CN108188411A - The preparation method of flake copper in a kind of acid medium - Google Patents

The preparation method of flake copper in a kind of acid medium Download PDF

Info

Publication number
CN108188411A
CN108188411A CN201810237826.8A CN201810237826A CN108188411A CN 108188411 A CN108188411 A CN 108188411A CN 201810237826 A CN201810237826 A CN 201810237826A CN 108188411 A CN108188411 A CN 108188411A
Authority
CN
China
Prior art keywords
acid
copper
sheet
preparation
template
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201810237826.8A
Other languages
Chinese (zh)
Inventor
刘福生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Forestry University
Original Assignee
Nanjing Forestry University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Forestry University filed Critical Nanjing Forestry University
Priority to CN201810237826.8A priority Critical patent/CN108188411A/en
Publication of CN108188411A publication Critical patent/CN108188411A/en
Priority to CN201910135153.XA priority patent/CN109877336B/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0551—Flake form nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The present invention provides a kind of preparation method of flake copper, this method is using water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt, acid, sheet acid compound crystallization template and reducing agent as raw material, using the method for chemical plating, template surface copper facing is crystallized in sheet acid compound, up to copper ion, the reaction was complete, after reaction, through separating-purifying and Treatment technique for processing process, without ball milling, flake copper is directly obtained.Technical solution of the present invention is with low energy consumption; environmental pollution is small; simple production process, process route is brief, and large-scale production equipment investment is small; production efficiency is high; production cost is low, and the dispersion performance of product and the series of advantages such as conduct electricity very well are suitable for large-scale production; solve the problems, such as that ball-milling method prepares flake copper technique, industrialization prospect is had an optimistic view of.

Description

The preparation method of flake copper in a kind of acid medium
Technical field
The present invention relates to a kind of preparation methods of flake copper in acid medium, belong to the technology of preparing of metal powder material Field.
Background technology
Metal powder is divided into spherical shape, irregular granules shape, sheet and four kinds of threadiness by grain shape.With globular metallic powder and Granulated metal powder is different, and flaky metal powder has excellent catalytic performance, excellent sintering character, excellent thixotropy Energy, excellent adhesive force, good screen effect, excellent reflection of electromagnetic wave ability and splendid electric conductivity, are changing it The fields such as catalysis, powder metallurgy, conductive coating, conductive adhesive, electrically conductive ink and electrocondution slurry are learned to have a wide range of applications.
At present, chemical catalysis, electromagnetic screen coating, reflection of radar wave coating, conductive coating, conductive adhesive, conductive oil Ink and electrocondution slurry field use globular metallic powder or granulated metal powder mostly.In terms of electric conductivity, compared to piece Shape metal powder, globular metallic powder and the intergranular contact of granulated metal powder are point contacts, and electric conductivity is poor, metal powder Last dosage is big, and use cost is high；And flaky metal powder particle not only large specific surface area, and intergranular contact be line contact and Face contacts so that the intergranular contact area of flaky metal powder increases considerably, therefore, with globular metallic powder and graininess Metal powder is compared, and the amount that flaky metal powder particle forms flaky metal powder needed for the conductive channel of same conductivity energy is bright It is aobvious to reduce, and also there is thixotropic property with the thickened product that flaky metal powder is prepared, the settlement stability performance of product is notable It improves；So using flaky metal powder prepare conduction electrons material be both remarkably improved the electric conductivity of product, adhesive force and Storage stability, and the dosage of metal powder can be greatly lowered, it economizes on resources, reduces production cost, increase economic efficiency. In terms of chemical catalysis, electromagnetic shielding and reflection of radar wave, since flaky metal powder is significantly than globular metallic powder and graininess The large specific surface area of metal powder shows excellent catalytic performance, capability of electromagnetic shielding and reflection of radar wave performance.Therefore, The technology of preparing of flaky metal powder is concerned.
