulate of formation.Reducing agent addition is less than the molal quantity of copper sulphate, and copper sulphate can not be reduced completely, and addition is more than 1.05 times of copper sulphate molal quantity, the spontaneous nucleation reaction that produces silver ion when causing follow-up displacement reaction; Dispersant used is the condensation product that aminated compounds and formolite reaction form, the Copper Powder Surface forming under the effect of this dispersant is bright and clean closely knit, copper powder is easily cleaned, aminated compounds used is urea, ethylenediamine, 1,3-propane diamine, 1,4-butanediamine, Isosorbide-5-Nitrae-cyclohexanediamine, the mol ratio of aminated compounds and formaldehyde is between 1:2～4; Prepare the activator that the ammonium sulfate forming in copper powder process can be used as Copper Powder Surface, remove the oxide forming at Copper Powder Surface in displacement reaction process, make displacement reaction can seek profit and carry out; The oxidation ascorbic acid forming and condensation product when silver ion and Copper Powder Surface carry out displacement reaction can with the absorption of copper ion chelating prevention copper ion on copper surface; Described copper ion chelating agent is N, N'-ethylene-[2-(2-hydroxy phenyl)] glycine and N, N'-bis-(2-acrinyl) ethylenediamine-N, a kind of in N'-oxalic acid, N as copper ion chelating agent, N'-ethylene-[2-(2-hydroxy phenyl)] glycine, N, N'-bis-(2-acrinyl) ethylenediamine-N, N'-oxalic acid has good water-soluble, there is the copper ion sequestering power higher than edta and its sodium salt, tartaric acid and natrium potassium salt thereof, can reduce the consumption of additive; In the displacement reaction later stage, add a small amount of weak reductant and mainly make residual silver ion reduction to silver-coated copper powder surface, described weak reductant is any one in formic acid, oxalic acid, tartaric acid, sodium tartrate and potassium sodium tartrate; The silver-coated copper powder of preparation is cladded type nucleocapsid structure, and stratum nucleare is yellow gold, and shell is silver; Silver-coated copper powder is spherical, is nucleocapsid structure, silver content by weight percentage between 35～65%, the silver content lower than 35%, the conductance of the electrode of making is poor.Concrete silver content is selected the content of coated with silver according to the size of copper powder size, the coated silver of the large need of particle diameter is just few, and the coated silver of the little need of particle diameter is just many.
Silver-coated copper powder prepared by the present invention, adopts SEM and its pattern of transmission electron microscope observation and covered effect.The actual silver content of silver-coated copper powder adopts chemical analysis to measure.Non-oxidizability adopts the sheet resistance of making electrode to express, and the sheet resistance non-oxidizability lower, explanation silver-coated copper powder of making electrode is better.With resistance meter, measure the sheet resistance of the electrode of being made by silver-coated copper powder.The making of electrode is that silver-coated copper powder, cryogenic glass powder, ethyl cellulose and terpinol are mixed, grind the slurry of making containing silver-coated copper powder 70%, glass dust 3% in proportion, then by slurry by serigraphy at Al
2o
3on potsherd, drying, in 800 ℃ in air sintering must test and use electrode sample.
Beneficial effect:
1. silver-coated copper powder of the present invention is in a reactor, to adopt one kettle way preparation, i.e. first preparation is containing the suspension of copper powder, then it is silver-colored in the coated growth of Copper Powder Surface to add liquor argenti nitratis ophthalmicus to make; The ammonium sulfate producing in preparing copper powder process can be eliminated and prepare cupric oxide and the cuprous oxide producing in copper powder process; play activation; make copper and the silver-colored displacement reaction need not inert gas shielding; under the condition that can exist at air, complete; save the pretreating process of Copper Powder Surface in general technology; and make coated silver layer finer and close, do not produce the separated of silver-colored shell and copper core, increased the obstruction ability of under high temperature and air existence, oxygen being passed to top layer.
2. the oxidation ascorbic acid that the present invention adopts ascorbic acid reduction copper ion to prepare to produce in the process of copper powder and as the condensation product of dispersant with hydroxyl, carbonyl and amino, there is the ability with copper ion chelating, be conducive to suppress copper ion in the absorption on silver-coated copper powder surface during displacement reaction, can form uniform cladded type structure, reduce the addition of copper ion chelating agent.
