CN109877336B - Preparation method of flaky copper powder - Google Patents
Preparation method of flaky copper powder Download PDFInfo
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Abstract
The invention discloses a preparation method of flake copper powder, which takes water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt, sublimable flake compound crystallization template or acidic compound-containing crystallization template or buccal tablet alkaline compound crystallization template and reducing agent as raw materials, adopts a chemical plating method to plate copper on the surface of the compound crystallization template until copper ions completely react, and directly obtains the flake copper powder without ball milling through separation purification and processing process after the reaction is finished. The technical scheme of the invention has the advantages of low energy consumption, small environmental pollution, simple production process, short process route, small investment on large-scale production equipment, high production efficiency, low production cost, good dispersion performance and conductivity of products and the like, is suitable for large-scale production, solves the problems in the process of preparing the flake copper powder by a ball milling method, and has good industrial prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of metal powder materials, and relates to a preparation method of flaky copper powder.
Background
The metal powder is classified into four types, spherical, random-particle, flake and linear, according to the particle shape. Unlike spherical metal powder and granular metal powder, flaky metal powder has excellent catalytic performance, excellent sintering performance, excellent thixotropic performance, excellent adhesion, good shielding effect, excellent electromagnetic wave reflecting capacity and excellent conductivity, so that the flaky metal powder has wide application in the fields of chemical catalysis, powder metallurgy, conductive coating, conductive adhesive, conductive ink, conductive slurry and the like.
Currently, spherical metal powder or granular metal powder is mostly used in the fields of chemical catalysis, electromagnetic shielding coating, radar wave reflection coating, conductive adhesive, conductive ink and conductive slurry. In the aspect of conductivity, compared with the flaky metal powder, the spherical metal powder and the granular metal powder are in point contact with each other, so that the conductivity is poor, the metal powder is used in a large amount, and the use cost is high; the flaky metal powder particles not only have large specific surface area, but also are in line contact and surface contact, so that the contact area among the flaky metal powder particles is greatly increased, and therefore, compared with spherical metal powder and granular metal powder, the amount of the flaky metal powder required by the flaky metal powder particles for forming a conductive channel with the same conductive performance is obviously reduced, a viscous product prepared from the flaky metal powder also has thixotropic performance, and the sedimentation stability of the product is obviously improved; therefore, the conductive electronic material prepared by adopting the flaky metal powder can not only obviously improve the conductivity, the adhesive force and the storage stability of the product, but also greatly reduce the consumption of the metal powder, save resources, reduce the production cost and improve the economic benefit. In the aspects of chemical catalysis, electromagnetic shielding and radar wave reflection, the flaky metal powder has a larger specific surface area than spherical metal powder and granular metal powder, so that the flaky metal powder has excellent catalytic performance, electromagnetic shielding performance and radar wave reflection performance. Therefore, techniques for producing flaky metal powders are attracting attention.
The technical reports of the chemical method for preparing the sheet metal powder are few, but the technical repeatability is poor, and the method can be applied to industrialization rarely. At present, most of sheet metal powder products sold on the market are obtained by ball milling spherical metal powder or granular metal powder under specific conditions, because inert gas is usually required for protection during ball milling, proper lubricant and dispersant are required to be added for ball milling to reach the required granularity, then classification, surface polishing and surface modification are carried out, and finally, sheet metal powder is obtained through purification treatment; therefore, the ball milling process is generally complex and tedious, the equipment requirement is high, the production period is long, the energy consumption is high, and the production cost is high; and the purity of the flake metal powder product obtained by ball milling is usually not high, the particle size is large, the surface of the flake particles is concave-convex rough, the shape is irregular, the thickness is uneven, the edge of the powder is cracked, and the specific surface area is small. Therefore, there is a great interest in using new and efficient methods for the production of sheet metal powder products.
Chemical plating is a treatment technique that can form a metal coating on the surface of various materials, and the technique is increasingly receiving attention because of simple process, energy conservation and environmental protection. The principle of chemical plating is simple, and unlike electroplating, chemical plating is a method of forming a plating layer by reducing metal ions to metal and depositing the metal ions on the surface of various materials by using the principle of oxidation-reduction reaction in a solution containing a reducing agent and metal ions without using electricity.
At present, chemical plating reported in the literature is mostly chemical plating on the surfaces of metal conductor materials and non-metal insulator materials, mainly achieves the aims of decorating and protecting substrate materials, and researches on chemical plating on the surfaces of compound crystals are rarely reported in the literature; the research of preparing the flaky metal powder by using flaky compound crystals as templates and a chemical plating method is more rarely reported in literatures. Therefore, the crystal of the sheet compound is taken as a template for chemical plating, reaction process conditions and technical schemes for chemical plating on the surface of the crystal template of the sheet compound are discussed, and the process technology for separating, purifying and processing the obtained chemical plating product to obtain the sheet metal powder are discussed, so that a brand new method for preparing the sheet metal powder is provided, and the method is undoubtedly significant.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide the preparation method of the flaky copper powder, which has the characteristics of low energy consumption, small environmental pollution, simple production process, short production process route, small large-scale production investment, high product purity and high yield.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a preparation method of flake copper powder comprises the following steps:
1) preparing a flaky acidic compound crystallization template or a flaky alkaline compound crystallization template;
2) preparing a mixture containing a sublimable flaky compound crystallization template and a copper salt; or preparing an acidic mixture containing a flaky acidic compound crystallization template and copper salt; or preparing an alkaline mixture containing a flaky alkaline compound crystallization template and copper salt;
3) mixing water and a reducing agent according to the mass percent of 0.1-30.0% to 70.0-99.9%, stirring and dissolving completely to prepare a reducing agent aqueous solution;