The technology report that chemical method prepares flaky metal powder is many, but these technology poor repeatabilities, available for industry That changes is few.At present, the flaky metal powder product of commercial type is mostly with globular metallic powder or granular metal powder End obtains under given conditions through ball milling, due to generally requiring inert gas shielding during ball milling, and must be added to appropriate lubrication Agent and dispersant ball milling are then classified, surface polishing and surface are modified to required granularity, last purified to handle To flaky metal powder；So ball-milling technology is generally all more complicated cumbersome, equipment requirement is high, and the production cycle is long, high energy consumption, Production cost is high；And the obtained flaky metal powder product purity of ball milling is not often high, grain size is big, sheet-like particle concave-convex surface Coarse, in irregular shape, became uneven, powder crack at edge, specific surface area is small.Therefore, it is prepared using new and effective method Flaky metal powder product is concerned.
Chemical plating is a kind for the treatment of technology that the coat of metal can be formed in surfaces of various materials, and the technology is because of technique letter Just, energy-saving and environmental protection and be increasingly subject to the concern of people.The principle of chemical plating is simple, different from plating, and chemical plating is that one kind is not required to Electricity consumption, but in the solution containing reducing agent and metal ion, using oxidation-reduction reaction principle, metal ion is restored Into metal and be deposited on a variety of materials surface formed coating method.
At present, have the chemical plating of document report, be mostly in metallic conductor and non-metallic isolator material surface The chemical plating of progress mainly achievees the purpose that basis material is decorated and protected, on compound crystal surface Learn the rarely seen document report of research of plating；Using flaky compound crystalline solid as template, sheet metal is prepared by the method for chemical plating The research of powder is even more rarely seen document report.Therefore, it using flaky compound crystalline solid as the template of chemical plating, inquires into flaking Reaction process condition and technical solution that object crystallization template surface carries out chemical plating are closed, inquires into and is carried from the separation of gained chemical plating product Pure and mild processing obtains the technical process and technology of flaky metal powder, provides a kind of completely new side for preparing flaky metal powder Method is undoubtedly of great significance.
The present invention provides one kind with water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt, acid, piece Shape acid compound crystallizes template and reducing agent as raw material, the method for preparing flake copper.This method is with low energy consumption, environment is dirty Contaminate the characteristics of small, simple production process, production process route are short, large-scale production investment is small, product purity is high and yield is high, production Industry promise well.At present, this method is there is not yet document report.
Invention content
The preparation method of flake copper in a kind of acid medium of the present invention, provides a kind of preparation side of flake copper Method, this method is with water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt, acid, sheet acid compound knot Crystal template and reducing agent are raw material, using the method for chemical plating, template surface copper facing are crystallized in sheet acid compound, until copper Ionic reaction is complete, after reaction, through separating-purifying and Treatment technique for processing process to get to flake copper.
1st, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that the system of flake copper It is standby to adopt the following technical scheme that：
1. sheet acid compound crystallizes the preparation of template：According to the matter of surfactant, acid compound crystallization and water It is (0.1%~30.0%): (0.1%~30.0%): the ratio of (55.0%~95.0%) to measure percentage, first by water and surface Activating agent mixes, to get to aqueous surfactant solution after stirring and dissolving is complete；Aqueous surfactant solution is heated to boiling It rises, adds in acid compound crystallization stirring to abundant dissolving, the saturated solution of acid compound crystallization is obtained by filtration while hot；It will be sour Property compound crystallization saturated solution be placed in temperature control crystallisation by cooling in 50 DEG C of insulating box, after temperature of charge drops to 50 DEG C, Material is taken out from insulating box, then allows material cooled to room temperature, makes crystallization complete；Material filtering obtains sheet acidity chemical combination Object crystallizes crude product, filters mother liquid obtained recycling, sheet acid compound crystallization crude product again by its quality, separately take 1~ Crystallization is obtained by filtration in 0~5 DEG C of cold water wash crystallization of 10 times of crystalline qualities 2~3 times, and crystallization, which is dried, obtains sheet acidity Compound crystallizes template；