3. the copper ion chelating agent that the present invention uses has good chelating to copper ion, can form water miscible chelate, can effectively suppress copper ion in the absorption on silver-coated copper powder surface, and displacement reaction can be carried out smoothly, improves silver-colored covered effect.
4. the silver-coated copper powder that prepared by the present invention is spherical, average grain diameter is between 0.8～5 micron, and in silver-coated copper powder, silver content, by weight percentage between 35～65%, can be directly used in the preparation of sintered electrode slurry in air, save a large amount of noble silvers, reduced the cost of making electrode slurry.
5. the method for preparing silver-coated copper powder provided by the invention, process conditions are simple, easy to operate, are applicable to industrial mass production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention prepares silver-coated copper powder.
Fig. 2 is the scanning electron microscope (SEM) photograph of the silver-coated copper powder of embodiment 1 gained.
The specific embodiment
One kettle way is prepared a method for fine and close silver-coated copper powder, and the method comprises the following steps:
The ammoniacal liquor that is 28% by copper sulphate and weight concentration preparation concentration of copper sulfate is that 50,120 or 200 grams per liters and ammonium hydroxide concentration are the cuprammonium aqueous solution of 22,45 or 86 grams per liters, preparation reductant concentration is that 55,150 or 232 grams per liters and dispersant concentration are the mixed aqueous solution of 8,12 or 15 grams per liters, under the mixing speed of 160 revs/min, by the mol ratio of reducing agent and copper sulphate, be two kinds of aqueous solution of 1,1.03 or 1.05, temperature is controlled at 30,60 or 90 ℃, under stirring, react 0.5,1.2 or 2 hour, obtain the suspension containing copper powder, the ammoniacal liquor that is 28% by silver nitrate and weight concentration preparation silver nitrate concentration is 30, 220 or 300 grams per liters and ammonium hydroxide concentration are 13, the silver-colored ammonia spirit of 85 or 124 grams per liters, under stirring by silver nitrate mole dosage 0.5, the copper ion chelating agent of 2 or 3 times is added in the suspension that contains copper powder, then under agitation pressing silver in silver-coated copper powder is 35:65 with copper mass ratio, the ratio of 40:45 or 65:35, silver-colored ammonia spirit is joined in described suspension, temperature is controlled at 30, 50 or 80 ℃, continue reaction 1, 1.5 or 2 hours, add again 10% of silver nitrate mole dosage, 30% or 50% weak reductant reaction 30 minutes, make residual silver ion reduction for silver, through standing, filter, washing, after dry processing, obtain granularity and be the silver-coated copper powder of 0.8～5 micron.In the present embodiment, described reducing agent is ascorbic acid; Described dispersant be formaldehyde and aminated compounds prepare containing methylol amine groups condensation product, aminated compounds used is urea, ethylenediamine, 1,3-propane diamine, Putriscine, 1,4-cyclohexanediamine, the mol ratio of aminated compounds and formaldehyde is between 1:2,1:3 or 1:4; Described weak reductant is any one in formic acid, oxalic acid, tartaric acid, sodium tartrate and potassium sodium tartrate; Described copper ion chelating agent is N, N'-ethylene-[2-(2-hydroxy phenyl)] glycine and N, N'-bis-(2-acrinyl) ethylenediamine-N, a kind of in N'-oxalic acid; Described silver-coated copper powder is spherical, is nucleocapsid structure, and silver content is by weight percentage between 36%, 50% or 65%.
The present invention prepares silver-coated copper powder process as shown in Figure 1, and below in conjunction with embodiment, the invention will be further described.
Embodiment 1
First prepare hydroxymethyl amino condensation product dispersant: get 9 grams of anhydrous ethylenediamines and be dissolved in 9 grams of deionized waters, then get the formalin that 50 gram mass marks are 37%, under agitation formalin is joined in ethylenediamine, react 2 hours, standby as dispersant.