4) preparation of flake copper powder: adding the mixture, the acidic mixture or the alkaline mixture in the step 2) into the reducing agent aqueous solution in the step 3), reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the crystal template until the copper ions completely react; when the reactant is a mixture, repeatedly washing and filtering solid substances obtained by filtering a reaction product for multiple times to obtain copper-plated sublimable flaky compound crystals, carrying out reduced pressure heat treatment on the materials at the temperature of 70-150 ℃ to sublimate the sublimable flaky compound crystals, carrying out sublimation recovery on the sublimable flaky compound crystals by using a cold trap after sublimation, and recycling the sublimable flaky compound crystals until the sublimable flaky compound crystals are removed to obtain a copper sheet, and carrying out the processes of adding absolute ethyl alcohol, stirring and dispersing, ultrasonic crushing for 1-6 h, filtering and drying on the obtained copper sheet; when the reactant is an acidic mixture or an alkaline mixture, heating the reaction product to boiling to dissolve the flaky compound crystallization template in boiling water, filtering while the solution is hot to obtain a copper sheet crude product, washing the copper sheet crude product with 50% ethanol water solution for multiple times, filtering, repeatedly purifying, adding absolute ethyl alcohol, stirring, dispersing, ultrasonically crushing for 1-6 hours by ultrasonic waves, filtering and drying; finally, flake copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm is obtained;
in the step 1), preparing a flaky acidic compound crystallization template: according to the mass percentage of the surfactant, the acidic compound crystal and the water being (0.1-30.0%): 0.1-30.0%: 55.0-95.0%, firstly mixing the water with the surfactant, stirring and dissolving completely to obtain a surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an acid compound crystal, stirring until the acid compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the acid compound crystal; placing the saturated solution of the acid compound crystals in a thermostat controlled at 50 ℃ for cooling and crystallizing, taking the materials out of the thermostat when the temperature of the materials is reduced to 50 ℃, and naturally cooling the materials to room temperature to ensure complete crystallization; filtering the materials to obtain a crude crystallization product of the flaky acidic compound, recycling the mother liquor obtained by filtering, washing the crude crystallization product of the flaky acidic compound for 2-3 times by taking cold water with the temperature of 0-5 ℃ and the mass of the product of the flaky acidic compound being 1-10 times of that of the crystallization product, filtering to obtain crystals, and drying the crystals to obtain the crystallization template of the flaky acidic compound.
In the step 1), preparing a flaky alkaline compound crystallization template: according to the mass percentage of (0.1-30.0%) to (55.0-95.0%) of surfactant, alkaline compound crystal and water, firstly mixing water and surfactant, and stirring and dissolving completely to obtain surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an alkaline compound crystal, stirring until the alkaline compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the alkaline compound crystal; placing the saturated solution of the alkaline compound crystal in a thermostat controlled at 50 ℃ for cooling crystallization, taking the material out of the thermostat when the temperature of the material is reduced to 50 ℃, and naturally cooling the material to room temperature to complete crystallization; filtering the materials to obtain a crude crystalline product of the flaky alkaline compound, recycling the mother liquor obtained by filtering, washing the crude crystalline product of the flaky alkaline compound with cold water at 0-5 ℃ of which the mass is 1-10 times that of the crystalline product for 2-3 times according to the mass of the crude crystalline product of the flaky alkaline compound, filtering to obtain crystals, and drying the crystals to obtain the crystalline template of the flaky alkaline compound.
In step 2): the method for preparing the mixture containing the sublimable plate-shaped compound crystallization template and the copper salt comprises the following steps: according to the mass percentage of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt and sublimable flaky compound crystallization template being 35.0-95.0 percent, 0.1-30.0 percent, 0.001-10.0 percent and 0.1-30.0 percent, firstly mixing the water, the copper salt, the complexing agent, the copper plating agent, the dispersant, the antioxidant and the nickel salt, stirring until all materials are completely dissolved, then adding the sublimable flaky compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and carrying out ultrasonic crushing on the sublimable flaky compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m, thus obtaining the sublimable flaky compound crystallization template and copper salt mixture.
In step 2): the method for preparing the acidic mixture containing the flaky acidic compound crystallization template and the copper salt comprises the following steps: according to the mass percentage of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt, acid and flaky acidic compound crystallization template being 35.0-95.0 percent, 0.1-30.0 percent, 0.001-10.0 percent, 0.1-30.0 percent, mixing water, copper salt, a complexing agent, a copper plating brightener, a dispersing agent, an antioxidant, a nickel salt and acid, stirring until all materials are completely dissolved, adding a flaky acidic compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and ultrasonically crushing the flaky acidic compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m to obtain an acid mixture containing the flaky acidic compound crystallization template and the copper salt.
In step 2): the method for preparing the alkaline mixture containing the flaky alkaline compound crystallization template and the copper salt comprises the following steps: according to the mass percentage of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt, alkali and flaky alkaline compound crystallization template of 35.0-95.0 percent, 0.1-30.0 percent, 0.001-10.0 percent, 0.1-30.0 percent, mixing water, copper salt, a complexing agent, a copper plating brightener, a dispersing agent, an antioxidant, a nickel salt and alkali, stirring until all materials are completely dissolved, adding a flaky alkaline compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and ultrasonically crushing the flaky alkaline compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m to obtain an alkaline mixture containing the flaky alkaline compound crystallization template and the copper salt.
In the preparation method of the flake copper powder, the acid is any one or more of benzenesulfonic acid, p-toluenesulfonic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, lactic acid, nitric acid, sulfuric acid, hydrochloric acid, fumaric acid and maleic acid.
In the preparation method of the flake copper powder, the used alkali is any one or more of ammonia, ammonia water, ethylenediamine, n-butylamine, n-pentylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
In the preparation method of the flake copper powder, the sublimable flake compound crystallization template is any one of borneol, benzoic acid, naphthalene and anthracene.
In the preparation method of the flake copper powder, the flake acidic compound crystallization template is any one of 4-methoxyphenol, benzoic acid, boric acid, 2, 6-dimethylphenol and sebacic acid.
In the preparation method of the flaky copper powder, the flaky basic compound crystallization template is one or more of acetanilide, p-toluidine, 1-naphthylamine and 2-naphthylamine.
In the preparation method of the flake copper powder, the copper salt is any one or more of copper citrate, copper sulfate, copper nitrate, copper tartrate, copper chloride and copper acetate.