2. acid compound containing sheet crystallizes the preparation of the acidic mixture of template and mantoquita：According to water, mantoquita, complexing Agent, copper brightener, dispersant, antioxidant, nickel salt, acid and sheet acid compound crystallization template mass percent be (35.0%~95.0%): (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%): the ratio of (0.1~30.0%) Water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt and acid are first mixed, stirred to all materials by example It is completely dissolved, adds sheet acid compound crystallization template, stir and handle 1~60min with ultrasonic echography, by sheet acid Property compound crystallization template to be ground into grain size with ultrasonic echography be to get to containing sheet after 0.5~20.0 μm of flaky crystal Acid compound crystallizes the acidic mixture of template and mantoquita；
3. the preparation of reducing agent aqueous solution：It is (0.1%~30.0%) according to the mass percent of reducing agent and water: The ratio of (70.0%~99.9%) mixes water with reducing agent, to get to reducing agent aqueous solution after stirring and dissolving is complete；
4. the preparation of flake copper：The acidic mixture room temperature that acid compound containing sheet is crystallized to template and mantoquita is cold Water-bath cooling makes reaction system maintain room temperature, under stirring condition, is gradually added reducing agent aqueous solution, copper ion is reduced into Metallic copper and chemical plating are plated to sheet acid compound crystallization template surface, and up to copper ion, the reaction was complete；Due to sheet acidity Compound crystallization template is only very slightly soluble in cold water, but be dissolved in hot water and boiling water, therefore, reaction product is heated to boiling, makes sheet Acid compound crystallization template is dissolved in boiling water, copper sheet crude product is obtained by filtration while hot, gained copper sheet crude product is through multiple 50% second After alcohol solution washing and filtering repetitive operation purification, then warp plus absolute ethyl alcohol and stirring are disperseed, ultrasonic echography crushes 1~6h, Filtering and dry technical process are to get to the sheet of copper that average grain diameter is 1.0~5.0 μm and average thickness is 10~40nm Powder；
Wherein, water used is any one of distilled water, deionized water, ultra-pure water and high purity water；
Wherein, ultrasonic wave used is the ultrasonic wave that frequency is 20KHz~1MHz, power is 30W~15KW.
2nd, in a kind of acid medium flake copper preparation method, it is characterised in that this method prepare flake copper technology Index is：
1) appearance：Brown powder；
2) purity：>=99.5%；
3) particle size range：0.2~10.0 μm；
4) average grain diameter：1.0~5.0 μm；
5) thickness range：5~70nm；
6) average thickness：10~40nm；
7) apparent density：1.9~2.9g/cm3；
8) tap density：2.5~3.4g/cm3。
3rd, in a kind of acid medium flake copper preparation method, it is characterised in that this method has following significant excellent Point：
(1) when preparing sheet acid compound crystallization template, the saturated solution that acid compound crystallizes is placed in temperature control and is existed Crystallisation by cooling in 50 DEG C of insulating box is to reduce the cooling velocity of material by reducing the temperature difference of material and environment, to reduce Crystallization rate, it is therefore an objective to make the flaky crystal to be formed more regular；The sheet acid compound crystallization crude product that material filtering obtains, 0~5 DEG C of cold water of 1~10 times of crystallization crude product quality is selected to wash 2~3 times, in order to reduce sheet acidity chemical combination The loss of object crystallization improves the preparation efficiency of sheet acid compound crystallization template；The crystallization of sheet acid compound refers to the acid Property compound crystal shape for flaky crystal, crystallized with sheet acid compound as template, copper is plated to sheet by chemical plating Acid compound crystallization template surface can form sheet of copper, and the preparation process of sheet of copper is simple；