The ammonia spirit of getting 18 grams of silver nitrates and 13 gram 28% is dissolved in and in 180 ml deionized water, is mixed with silver-colored ammonia spirit; The ammonia spirit of getting 43 grams of copper sulphate and 33 gram 28% is dissolved in and in 500 ml deionized water, is mixed with the cuprammonium aqueous solution; Get 48 grams of ascorbic acid and 12 grams of hydroxymethyl amino condensation product dispersant solutions are dissolved in the mixed aqueous solution that is mixed with reducing agent and dispersant in 500 ml deionized water altogether.Under the mixing speed of 160 revs/min, the cuprammonium aqueous solution is added to mixing of being formed with dispersant by reducing agent water-soluble in, temperature is controlled at 70 ℃, reacts and after 2 hours, obtain the suspension containing copper powder under stirring; By 24 grams of N, N'-bis-(2-acrinyl) ethylenediamine-N, N'-oxalic acid adds to containing in copper powder suspension, the silver-colored ammonia spirit of silver nitrate is added in suspension, temperature is controlled at 35 ℃ again, reacts and after 1 hour, adds 1 gram of formic acid, react again after 30 minutes and stop, standing, to filter, with deionized water washing, only wash electrical conductivity of water be 10～20 micro-Siemens/cm, then with ethanol washing, after oven dry silver-coated copper powder.As shown in Figure 2, silver is piled up closely knit, average grain diameter 3.9 μ m at Copper Powder Surface to the pattern of silver-coated copper powder, actual silver content 46%, and the sheet resistance of the electrode of preparing with silver-coated copper powder is 30m Ω/.
Embodiment 2
The ammonia spirit of getting 30 grams of silver nitrates and 22 gram 28% is dissolved in and in 300 ml deionized water, is mixed with silver-colored ammonia spirit; The ammonia spirit of getting 43 grams of copper sulphate and 33 gram 28% is dissolved in and in 500 ml deionized water, is mixed with the cuprammonium aqueous solution; Get 48 grams of ascorbic acid and 14 grams of hydroxymethyl amino condensation product dispersant solutions are dissolved in the mixed aqueous solution that is mixed with reducing agent and dispersant in 500 ml deionized water altogether.Under the mixing speed of 160 revs/min, the cuprammonium aqueous solution is added to mixing of being formed with dispersant by reducing agent water-soluble in, temperature is controlled at 70 ℃, reacts and after 2 hours, obtain the suspension containing copper powder under stirring; By 35 grams of N, N'-bis-(2-acrinyl) ethylenediamine-N, N'-oxalic acid adds to containing in copper powder suspension, the silver-colored ammonia spirit of silver nitrate is added in suspension, temperature is controlled at 35 ℃ again, reacts and after 1 hour, adds 2 grams of oxalic acid, react again after 30 minutes and stop, standing, to filter, with deionized water washing, only wash electrical conductivity of water be 10～20 micro-Siemens/cm, then with ethanol washing, after oven dry silver-coated copper powder.The average grain diameter 1.1 μ m of silver-coated copper powder, actual silver content 63%, the sheet resistance of the electrode of preparing with silver-coated copper powder is 16m Ω/.
Comparative example 1
The ammonia spirit of getting 30 grams of silver nitrates and 22 gram 28% is dissolved in and in 300 ml deionized water, is mixed with silver-colored ammonia spirit; The ammonia spirit of getting 65 grams of Gerhardites and 33 gram 28% is dissolved in 500 milliliters and is mixed with copper ammon solution, gets 48 grams of ascorbic acid and 8 grams of polyvinylpyrrolidones are dissolved in the mixed aqueous solution that is mixed with reducing agent and dispersant in 500 ml deionized water altogether.Under the mixing speed of 160 revs/min, the cuprammonium aqueous solution is added to mixing of being formed with dispersant by reducing agent water-soluble in, temperature is controlled at 70 ℃, reacts and after 2 hours, obtain the suspension containing copper powder under stirring; 35 grams of disodium EDTAs are added in the suspension containing copper powder, again silver-colored ammonia spirit is joined in the suspension containing copper powder, temperature is controlled at 35 ℃, after 1 hour, stop reaction, standing, to filter, with deionized water washing, only wash electrical conductivity of water be 10～20 micro-Siemens/cm, with ethanol washing, finally dry again.Silver-coated copper powder average grain diameter 1.04 μ m, actual silver content 63%, the sheet resistance of the electrode of preparing with silver-coated copper powder is 20 Ω/.