In the preparation method of the flake copper powder, the nickel salt is any one or more of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel citrate and nickel tartrate.
The antioxidant used in the preparation method of the flake copper powder is any one or more of benzotriazole, mercaptobenzothiazole, aminothiol, n-propyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, isobutyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, isopentyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, benzyl mercaptan and phenethyl mercaptan.
The preparation method of the flake copper powder comprises the step of using the complexing agent to be any one or more of N-hydroxyethyl ethylenediamine triacetic acid, N-hydroxyethyl ethylenediamine triacetic acid trisodium, nitrilotriacetic acid trisodium, ethylenediamine tetraacetic acid disodium, citric acid, sodium citrate, potassium citrate, ammonium citrate, tartaric acid, sodium tartrate, potassium sodium tartrate, glycerol, triethanolamine, antimony potassium tartrate and ammonium tartrate.
The copper plating brightener is any one or more of 2-aminoethanethiol, thiourea, sodium dithiocarbamate, sodium polydithio-dipropanesulfonate, 2-mercaptobenzimidazole and 1, 2-ethylidene thiourea.
In the preparation method of the flake copper powder, the used dispersing agent is any one or more of polyvinylpyrrolidone, carboxymethyl cellulose, sodium carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gelatin, polyacrylic acid, sodium polyacrylate, ammonium polyacrylate, potassium polyacrylate, polyvinyl alcohol, gum arabic and polyethylene glycol.
The reducing agent is any one or more of formaldehyde, hypophosphorous acid, sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine sulfate, dimethylamino borane, glyoxylic acid and methylglyoxal.
The flake copper powder obtained by the preparation method of the flake copper powder has the technical indexes that: appearance: brown powder; pureDegree: not less than 99.5%; particle size range: 0.2 to 10.0 μm; average particle size: 1.0-5.0 μm; thickness range: 5-70 nm; average thickness: 10-40 nm; apparent density: 1.9-2.9 g/cm3(ii) a Tap density: 2.5 to 3.4g/cm3。
In step 4), preparing flake copper powder: gradually adding a reducing agent aqueous solution into a mixture containing the sublimable flaky compound crystallization template and copper salt under the stirring condition, reducing copper ions into metallic copper, and chemically plating the metallic copper on the surfaces of the sublimable flaky compound crystallization templates until the copper ions completely react; and (3) repeatedly washing and filtering solid substances obtained by filtering reaction products to obtain copper-plated sublimable flaky compound crystals, carrying out reduced pressure heat treatment on the materials at the temperature of 70-150 ℃, sublimating the sublimable flaky compound crystals, using a cold trap to desublimate and recover the sublimable flaky compound crystals for recycling until the sublimable flaky compound crystals are removed to obtain copper sheets, and carrying out the processes of adding absolute ethyl alcohol, stirring and dispersing, ultrasonic crushing for 1-6 hours, filtering and drying on the obtained copper sheets to obtain the flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm.
In step 4), preparing flake copper powder: cooling an acidic mixture containing the flaky acidic compound crystallization template and the copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky acidic compound crystallization template until the copper ions are completely reacted; because the flaky acidic compound crystallization template is only slightly soluble in cold water but is soluble in hot water and boiling water, a reaction product is heated to boil, the flaky acidic compound crystallization template is dissolved in the boiling water, the hot solution is filtered to obtain a copper sheet crude product, the obtained copper sheet crude product is washed by 50% ethanol water solution for many times and filtered for repeated operation and purification, and then the anhydrous ethanol is added for stirring and dispersion, ultrasonic crushing is carried out for 1-6 hours, and the processes of filtering and drying are carried out, so that the flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm is obtained.
In step 4), preparing flake copper powder: cooling an alkaline mixture containing a flaky alkaline compound crystallization template and copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky alkaline compound crystallization template until the copper ions completely react; because the flaky alkaline compound crystallization template is only slightly soluble in cold water but is soluble in hot water and boiling water, a reaction product is heated to boil, the flaky alkaline compound crystallization template is dissolved in the boiling water, the hot solution is filtered to obtain a copper sheet crude product, the obtained copper sheet crude product is washed by 50% ethanol water solution for many times and filtered for repeated operation and purification, and then the anhydrous ethanol is added for stirring and dispersion, ultrasonic crushing is carried out for 1-6 hours, and the processes of filtering and drying are carried out, so that the flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm is obtained.
In the preparation method of the flake copper powder, the used water is any one of distilled water, deionized water, ultrapure water and high-purity water;
the preparation method of the flake copper powder uses ultrasonic waves with the frequency of 20 KHz-1 MHz and the power of 30W-15 KW.
Has the advantages that: compared with the prior art, the preparation method of the flake copper powder provided by the invention has the following remarkable advantages:
1) the sublimable flaky compound crystal is used as a template, so that after a solid product obtained by chemical plating is repeatedly washed with water and filtered to remove water-soluble impurities, the template can be directly removed by a sublimation method, the template is extremely easy to remove, the purification process is very simple, quick and efficient, high-purity flaky copper powder can be prepared, the purity of the copper powder can reach more than 99.5%, and the purity of the product is high.
2) Under the condition that the dosage of the copper salt is determined, the thickness of the flaky copper powder can be effectively controlled by changing the dosage of the sublimable flaky compound crystallization template and adjusting the proportion of the copper salt to the sublimable flaky compound crystallization template; ultrasonic crushing sublimable flaky compound crystallization templates and flaky copper obtained by chemical plating by using ultrasonic waves, adjusting ultrasonic crushing time, effectively controlling particle size of flaky copper powder, and having a simple, convenient and effective particle size control method; therefore, the method can effectively control the thickness of the flake copper powder and the particle size of the flake copper powder, can prepare the flake copper powder with high specific surface area which is 3-10 times of the particle copper powder,
3) in the preparation process of the flake copper powder, a copper plating brightener is added for brightening and flattening the chemical copper plating layer and improving the flatness and the smoothness of the surface of the flake copper powder particles; in the preparation process of the flake copper powder, the purpose of adding the complexing agent is to form dynamic balance of free copper ions and copper complex ions in a reaction system, so as to effectively control the concentration of the free copper ions and further control the reduction reaction speed of the copper ions and the deposition speed of copper, so as to obtain a uniform copper coating, and also to ensure that a chemical copper plating layer is bright and smooth and effectively improve the smoothness and finish of the surface of flake copper powder particles; the method is favorable for improving the contact area among the flaky copper powder particles and the conductivity of a product prepared from the flaky copper powder particles, and compared with the flaky copper powder prepared without adding a copper plating brightener and a complexing agent, the conductivity of the flaky copper powder prepared by the method can be improved by about 35 percent, and the improvement effect is obvious.