(2) the sheet acid compound crystallization template selected must be slightly soluble in cold water, be dissolved in hot water and boiling water, in this way can be with After reaction product is heated to boiling, sheet acid compound crystallization template is made to be dissolved in boiling water, after filtering while hot, then through multiple 50% ethanol water wash and filtering repetitive operation, you can remove impurity and sheet acid compound crystallization template, impurity and Template is easy to remove, and purifying technique simply, quickly and efficiently, is conducive to be prepared the flake copper of high-purity, copper powder purity Up to more than 99.5%, product purity is high；
(3) firstly, since the sheet acid compound crystallization template selected is slightly soluble in cold water, hot water and boiling water are dissolved in, institute With the preparation reaction of sheet of copper is optimally maintained to be carried out at room temperature, is conducive to during the reaction, keep sheet acidification in this way The amount for closing object crystallization template is not reduced due to dissolving, and the amount of sheet acid compound crystallization template is just stablized, to flake copper thickness The controllability of degree is with regard to strong；Secondly as the sheet acid compound crystallization template selected belongs to acid compounds, reaction must be It is carried out under acidic environment, so, reactant must keep pH ＜ 7, avoid the amount of sheet acid compound crystallization template in alkalinity It is reduced due to acid-base neutralization reaction in environment, in this way, the amount of sheet acid compound crystallization template is just stablized, to flake copper thickness The controllability of degree is with regard to strong；In the case that mantoquita dosage determines, the use of template is crystallized by changing sheet acid compound for third Amount adjusts the ratio of mantoquita and sheet acid compound crystallization template, you can the effectively thickness of control flake copper；4th, it uses Ultrasonic echography crushes the sheet of copper that sheet acid compound crystallization template and chemical plating obtain, when adjusting ultrasonic echography crushing Between, the grain size of flake copper can be effectively controlled, size controlling method is simple and effective；In short, the present invention both can effectively control sheet The thickness of copper powder, and the grain size of flake copper can be effectively controlled, the flake copper of high-specific surface area, specific surface area can be prepared It is 3~10 times of particle copper powder；
(4) in the preparation process of flake copper, the purpose of copper brightener is added, is to put down chemical plating copper layer light It is whole, improve the flatness and finish of flake copper particle surface；In the preparation process of flake copper, the mesh of complexing agent is added , be the dynamic equilibrium in order to form free copper ion and copper complex ion in the reaction system, with effectively control free copper from The concentration of son, and then the reduction reaction speed of copper ion and the deposition velocity of copper are controlled, to obtain uniform copper coating and be Make chemical plating copper layer light smooth, can also effectively improve the flatness and finish of flake copper particle surface；This is all advantageous In improving the intergranular contact area of flake copper, the electric conductivity of the product with flake copper particle formulation is improved, with not adding The flake copper that copper brightener is prepared with complexing agent is added to compare, the electric conductivity of flake copper prepared by the present invention can improve 30% or so, improvement effect is apparent；
(5) in the preparation process of flake copper, the purpose of dispersant is added, is particle agglomeration in order to prevent, improves sheet The dispersibility of copper powder particle, so that flake copper is easily dispersed when preparing product with flake copper, user is easy to use, improves The performance of flake copper；
(6) it compared with using the thick product that spherical copper powder is prepared, is prepared using flake copper produced by the invention Thick product, such as conductive adhesive, electrocondution slurry, conductive coating and electrically conductive ink, since flake copper is in sticky system In have thixotropic property, make product sedimentation stability and storage stability improve 50% or so, the product stability of preparation is good；
(7) copper belongs to soft metal, and copper powder particle is pressurized or is impacted and can be laminated agglomerating, therefore, ball mill grinding and grinds Be milled it is broken can cause to be laminated agglomerating and reunite between copper powder particle, the present invention is using ultrasonic echography comminuting method by copper sheet powder Average grain diameter is broken into as 1.0~5.0 μm of flake coppers, copper powder particle can be effectively prevent to reunite；