Claims (5)
1. one kettle way is prepared a method for fine and close silver-coated copper powder, it is characterized in that, the method comprises the following steps:
The ammoniacal liquor that is 28% by copper sulphate and weight concentration preparation concentration of copper sulfate is that 50～200 grams per liters and ammonium hydroxide concentration are the cuprammonium aqueous solution of 22～86 grams per liters, preparation reductant concentration is that 55～232 grams per liters and dispersant concentration are the mixed aqueous solution of 8～15 grams per liters, two kinds of aqueous solution that are 1～1.05 by the mol ratio of reducing agent and copper sulphate under the mixing speed of 160 revs/min, temperature is controlled at 30～90 ℃, under stirring, react 0.5～2 hour, obtain the suspension containing copper powder, described reducing agent is ascorbic acid, the ammoniacal liquor that is 28% by silver nitrate and weight concentration preparation silver nitrate concentration is that 30～300 grams per liters and ammonium hydroxide concentration are the silver-colored ammonia spirit of 13～124 grams per liters, under stirring, the copper ion chelating agent of 0.5～3 times of silver nitrate mole dosage is added in the suspension that contains copper powder, then under agitation in silver in silver-coated copper powder with copper mass than being the ratio of 35:65～65:35, silver-colored ammonia spirit is joined in described suspension, temperature is controlled at 30～80 ℃, continue reaction 1～2 hour, add again 10%～50% the weak reductant reaction 30 minutes of silver nitrate mole dosage, make residual silver ion reduction for silver, through standing, filter, washing, after dry processing, obtain granularity and be the silver-coated copper powder of 0.8～5 micron.
2. one kettle way according to claim 1 is prepared the method for fine and close silver-coated copper powder, it is characterized in that, described dispersant be formaldehyde and aminated compounds prepare containing methylol amine groups condensation product, aminated compounds used is urea, ethylenediamine, 1,3-propane diamine, 1,4-butanediamine, Isosorbide-5-Nitrae-cyclohexanediamine, the mol ratio of aminated compounds and formaldehyde is between 1:2～4.
3. one kettle way according to claim 1 is prepared the method for fine and close silver-coated copper powder, it is characterized in that, described weak reductant is any one in formic acid, oxalic acid, tartaric acid, sodium tartrate and potassium sodium tartrate.
4. one kettle way according to claim 1 is prepared the method for fine and close silver-coated copper powder, it is characterized in that, described copper ion chelating agent is N, N'-ethylene-[2-(2-hydroxy phenyl)] glycine and N, N'-bis-(2-acrinyl) ethylenediamine-N, a kind of in N'-oxalic acid.
5. one kettle way according to claim 1 is prepared the method for fine and close silver-coated copper powder, it is characterized in that, described silver-coated copper powder is spherical, is nucleocapsid structure, and silver content is by weight percentage between 36%～65%.
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Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01119602A (en) * | 1987-11-02 | 1989-05-11 | Mitsui Mining & Smelting Co Ltd | Production of silver-coated copper powder |
| JP2832247B2 (en) * | 1990-07-24 | 1998-12-09 | 三井金属鉱業株式会社 | Method for producing silver-coated copper powder |
| CN1061579C (en) * | 1995-03-08 | 2001-02-07 | 上海市合成树脂研究所 | Process for preparing copper powder for electromagnetic shield conducting paint |
| CN1704191A (en) * | 2004-05-25 | 2005-12-07 | 桂林工学院 | Silver-copper alloy powder and preparation method thereof |
| EP2303492A1 (en) * | 2008-06-23 | 2011-04-06 | Yissum Research Development Company of the Hebrew University of Jerusalem, Ltd. | Core-shell metallic nanoparticles, methods of production thereof, and ink compositions containing same |
| CN101391308A (en) * | 2008-10-10 | 2009-03-25 | 北京工业大学 | Preparation method of cuprum argentum composite powder |
| CN101704109B (en) * | 2009-09-25 | 2011-04-20 | 东南大学 | Method for preparing spherical silver powder by using hydroxymethyl amino condensation product as dispersant |
| CN102161104A (en) * | 2011-04-02 | 2011-08-24 | 东南大学 | Preparation method of copper-silver composite powder |
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