4) In the preparation process of the flake copper powder, the dispersant is added for preventing particle agglomeration and improving the dispersibility of the flake copper powder particles, so that the flake copper powder is easy to disperse when the flake copper powder is used for preparing a product, the flake copper powder is convenient to use by a user, and the service performance of the flake copper powder is improved.
5) Compared with the viscous product prepared by spherical copper powder, the viscous product prepared by the flaky copper powder produced by the invention, such as conductive adhesive, conductive paste, conductive coating, conductive ink and the like, has the advantages that the sedimentation stability and the storage stability of the product are improved by about 50 percent due to the thixotropic property of the flaky copper powder in a viscous system, and the stability of the product is good.
6) Copper belongs to soft metal, and copper powder particles are pressed into clusters when being pressed or impacted, so that the copper powder particles are pressed into clusters and agglomerated together when being subjected to ball milling crushing and grinding crushing.
7) After the reaction for preparing the flaky copper powder is completed, filtering a reaction product to obtain a solid product, washing the solid product for multiple times, filtering and repeating the operations to remove water-soluble impurities to obtain copper-plated sublimable flaky compound crystals, sublimating the sublimable flaky compound crystals by carrying out reduced pressure heat treatment on the material at the temperature of 70-150 ℃, and sublimating the sublimable flaky compound crystals for recycling by using a cold trap for sublimation, so that template resources are saved, the production cost is reduced, the emission of pollutants is reduced, and the economic benefit and the environmental benefit are improved.
8) The reported process for preparing the flake copper powder by the soft membrane plate method has high requirements and harsh reaction conditions, and the granular copper powder rather than the flake copper powder is usually obtained when the control is improper, so the process for preparing the flake copper powder by the soft membrane plate method has poor repeated stability, the product quality is unstable, even the flake copper powder cannot be obtained, and the product production success rate is not high; the reported technology for preparing the flake copper powder by the hard mask method has the problems that the template is difficult to remove or even cannot be removed, or the process for removing the template is complex and the treatment cost is high, and the like, for example, when the copper powder is prepared by taking titanium dioxide, porous alumina and other substances as the template, the template is difficult to remove or even cannot be removed, even if the template is removed by using a complex process, the template is difficult to remove, the treatment cost is high, the product purity is not high, and the flake copper powder cannot be obtained; the operation process for preparing the flaky copper powder by using the biological template is complex, the control difficulty is high, the reaction process is slow, and the production efficiency is low. The success rate of the preparation of the flake copper powder by the technical scheme of the invention is 100%, the template is easy to remove, the product purity is over 99.5%, the production cost is low, and the production efficiency is high.
9) The purpose of using the antioxidant in the process of preparing the flake copper powder is to form a protective film on the surface of a copper plating layer so as to prevent the copper plating layer on the surface of the sublimable flake compound crystallization template from being oxidized.
10) The nickel salt is used in the process of preparing the flaky copper powder, and the nickel salt has strong catalytic action on the oxidation-reduction reaction of chemical copper plating, so that the chemical copper plating reaction on the surface of the sublimable flaky compound crystal template is smoothly carried out.
11) The technical scheme of the invention has the advantages of low energy consumption, small environmental pollution, simple production process, short process route, small investment on large-scale production equipment, high production efficiency, low production cost and good dispersion performance and conductivity of products, is suitable for large-scale production, solves the problems in the prior art of preparing the flake copper powder by a ball milling method and a template method, and has good industrialization prospect.
12) When preparing a flaky acidic compound crystallization template, placing a saturated solution of acidic compound crystallization in a thermostat controlled at 50 ℃ for cooling crystallization, wherein the cooling speed of the material is reduced by reducing the temperature difference between the material and the environment so as to reduce the crystallization speed, so that the formed flaky crystallization is more regular; washing a flaky acidic compound crystallization crude product obtained by filtering the material for 2-3 times by using cold water with the temperature of 0-5 ℃ and the mass of 1-10 times that of the crystallization crude product, so as to reduce the loss of the flaky acidic compound crystallization and improve the preparation efficiency of a flaky acidic compound crystallization template; the flaky acidic compound crystal means that the crystal shape of the acidic compound is flaky, the flaky acidic compound crystal is used as a template, copper is plated on the surface of the flaky acidic compound crystal template through chemical plating to form flaky copper, and the preparation process of the flaky copper is simple.
13) The selected flaky acidic compound crystallization template is slightly soluble in cold water and dissolved in hot water and boiling water, so that after a reaction product is heated to be boiled, the flaky acidic compound crystallization template is dissolved in the boiling water, and after the reaction product is filtered while hot, impurities and the flaky acidic compound crystallization template can be removed through repeated operations of washing and filtering with 50% ethanol aqueous solution for many times, the impurities and the template are easy to remove, the purification process is simple, quick and efficient, the preparation of high-purity flaky copper powder is facilitated, the purity of the copper powder can reach more than 99.5%, and the purity of the product is high.
