CN103128308A - 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 prepares 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 have the specific insulation close with silver, oxidized but copper powder is easy in preparation and use procedure, make the electric conductivity of material reduce.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 have development prospect widely.
The preparation method of silver-coated copper powder has a variety of, and what the most generally adopt is the chemical replacement reducing process, namely 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 at first this method needs copper powder to be carried out the pretreatment such as cleaning surfaces, activation, sensitization, and in preprocessing process, copper is easy to again oxidized.Displacement reaction is slower in addition, the copper ion that displaces is better than silver ion and is adsorbed on the copper particle surface, hinder silver ion in the further displacement of copper particle surface, be difficult to form uniform coating, cause coating imprecision, and surface coated silver layer is thinner, is easy to during high temperature sintering oxidizedly in air, is difficult to form uniform conductive layer.Sometimes also adopt the method for introducing reducing agent to promote the reduction of silver ion, have the silver coating of certain thickness even compact with acquisition, but add reducing agent easily to cause the homogeneous nucleation of silver, 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 is take copper powder as raw material, select edta and its sodium salt as the copper ion chelating agent, oxalic acid or tartaric acid are as reducing agent, the high silver content in the 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 cleaning, activation, sensitization before this method copper powder plating and adopts ultrasonic wave auxiliary, and the 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 that adopts, hydrazine hydrate make reaction speed fast, be not easy to reduce the spontaneous nucleation growth of silver, 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 the nanoscale structures surface, although reduced surperficial sintering or melt temperature, but when high temperature sintering, oxygen is easy to pass the top layer and makes the copper oxidation, and this system does not use surfactant or ultrasonic dispersion auxiliary in addition, system dispersed relatively poor, between particle, collision is easily reunited in preparation process, particle size were is distributed wide.
Summary of the invention
Technical problem: the one kettle way that the purpose of this invention is to provide a kind of with low cost, simple to operate, easy control of reaction, good reproducibility prepares 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 fit to make 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:
Be that 28% ammoniacal liquor 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 with copper sulphate and weight concentration; The preparation reductant concentration is that 55～232 grams per liters and dispersant concentration are the mixed aqueous solution of 8～15 grams per liters, be two kinds of aqueous solution of 1:1.05 with copper sulphate and reducing agent mol ratio under the mixing speed of 160 rev/mins, temperature is controlled at 30～90 ℃, reacted under stirring 0.5～2 hour, and obtained containing the suspension of copper powder.be that 28% ammoniacal liquor 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 with silver nitrate and weight concentration, copper ion chelating agent with 0.5～3 times of silver nitrate mole dosage under stirring 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 be silver, through standing, filter, washing, obtain granularity after dry the processing 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.The reducing agent addition is less than the molal quantity of copper sulphate, and copper sulphate can not be reduced fully, and addition produces the spontaneous nucleation reaction of silver ion more than 1.05 times of the copper sulphate molal quantity in the time of will causing follow-up displacement reaction; Dispersant used is the condensation product that aminated compounds and formolite reaction form, the Copper Powder Surface that forms 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; The ammonium sulfate that forms in preparation copper powder process can be used as the activator of Copper Powder Surface, removes the oxide that forms at Copper Powder Surface in the displacement reaction process, makes displacement reaction can seek profit and carries out; The oxidation ascorbic acid that forms and condensation product can be with copper ion chelating prevention copper ion at the copper surface sorptions when silver ion and Copper Powder Surface carry out displacement reaction; Described copper ion chelating agent is N, N'-ethylene-[2-(2-hydroxy phenyl)] glycine and N, N'-two (2-acrinyl) ethylenediamine-N, a kind of in the N'-oxalic acid, N as the copper ion chelating agent, N'-ethylene-[2-(2-hydroxy phenyl)] glycine, N, N'-two (2-acrinyl) ethylenediamine-N, the N'-oxalic acid has good water-soluble, have 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; Add a small amount of weak reductant in the displacement reaction later stage and mainly make residual silver ion reduction to the 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 the 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 relatively poor.Concrete silver content is selected the content of coated with silver according to the size of copper powder size, the large silver that need coat of particle diameter is just few, and the little silver of coating that needs of particle diameter is just many.