(8) after preparing flake copper the reaction was complete, when reaction product is heated to boiling, due to sheet acid compound Crystallization template is slightly soluble in cold water, but be dissolved in hot water and boiling water, therefore, after filtering to take out copper sheet while hot, sheet acid compound knot Crystal template is stayed in the mother liquor of filtering gained, and after mother liquor cooling, sheet acid compound crystallization template crystallizes precipitation again, precipitation Again with after the method separating-purifying of recrystallization, sheet acid compound crystallization template can recycle, and therefore, both save for crystallization Template resource and production cost is reduced, and reduce the discharge of pollutant, improve economic benefit and environmental benefit；
(9) technological requirement that the mantle plate method reported prepares flake copper is high, severe reaction conditions, and control is improper often What is obtained is graininess copper powder rather than flake copper, and therefore, the technique repetition stability that mantle plate method prepares flake copper is poor, Unstable product quality or even it cannot get flake copper, production success rate is not high；The dura mater plate method reported prepares sheet Complex process and processing cost height that the technology of copper powder is difficult to remove there are template again, even can not remove or remove template etc. Problem, such as copper powder is prepared as template using titanium dioxide, Woelm Alumina substance, template is not only difficult to remove or even can not remove Go, i.e., remove template using complicated technology, template is also difficult to cleared, and processing cost is high, and product purity is not high, and often also no To flake copper；Biological template prepares flake copper operating procedure complexity, and control difficulty is high, and reaction process is slower, production Efficiency is low；The success rate that technical solution of the present invention prepares flake copper is 100%, and template easily removes, and product purity exists More than 99.5%, production cost is low, and production efficiency is high；
(10) it is to form one layer of protection in copper coating surface to prepare during flake copper using the purpose of antioxidant Film, the copper coating to prevent limited step shape acid compound crystallization template surface are aoxidized；
(11) nickel salt is used during preparing flake copper, is to have using nickel salt to the redox reaction of electroless copper There is very strong catalytic action, be smoothed out the electroless copper reaction of sheet acid compound crystallization template surface；
(12) technical solution of the present invention have low energy consumption, environmental pollution is small, simple production process, process route letter Short, large-scale production equipment investment is small, and production efficiency is high, and production cost is low, the dispersion performance of product and the system that conducts electricity very well Row advantage, is suitable for large-scale production, solves the problems, such as that existing ball-milling method and template prepare flake copper technique, Industrialization prospect is had an optimistic view of.
4th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that ultrasonic wave used It is the ultrasonic wave that frequency is 20KHz~1MHz, power is 30W~15KW.
5th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that surface used live Property agent is lauryl sodium sulfate, ammonium lauryl sulfate, dodecyl sulphate potassium, dodecyl sulphate monoethanolamine, 12 Alkylsurfuric acid diethanol amine, dodecyltriethanolamine sulfate, sodium hexadecyl sulfate, hexadecyl hydrosulfate ammonium, cetyl Potassium sulfate, hexadecyl hydrosulfate monoethanolamine, hexadecyl hydrosulfate diethanol amine, hexadecyl hydrosulfate triethanolamine, dodecane Base polyethenoxy ether sodium sulfate, dodecyl polyoxyethylene ether ammonium sulfate, dodecyl polyoxyethylene ether potassium sulfate, dodecyl Polyoxyethylene ether diethanolamine, dodecyl polyoxyethylene ether sulfate, dodecyl polyoxyethylene ether sulfuric acid Triethanolamine, sodium cetanesulfonate, cetyl ichthyodin, cetyl potassium sulfonate, cetyl sulfonic acid monoethanolamine, ten Six alkyl sulfonic acid diethanol amine, cetyl sulfonic acid triethanolamine, neopelex, dodecyl benzene sulfonic acid ammonium, ten Dialkyl benzene sulfonic acids potassium, dodecyl benzene sulfonic acid monoethanolamine, dodecyl benzene sulfonic acid diethanol amine, dodecyl benzene sulfonic acid three Ethanol amine, nonylphenol polyoxyethylene ether sulfate, nonylphenol polyoxyethylene ether ammonium sulfate, nonylphenol polyoxyethylene ether potassium sulfate, Nonylphenol polyoxyethylene ether diethanolamine, nonylphenol polyoxyethylene ether sulfate, nonylphenol polyoxyethylene ether sulphur Triethylenetetraminehexaacetic acid hydramine, coconut oil alkanolamide, lauroylamidopropyl betaine, Cocoamidopropyl betaine, soyamide propyl Glycine betaine, octadecyl dimethyl amine oxide and dodecyldimethylamine oxide any one or more of.