14) Firstly, because the selected flaky acidic compound crystallization template is slightly soluble in cold water and soluble in hot water and boiling water, the preparation reaction of the flaky copper is best maintained at room temperature, so that the amount of the flaky acidic compound crystallization template is kept not to be reduced due to dissolution in the reaction process, the amount of the flaky acidic compound crystallization template is stable, and the controllability on the thickness of the flaky copper powder is strong; secondly, because the selected flaky acidic compound crystallization template belongs to an acid compound, and the reaction must be carried out in an acidic environment, the pH of the reactant must be kept less than 7, so that the reduction of the amount of the flaky acidic compound crystallization template in an alkaline environment due to acid-base neutralization reaction is avoided, and thus, the amount of the flaky acidic compound crystallization template is stable, and the controllability on the thickness of the flaky copper powder is strong; thirdly, under the condition that the dosage of the copper salt is determined, the thickness of the flake copper powder can be effectively controlled by changing the dosage of the flake acidic compound crystallization template and adjusting the proportion of the copper salt to the flake acidic compound crystallization template; fourthly, ultrasonic crushing the flaky acidic compound crystallization template and the flaky copper obtained by chemical plating by using ultrasonic waves, adjusting the ultrasonic crushing time, effectively controlling the particle size of the flaky copper powder, and ensuring that the particle size control method is simple, convenient and effective; in a word, the method can effectively control the thickness of the flake copper powder and the particle size of the flake copper powder, and can prepare the flake copper powder with high specific surface area which is 3-10 times of that of the particle copper powder.
15) After the reaction for preparing the flake copper powder is completed, when a reaction product is heated to boiling, because the flake acidic compound crystallization template is slightly soluble in cold water but is soluble in hot water and boiling water, after the copper sheet is taken out by filtering while hot, the flake acidic compound crystallization template is remained in the filtered mother solution, after the mother solution is cooled, the flake acidic compound crystallization template is crystallized and separated out, and the separated crystal is separated and purified by a recrystallization method, the flake acidic compound crystallization template can be recycled, so that the template resource is saved, the production cost is reduced, the discharge of pollutants is reduced, and the economic benefit and the environmental benefit are improved.
16) When preparing a flaky alkaline compound crystallization template, placing a saturated solution of alkaline compound crystals in a thermostat with the temperature controlled at 50 ℃ for cooling crystallization, and reducing the cooling speed of the material by reducing the temperature difference between the material and the environment so as to reduce the crystallization speed and ensure that the formed flaky crystals are more regular; the method comprises the following steps of (1) filtering a material to obtain a crude crystallization product of a flaky alkaline compound, and washing the crude crystallization product of the flaky alkaline compound for 2-3 times by using cold water at 0-5 ℃ which is 1-10 times of the mass of the crude crystallization product, so as to reduce the loss of the crystallization of the flaky alkaline compound and improve the preparation efficiency of a crystallization template of the flaky alkaline compound; the flaky alkaline compound crystal is characterized in that the crystal shape of the alkaline compound is flaky, the flaky alkaline compound crystal is used as a template, copper is plated on the surface of the flaky alkaline compound crystal template through chemical plating to form flaky copper, and the preparation process of the flaky copper is simple.
17) The selected flaky alkaline compound crystallization template is slightly soluble in cold water and dissolved in hot water and boiling water, so that after a reaction product is heated to be boiled, the flaky alkaline compound crystallization template is dissolved in the boiling water, and after the reaction product is filtered while hot, the flaky alkaline compound crystallization template is repeatedly washed by 50% ethanol water solution and filtered, impurities and the flaky alkaline compound crystallization template can be removed, the impurities and the template are easy to remove, the purification process is simple, quick and efficient, the preparation of high-purity flaky copper powder is facilitated, the purity of the copper powder can reach more than 99.5%, and the product purity is high.
18) Firstly, because the selected flaky alkaline compound crystallization template is slightly soluble in cold water and soluble in hot water and boiling water, the preparation reaction of the flaky copper is best maintained at room temperature, so that the amount of the flaky alkaline compound crystallization template is favorably kept not to be reduced due to dissolution in the reaction process, the amount of the flaky alkaline compound crystallization template is stable, and the controllability on the thickness of the flaky copper powder is strong; secondly, because the selected flaky alkaline compound crystallization template belongs to an alkaline compound, and the reaction must be carried out in an alkaline environment, the pH of the reactant must be kept to be more than 7, so that the reduction of the amount of the flaky alkaline compound crystallization template in an acidic environment due to acid-base neutralization reaction is avoided, and thus, the amount of the flaky alkaline compound crystallization template is stable, and the controllability on the thickness of the flaky copper powder is strong; thirdly, under the condition that the dosage of the copper salt is determined, the thickness of the flake copper powder can be effectively controlled by changing the dosage of the flake alkaline compound crystallization template and adjusting the proportion of the copper salt and the flake alkaline compound crystallization template; fourthly, ultrasonic crushing the flaky alkaline compound crystallization template and flaky copper obtained by chemical plating by using ultrasonic waves, adjusting the ultrasonic crushing time, effectively controlling the particle size of the flaky copper powder, and ensuring that the particle size control method is simple, convenient and effective; in a word, the method can effectively control the thickness of the flake copper powder and the particle size of the flake copper powder, and can prepare the flake copper powder with high specific surface area which is 3-10 times of that of the particle copper powder.
19) After the reaction for preparing the flake copper powder is completed, when a reaction product is heated to boiling, the flake alkaline compound crystallization template is slightly soluble in cold water but is soluble in hot water and boiling water, so after the copper flake is filtered and taken out while the reaction product is hot, the flake alkaline compound crystallization template is remained in the filtered mother liquor, the flake alkaline compound crystallization template is crystallized and separated out after the mother liquor is cooled, the separated crystal is separated and purified by a recrystallization method, and the flake alkaline compound crystallization template can be recycled, so that the template resource is saved, the production cost is reduced, the discharge of pollutants is reduced, and the economic benefit and the environmental benefit are improved.
Detailed Description
The present invention will be described in further detail with reference to examples. In the following examples, all percentages are by mass unless otherwise specified.
Example 1
A preparation method of flake copper powder comprises the following specific steps:
1) preparation of a mixture containing sublimable plate-like compound crystallization template and copper salt: according to the mass percentages of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt and sublimable flaky compound crystallization template of products 1-8 in table 1, firstly mixing water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant and nickel salt, stirring until all materials are completely dissolved, then adding sublimable flaky compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and ultrasonically crushing the sublimable flaky compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m to obtain the sublimable flaky compound crystallization template and copper salt-containing mixture.