The silver-coated copper powder of the present invention's preparation 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 of making electrode is lower, the non-oxidizability of explanation silver-coated copper powder is better.Measure the sheet resistance of the electrode of being made by silver-coated copper powder with resistance meter.The making of electrode is that silver-coated copper powder, cryogenic glass powder, ethyl cellulose and terpinol are mixed in proportion, grind and make the slurry that contains silver-coated copper powder 70%, glass dust 3%, then with slurry by serigraphy at Al
2O
3On potsherd, drying, in 800 ℃ in air sintering must test and use the electrode sample.
Beneficial effect:
1. silver-coated copper powder of the present invention is to adopt the one kettle way preparation in a reactor, and namely first preparation contains the suspension of copper powder, then adds liquor argenti nitratis ophthalmicus to make silver coat growth at Copper Powder Surface; The ammonium sulfate that produces in preparation copper powder process can be eliminated cupric oxide and the cuprous oxide that produces in preparation copper powder process; play activation; make copper and the displacement reaction of silver need not inert gas shielding; can complete under the condition that air exists; save the pretreating process of Copper Powder Surface in the general technology; and make the silver layer of coating finer and close, do not produce separating of silver-colored shell and copper core, increased the obstruction ability of under the existence of high temperature and air, oxygen being passed the top layer.
The present invention's oxidation ascorbic acid of adopting 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, has the ability with the copper ion chelating, be conducive to suppress copper ion at the silver-coated copper powder surface sorption during displacement reaction, can form uniform cladded type structure, reduce the addition of copper ion chelating agent.
3. the copper ion chelating agent of the present invention's use has chelating preferably to copper ion, can form water miscible chelate, can effectively suppress copper ion at the silver-coated copper powder surface sorption, and displacement reaction can be carried out smoothly, improves the covered effect of silver.
4. the silver-coated copper powder of the present invention's preparation is spherical, average grain diameter is between 0.8～5 micron, and in silver-coated copper powder, silver content between 35～65%, can be directly used in the preparation of sintered electrode slurry in air by weight percentage, 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 fit to industrial mass production.
Description of drawings
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
A kind of one kettle way prepares the method for fine and close silver-coated copper powder, and the method comprises the following steps:
be that 28% ammoniacal liquor 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 with copper sulphate and weight concentration, the 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, be two kinds of aqueous solution of 1,1.03 or 1.05 with the mol ratio of reducing agent and copper sulphate under the mixing speed of 160 rev/mins, temperature is controlled at 30,60 or 90 ℃, reacted under stirring 0.5,1.2 or 2 hour, and obtained containing the suspension of copper powder, be that 28% ammoniacal liquor preparation silver nitrate concentration is 30 with silver nitrate and weight concentration, 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 with 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 press in silver-coated copper powder silver with copper mass than being 35:65, 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 be silver, through standing, filter, washing, obtain granularity after dry the processing 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 the preparation of formaldehyde and aminated compounds contain methylol amine groups condensation product, aminated compounds used is urea, ethylenediamine, 1,3-propane diamine, Putriscine, 1, the 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'-two (2-acrinyl) ethylenediamine-N, a kind of in the 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 the silver-coated copper powder process as shown in Figure 1, and the invention will be further described below in conjunction with embodiment.
Embodiment 1
At first prepare the hydroxymethyl amino condensation product dispersant: get 9 gram anhydrous ethylenediamines and be dissolved in 9 gram deionized waters, then to get 50 gram mass marks be 37% formalin, under agitation formalin is joined in ethylenediamine, reacted 2 hours, standby as dispersant.
The ammonia spirit of getting 18 gram silver nitrates and 13 grams 28% is dissolved in and is mixed with silver-colored ammonia spirit in 180 ml deionized water; The ammonia spirit of getting 43 gram copper sulphate and 33 grams 28% is dissolved in and is mixed with the cuprammonium aqueous solution in 500 ml deionized water; Get 48 gram ascorbic acid and 12 gram 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 rev/mins, the cuprammonium aqueous solution is added to water-soluble by mixing of forming of reducing agent and dispersant in, temperature is controlled at 70 ℃, reaction obtains containing the suspension of copper powder after 2 hours under stirring; With 24 gram N, N'-two (2-acrinyl) ethylenediamine-N, the N'-oxalic acid adds to and contains in copper powder suspension, silver-colored ammonia spirit with silver nitrate is added in suspension again, and temperature is controlled at 35 ℃, reacts and adds 1 gram formic acid after 1 hour, react again after 30 minutes and stop, standing, to filter, only wash electrical conductivity of water with the deionized water washing be 10～20 little Siemens/cm, then with the ethanol washing, after oven dry silver-coated copper powder.The pattern of 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, actual silver content 46% is 30m Ω/ with the sheet resistance of the electrode of silver-coated copper powder preparation.