6th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that：
1. sheet acid compound crystallization template used is 4- metoxyphenols, benzoic acid, boric acid, 2,6- dimethyl benzenes Any one of phenol and decanedioic acid；
2. mantoquita used is any in copper citrate, copper sulphate, copper nitrate, cupric tartrate, copper chloride and copper acetate Kind is a variety of；
3. antioxidant used is benzotriazole, mercapto benzothiazole, amineothiot, n-propyl mercaptan, isopropyl Mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, iso-butyl mercaptan, butyl mercaptan, tertiary butyl mercaptan, isoamyl mercaptan, n-pentyl Mercaptan, n-hexyl mercaptan, n octylmercaptan, n-nonyl mercaptan, n-dodecyl mercaptan, tert-dodecylmercaotan, myristyl Mercaptan, hexadecyl mercaptan, Stearyl mercaptan, benzyl mercaptan and phenethyl mercaptan any one or more of；
4. nickel salt used is any in nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, citric acid nickel and tartaric acid nickel Kind is a variety of.
7th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that complexing agent used It is N-hydroxyethyl-ethylenediamine triacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid trisodium, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, ethylenediamine Tetraacethyl, disodium ethylene diamine tetraacetate, citric acid, sodium citrate, potassium citrate, ammonium citrate, tartaric acid, sodium tartrate, wine Stone acid potassium, sodium potassium tartrate tetrahydrate, glycerine, triethanolamine, potassium antimony tartrate and ammonium tartrate any one or more of.
8th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that plating bronzing used Bright dose be 2- aminoothyl mercaptans, thiocarbamide, nabam, sodium polydithio-dipropyl sulfonate, 2-mercaptobenzimidazole and 1,2- ethylene thiourea any one or more of.
9th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that dispersant used It is polyvinylpyrrolidone, carboxymethyl cellulose, sodium carboxymethylcellulose, methylcellulose, hydroxyethyl cellulose, methylol fibre Tie up element, hydroxypropyl cellulose, gelatin, polyacrylic acid, Sodium Polyacrylate, ammonium polyacrylate, polyacrylic acid potassium, polyvinyl alcohol, Ah Draw uncle's natural gum and polyethylene glycol any one or more of.
10th, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that acid used is Benzene sulfonic acid, p-methyl benzenesulfonic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, lactic acid, nitric acid, sulfuric acid, hydrochloric acid, fumaric acid With maleic acid any one or more of.
11st, in a kind of acid medium of the present invention flake copper preparation method, it is characterised in that reduction used Agent is ortho phosphorous acid, sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine, hydrazine sulfate, dimethylamino borine, glyoxalic acid and acetone Aldehyde any one or more of.
Specific embodiment
The present invention is described in further detail with reference to embodiment.It should be noted that it is of the present invention below A kind of acid medium in flake copper preparation method nonlimiting examples, providing for these embodiments be only Achieve the purpose that be described in further detail the present invention, not to the present invention in any form with substantial limitation；It must Note that it is assumed that for those skilled in the art, under the premise of the method for the present invention is not departed from, those skilled in the art Several improvement, supplement and optimization can also be made, these, which improve, supplement and optimize, also should be regarded as protection scope of the present invention；Institute Have and be familiar with those skilled in the art, in the case where not departing from the method for the present invention range, utilize technical solution of the present invention Process modification, scheme supplement and raw material proportioning optimization are carried out with technology contents, is accordingly to be regarded as the equivalent embodiment of the present invention；Meanwhile Substantial technological any equivalent improvement made for the present invention, supplement and the optimization of all methods according to the present invention, also belong to this hair The technical scope of bright method；In the examples below that, unless stated otherwise, all percentage is all referring to mass percent.