2) Preparation of a reducing agent aqueous solution: according to the mass percentage of the reducing agent to water of the products 1-8 in the table 1, mixing water and the reducing agent, and stirring and dissolving completely to obtain the reducing agent water solution.
3) Preparation of flake copper powder: gradually adding a reducing agent aqueous solution into a mixture containing the sublimable flaky compound crystallization template and copper salt under the stirring condition, reducing copper ions into metallic copper, and chemically plating the metallic copper on the surfaces of the sublimable flaky compound crystallization templates until the copper ions completely react; washing the solid substance obtained by filtering the reaction product for multiple times, filtering and repeating the operations to obtain copper-plated sublimable flaky compound crystals, carrying out reduced pressure heat treatment on the material at the temperature of 70-150 ℃, subliming the sublimable flaky compound crystals, recovering the sublimable flaky compound crystals by using a cold trap for sublimation and recycling the sublimable flaky compound crystals until the sublimable flaky compound crystals are removed to obtain copper sheets, and carrying out the processes of adding absolute ethyl alcohol, stirring and dispersing the obtained copper sheets, carrying out ultrasonic wave (the frequency is 20 KHz-1 MHz, the power is 30W-15 KW), crushing for 1-6 h, filtering and drying on the obtained copper sheets to obtain flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm;
table 1, 1-8 raw materials and proportions of products
Note [1 ]: pengshuai, Zhu Xiao Yun. And (3) researching the influence of the precursor on the compactness of the copper powder in a two-step liquid-phase reduction method. Functional material, 2014, 24 (45): 24144-24147, 24152.
Example 2
A method for preparing flake copper powder in an acidic medium comprises the following steps:
1) preparing a flaky acidic compound crystallization template: according to the mass percentages of the surfactant, the acidic compound crystals and the water of the products 1-8 in the table 2, firstly mixing the water with the surfactant, and stirring and dissolving completely to obtain a surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an acid compound crystal, stirring until the acid compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the acid compound crystal; placing the saturated solution of the acid compound crystals in a thermostat controlled at 50 ℃ for cooling and crystallizing, taking the materials out of the thermostat when the temperature of the materials is reduced to 50 ℃, and naturally cooling the materials to room temperature to ensure complete crystallization; filtering the materials to obtain a crude crystallization product of the flaky acidic compound, recycling the mother liquor obtained by filtering, washing the crude crystallization product of the flaky acidic compound for 2-3 times by taking cold water with the temperature of 0-5 ℃ and the mass of the product of the flaky acidic compound being 1-10 times of that of the crystallization product, filtering to obtain crystals, and drying the crystals to obtain the crystallization template of the flaky acidic compound.
2) Preparing an acidic mixture containing a flaky acidic compound crystallization template and a copper salt: according to the mass percentages of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt, acid and flaky acidic compound crystallization template in the products 1-8 in the table 2, firstly mixing the water, the copper salt, the complexing agent, the copper plating brightener, dispersant, antioxidant, nickel salt and acid, stirring until all the materials are completely dissolved, then adding the flaky acidic compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and carrying out ultrasonic crushing on the flaky acidic compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m to obtain an acidic mixture containing the flaky acidic compound crystallization template and the copper salt.
3) Preparation of a reducing agent aqueous solution: according to the mass percentage of the reducing agent and the water in the embodiment 1-8 in the table I, the water and the reducing agent are mixed, stirred and dissolved completely, and then the reducing agent water solution is obtained.
4) Preparation of flake copper powder: cooling an acidic mixture containing the flaky acidic compound crystallization template and the copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky acidic compound crystallization template until the copper ions are completely reacted; because the flaky acidic compound crystallization template is only slightly soluble in cold water but soluble in hot water and boiling water, a reaction product is heated to boil, the flaky acidic compound crystallization template is dissolved in the boiling water, the hot solution is filtered to obtain a copper sheet crude product, the obtained copper sheet crude product is washed by 50% ethanol water solution for multiple times and is filtered and purified repeatedly, and then the anhydrous ethanol is added, the mixture is stirred and dispersed, ultrasonic waves (the frequency is 20 KHz-1 MHz, and the power is 30W-15 KW) are added, the mixture is crushed for 1-6 hours, and the processes of filtering and drying are carried out, so that the flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm is obtained.
Table 2, 1-8 raw materials and proportions of products
Note [1 ]: pengshuai, Zhu Xiao Yun. And (3) researching the influence of the precursor on the compactness of the copper powder in a two-step liquid-phase reduction method. Functional material, 2014, 24 (45): 24144-24147, 24152.
Example 3
A method for preparing flake copper powder in an acidic medium comprises the following steps:
1) preparing a flaky basic compound crystallization template: according to the mass percentages of the surfactant, the alkaline compound crystals and the water of the products 1-8 in the table 3, firstly mixing the water with the surfactant, and stirring and dissolving completely to obtain a surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an alkaline compound crystal, stirring until the alkaline compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the alkaline compound crystal; placing the saturated solution of the alkaline compound crystal in a thermostat controlled at 50 ℃ for cooling crystallization, taking the material out of the thermostat when the temperature of the material is reduced to 50 ℃, and naturally cooling the material to room temperature to complete crystallization; filtering the materials to obtain a crude crystalline product of the flaky alkaline compound, recycling the mother liquor obtained by filtering, washing the crude crystalline product of the flaky alkaline compound with cold water at 0-5 ℃ of which the mass is 1-10 times that of the crystalline product for 2-3 times according to the mass of the crude crystalline product of the flaky alkaline compound, filtering to obtain crystals, and drying the crystals to obtain a crystalline template of the flaky alkaline compound;
2) preparing an alkaline mixture containing a flaky alkaline compound crystallization template and a copper salt: according to the mass percentages of water, copper salt, complexing agent, copper plating brightener, dispersant, antioxidant, nickel salt, alkali and flaky alkaline compound crystallization template in the products 1-8 in the table 3, firstly mixing the water, the copper salt, the complexing agent, the copper plating brightener, dispersant, antioxidant, nickel salt and alkali, stirring until all materials are completely dissolved, then adding the flaky alkaline compound crystallization template, stirring and carrying out ultrasonic treatment for 1-60 min, and carrying out ultrasonic crushing on the flaky alkaline compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m to obtain an alkaline mixture containing the flaky alkaline compound crystallization template and the copper salt;
3) preparation of a reducing agent aqueous solution: according to the mass percentage of the reducing agent and the water in the embodiment 1-8 in the table I, mixing the water and the reducing agent, and stirring and dissolving completely to obtain a reducing agent water solution;
4) preparation of flake copper powder: cooling an alkaline mixture containing a flaky alkaline compound crystallization template and copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky alkaline compound crystallization template until the copper ions completely react; because the flaky alkaline compound crystallization template is only slightly soluble in cold water but soluble in hot water and boiling water, a reaction product is heated to boil, the flaky alkaline compound crystallization template is dissolved in the boiling water, the hot solution is filtered to obtain a copper sheet crude product, the obtained copper sheet crude product is washed by 50% ethanol water solution for many times, filtered and purified repeatedly, and then is stirred and dispersed by adding absolute ethanol, crushed for 1-6 hours by ultrasonic waves (the frequency is 20 KHz-1 MHz, and the power is 30W-15 KW), filtered and dried, and the flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm is obtained.