Embodiment 2
The ammonia spirit of getting 30 gram silver nitrates and 22 grams 28% is dissolved in and is mixed with silver-colored ammonia spirit in 300 ml deionized water; The ammonia spirit of getting 43 gram copper sulphate and 33 grams 28% is dissolved in and is mixed with the cuprammonium aqueous solution in 500 ml deionized water; Get 48 gram ascorbic acid and 14 gram 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 rev/mins, the cuprammonium aqueous solution is added to water-soluble by mixing of forming of reducing agent and dispersant in, temperature is controlled at 70 ℃, reaction obtains containing the suspension of copper powder after 2 hours under stirring; With 35 gram N, N'-two (2-acrinyl) ethylenediamine-N, the N'-oxalic acid adds to and contains in copper powder suspension, silver-colored ammonia spirit with silver nitrate is added in suspension again, and temperature is controlled at 35 ℃, reacts and adds 2 gram oxalic acid after 1 hour, react again after 30 minutes and stop, standing, to filter, only wash electrical conductivity of water with the deionized water washing be 10～20 little Siemens/cm, then with the 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% is 16m Ω/ with the sheet resistance of the electrode of silver-coated copper powder preparation.
Comparative Examples 1
The ammonia spirit of getting 30 gram silver nitrates and 22 grams 28% is dissolved in and is mixed with silver-colored ammonia spirit in 300 ml deionized water; The ammonia spirit of getting 65 gram Gerhardites and 33 grams 28% is dissolved in 500 milliliters and is mixed with copper ammon solution, gets 48 gram ascorbic acid and 8 gram 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 rev/mins, the cuprammonium aqueous solution is added to water-soluble by mixing of forming of reducing agent and dispersant in, temperature is controlled at 70 ℃, reaction obtains containing the suspension of copper powder after 2 hours under stirring; 35 gram disodium EDTAs are added in the suspension that contains copper powder, again silver-colored ammonia spirit is joined in the suspension that contains copper powder, temperature is controlled at 35 ℃, stopped reaction after 1 hour, standing, to filter, only wash electrical conductivity of water with the deionized water washing be 10～20 little Siemens/cm, again with ethanol washing, oven dry at last.Silver-coated copper powder average grain diameter 1.04 μ m, actual silver content 63% is 20 Ω/ with the sheet resistance of the electrode of silver-coated copper powder preparation.
Claims (6)
1. an one kettle way prepares the method for fine and close silver-coated copper powder, it is characterized in that, the method comprises the following steps:
be that 28% ammoniacal liquor 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 with copper sulphate and weight concentration, the preparation reductant concentration is that 55～232 grams per liters and dispersant concentration are the mixed aqueous solution of 8～15 grams per liters, be two kinds of aqueous solution of 1～1.05 with the mol ratio of reducing agent and copper sulphate under the mixing speed of 160 rev/mins, temperature is controlled at 30～90 ℃, reacted under stirring 0.5～2 hour, and obtained containing the suspension of copper powder, be that 28% ammoniacal liquor 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 with silver nitrate and weight concentration, copper ion chelating agent with 0.5～3 times of silver nitrate mole dosage under stirring is added in the suspension that contains copper powder, then under agitation in silver-coated copper powder silver 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 be silver, through standing, filter, washing, obtain granularity after dry the processing and be the silver-coated copper powder of 0.8～5 micron.
2. one kettle way according to claim 1 prepares the method for fine and close silver-coated copper powder, it is characterized in that, described reducing agent is ascorbic acid.
3. one kettle way according to claim 1 prepares the method for fine and close silver-coated copper powder, it is characterized in that, described dispersant be the preparation of formaldehyde and aminated compounds contain 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.
4. one kettle way according to claim 1 prepares 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.
5. one kettle way according to claim 1 prepares 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'-two (2-acrinyl) ethylenediamine-N, a kind of in the N'-oxalic acid.
6. one kettle way according to claim 1 prepares 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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