Table 3, 1-8 raw materials and proportions of products
Note [1 ]: pengshuai, Zhu Xiao Yun. And (3) researching the influence of the precursor on the compactness of the copper powder in a two-step liquid-phase reduction method. Functional material, 2014, 24 (45): 24144-24147, 24152.
Claims (1)
1. A preparation method of flake copper powder is characterized by comprising the following steps:
preparing a mixture containing sublimable flaky compound crystallization templates and copper salts: according to the mass percentage of (35.0% -95.0%) water, copper salt, complexing agent, copper plating brightener, dispersing agent, antioxidant, nickel salt and sublimable flaky compound crystallization template: (0.1% -30.0%): (0.1% -30.0%): (0.001% -10.0%): (0.1% -30.0%): (0.001% -10.0%): (0.001% -10.0%): (0.1-30.0%) mixing water, copper salt, a complexing agent, a copper plating brightener, a dispersing agent, an antioxidant and nickel salt, stirring until all materials are completely dissolved, adding a sublimable flaky compound crystallization template, stirring, performing ultrasonic treatment for 1-60 min, ultrasonically crushing the sublimable flaky compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m, and obtaining a sublimable flaky compound crystallization template and copper salt-containing mixture;
preparing a reducing agent aqueous solution: according to the mass percentage of (0.1% -30.0%) of the reducing agent and the water: (70.0% -99.9%) mixing water and a reducing agent, and stirring and dissolving completely to obtain a reducing agent aqueous solution;
preparing the flaky copper powder: gradually adding a reducing agent aqueous solution into a mixture containing the sublimable flaky compound crystallization template and copper salt under the stirring condition, reducing copper ions into metallic copper, and chemically plating the metallic copper on the surfaces of the sublimable flaky compound crystallization templates until the copper ions completely react; washing the solid matter obtained by filtering the reaction product for multiple times, filtering and repeating the operation to obtain copper-plated sublimable flaky compound crystals, sublimating the sublimable flaky compound crystals by carrying out reduced pressure heat treatment on the material at the temperature of 70-150 ℃, sublimating the sublimable flaky compound crystals by using a cold trap, recovering the sublimable flaky compound crystals and recycling the sublimable flaky compound crystals until the sublimable flaky compound crystals are removed to obtain copper sheets, and stirring and dispersing the obtained copper sheets by adding absolute ethyl alcohol, carrying out ultrasonic crushing for 1-6 hours, filtering and drying to obtain flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm;
wherein the water used is any one of distilled water, deionized water, ultrapure water and high-purity water;
wherein the ultrasonic waves are ultrasonic waves with the frequency of 20 KHz-1 MHz and the power of 30W-15 KW;
or, the steps are as follows:
firstly, preparing a flaky acidic compound crystallization template: according to the mass percentage of (0.1% -30.0%) of a surfactant, acidic compound crystals and water: (0.1% -30.0%): (55.0% -95.0%) by mixing water and a surfactant, and stirring and dissolving completely to obtain a surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an acid compound crystal, stirring until the acid compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the acid compound crystal; placing the saturated solution of the acid compound crystals in a thermostat controlled at 50 ℃ for cooling and crystallizing, taking the materials out of the thermostat when the temperature of the materials is reduced to 50 ℃, and naturally cooling the materials to room temperature to ensure complete crystallization; filtering the materials to obtain a crude crystallization product of the flaky acidic compound, recycling the mother liquor obtained by filtering, washing the crude crystallization product of the flaky acidic compound for 2-3 times by taking cold water with the temperature of 0-5 ℃ and the mass of the product of the flaky acidic compound being 1-10 times of that of the crystallization product, filtering to obtain crystals, and drying the crystals to obtain a crystallization template of the flaky acidic compound;
preparing an acidic mixture containing a crystalline template of a flaky acidic compound and copper salt: according to the mass percentage of (35.0% -95.0%) water, copper salt, complexing agent, copper plating brightener, dispersing agent, antioxidant, nickel salt, acid and flaky acidic compound crystallization template: (0.1% -30.0%): (0.1% -30.0%): (0.001% -10.0%): (0.1% -30.0%): (0.001% -10.0%): (0.001% -10.0%): (0.1% -30.0%): (0.1-30.0%) mixing water, copper salt, a complexing agent, a copper plating brightener, a dispersing agent, an antioxidant, a nickel salt and acid, stirring until all materials are completely dissolved, adding a flaky acidic compound crystallization template, stirring, performing ultrasonic treatment for 1-60 min, ultrasonically crushing the flaky acidic compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m, and obtaining an acid mixture containing the flaky acidic compound crystallization template and the copper salt;
preparing a reducing agent aqueous solution: according to the mass percentage of (0.1% -30.0%) of the reducing agent and the water: (70.0% -99.9%) mixing water and a reducing agent, and stirring and dissolving completely to obtain a reducing agent aqueous solution;
preparing flake copper powder: cooling an acidic mixture containing the flaky acidic compound crystallization template and the copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky acidic compound crystallization template until the copper ions are completely reacted; the method comprises the following steps of heating a reaction product to boiling because a flaky acidic compound crystallization template is only slightly soluble in cold water but is soluble in hot water and boiling water, dissolving the flaky acidic compound crystallization template in the boiling water, filtering while the flaky acidic compound crystallization template is hot to obtain a copper sheet crude product, washing the copper sheet crude product with 50% ethanol water solution for many times, filtering, repeatedly operating and purifying, adding absolute ethyl alcohol, stirring and dispersing, ultrasonically crushing for 1-6 hours by ultrasonic waves, filtering and drying to obtain flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm;
wherein the water used is any one of distilled water, deionized water, ultrapure water and high-purity water;
wherein the ultrasonic waves are ultrasonic waves with the frequency of 20 KHz-1 MHz and the power of 30W-15 KW;
or, the steps are as follows:
firstly, preparing a flaky alkaline compound crystallization template: according to the mass percentage of (0.1% -30.0%) of a surfactant, alkaline compound crystals and water: (0.1% -30.0%): (55.0% -95.0%) by mixing water and a surfactant, and stirring and dissolving completely to obtain a surfactant aqueous solution; heating a surfactant aqueous solution to boiling, adding an alkaline compound crystal, stirring until the alkaline compound crystal is fully dissolved, and filtering while the solution is hot to obtain a saturated solution of the alkaline compound crystal; placing the saturated solution of the alkaline compound crystal in a thermostat controlled at 50 ℃ for cooling crystallization, taking the material out of the thermostat when the temperature of the material is reduced to 50 ℃, and naturally cooling the material to room temperature to complete crystallization; filtering the materials to obtain a crude crystalline product of the flaky alkaline compound, recycling the mother liquor obtained by filtering, washing the crude crystalline product of the flaky alkaline compound with cold water at 0-5 ℃ of which the mass is 1-10 times that of the crystalline product for 2-3 times according to the mass of the crude crystalline product of the flaky alkaline compound, filtering to obtain crystals, and drying the crystals to obtain a crystalline template of the flaky alkaline compound;
preparing an alkaline mixture containing a crystalline template of a flaky alkaline compound and copper salt: according to the mass percentage of (35.0-95.0%) water, copper salt, complexing agent, copper plating brightener, dispersing agent, antioxidant, nickel salt, alkali and flaky alkaline compound crystallization template: (0.1% -30.0%): (0.1% -30.0%): (0.001% -10.0%): (0.1% -30.0%): (0.001% -10.0%): (0.001% -10.0%): (0.1% -30.0%): (0.1-30.0%) mixing water, copper salt, a complexing agent, a copper plating brightener, a dispersing agent, an antioxidant, a nickel salt and alkali, stirring until all materials are completely dissolved, adding a flaky alkaline compound crystallization template, stirring, performing ultrasonic treatment for 1-60 min, ultrasonically crushing the flaky alkaline compound crystallization template into flaky crystals with the particle size of 0.5-20.0 mu m, and obtaining an alkaline mixture containing the flaky alkaline compound crystallization template and the copper salt;
preparing a reducing agent aqueous solution: according to the mass percentage of (0.1% -30.0%) of the reducing agent and the water: (70.0% -99.9%) mixing water and a reducing agent, and stirring and dissolving completely to obtain a reducing agent aqueous solution;
preparing flake copper powder: cooling an alkaline mixture containing a flaky alkaline compound crystallization template and copper salt by using a room-temperature cold water bath to maintain the reaction system at room temperature, gradually adding a reducing agent aqueous solution under the stirring condition, reducing copper ions into metal copper, and chemically plating the metal copper on the surface of the flaky alkaline compound crystallization template until the copper ions completely react; the method comprises the following steps of heating a reaction product to boiling because a flaky alkaline compound crystallization template is only slightly soluble in cold water but is soluble in hot water and boiling water, dissolving the flaky alkaline compound crystallization template in the boiling water, filtering while the flaky alkaline compound crystallization template is hot to obtain a copper sheet crude product, washing the copper sheet crude product with 50% ethanol water solution for many times, filtering, repeatedly operating and purifying, adding absolute ethyl alcohol, stirring and dispersing, ultrasonically crushing for 1-6 hours by ultrasonic waves, filtering and drying to obtain flaky copper powder with the average particle size of 1.0-5.0 mu m and the average thickness of 10-40 nm;
wherein the water used is any one of distilled water, deionized water, ultrapure water and high-purity water;
wherein the ultrasonic waves are ultrasonic waves with the frequency of 20 KHz-1 MHz and the power of 30W-15 KW.
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| CN201810237827.2A CN108405876A (en) | 2018-03-16 | 2018-03-16 | The preparation method of flake copper powder in a kind of alkaline medium |
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| CN111922360B (en) * | 2020-10-19 | 2021-01-01 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
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| CN101274368B (en) * | 2008-04-30 | 2010-06-09 | 武汉理工大学 | Method for preparing nano-Cu uniformly coated Zn4Sb3 powder |
| JP5669265B2 (en) * | 2011-06-06 | 2015-02-12 | 独立行政法人物質・材料研究機構 | Porous copper sulfide, its production method and its use |
| CN102489318B (en) * | 2011-12-02 | 2013-06-19 | 南京林业大学 | Preparation method for porous nano p-CuS/n-CdS compound semiconductor photochemical catalyst |
| JP5563607B2 (en) * | 2012-01-20 | 2014-07-30 | 東洋アルミニウム株式会社 | Flaky conductive filler |
| CN104259472B (en) * | 2014-09-03 | 2016-09-28 | 江苏科技大学 | A kind of organic composite of superfine sheet copper powder and preparation method thereof |
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| CN108405876A (en) * | 2018-03-16 | 2018-08-17 | 南京林业大学 | The preparation method of flake copper powder in a kind of alkaline medium |
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