Table one, Examples 1 to 8 raw material and proportioning
It notes [1]：Peng Shuai, Zhu Xiaoyun.Influence research of the presoma to copper powder density in liquid-phase reduction two-step method.Function material Material, 2014,24 (45)：24144-24147,24152.
According to the raw material and proportioning of Examples 1 to 8 in table one, the detailed technology scheme and preparation process of Examples 1 to 8 walk It is rapid as follows：
1. sheet acid compound crystallizes the preparation of template：According to the surfactant of Examples 1 to 8, acidity in table one Compound crystallizes and the mass percent of water, and first water is mixed with surfactant, is lived after stirring and dissolving is complete to get to surface Property agent aqueous solution；Aqueous surfactant solution is heated to boiling, acid compound crystallization stirring is added in and is dissolved to abundant, while hot The saturated solution of acid compound crystallization is obtained by filtration；The saturated solution that acid compound crystallizes is placed in perseverance of the temperature control at 50 DEG C Crystallisation by cooling in incubator after temperature of charge drops to 50 DEG C, takes out material, then material is allowed to naturally cool to room from insulating box Temperature makes crystallization complete：Material filtering obtains sheet acid compound crystallization crude product, filters mother liquid obtained recycling, sheet Acid compound crystallization crude product separately takes 0~5 DEG C of cold water wash crystallization 2~3 of 1~10 times of crystalline quality again by its quality It is secondary, crystallization is obtained by filtration, crystallization, which is dried, obtains sheet acid compound crystallization template；
2. acid compound containing sheet crystallizes the preparation of the acidic mixture of template and mantoquita：According to embodiment 1 in table one Water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt, acid and sheet acid compound crystallizing mould in~8 Water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt and acid are first mixed, stirred by the mass percent of plate Mix to all materials and be completely dissolved, add sheet acid compound crystallization template, stir and with ultrasonic echography processing 1~ Sheet acid compound crystallization template is ground into the flaky crystal that grain size is 0.5~20.0 μm by 60min with ultrasonic echography Afterwards to get crystallizing the acidic mixture of template and mantoquita to acid compound containing sheet；
3. the preparation of reducing agent aqueous solution：It, will according to the mass percent of reducing agent and water in Examples 1 to 8 in table one Water is mixed with reducing agent, to get to reducing agent aqueous solution after stirring and dissolving is complete；
4. the preparation of flake copper：The acidic mixture room temperature that acid compound containing sheet is crystallized to template and mantoquita is cold Water-bath cooling makes reaction system maintain room temperature, under stirring condition, is gradually added reducing agent aqueous solution, copper ion is reduced into Metallic copper and chemical plating are plated to sheet acid compound crystallization template surface, and up to copper ion, the reaction was complete；Due to sheet acidity Compound crystallization template is only very slightly soluble in cold water, but be dissolved in hot water and boiling water, therefore, reaction product is heated to boiling, makes sheet Acid compound crystallization template is dissolved in boiling water, copper sheet crude product is obtained by filtration while hot, gained copper sheet crude product is through multiple 50% second After alcohol solution washing and filtering repetitive operation purification, then warp plus absolute ethyl alcohol and stirring are disperseed, ultrasonic echography crushes 1~6h, Filtering and dry technical process are to get to the sheet of copper that average grain diameter is 1.0~5.0 μm and average thickness is 10~40nm Powder；
Wherein, ultrasonic wave used is the ultrasonic wave that frequency is 20KHz~1MHz, power is 30W~15KW.

Claims (10)

1. a kind of preparation method of flake copper in acid medium, it is characterised in that：
1. sheet acid compound crystallizes the preparation of template：According to the quality hundred of surfactant, acid compound crystallization and water Divide than being (0.1%~30.0%): (0.1%~30.0%): the ratio of (55.0%~95.0%), first by water and surface-active Agent mixes, to get to aqueous surfactant solution after stirring and dissolving is complete；Aqueous surfactant solution is heated to boiling, is added Enter acid compound crystallization stirring to abundant dissolving, the saturated solution of acid compound crystallization is obtained by filtration while hot；By acidification The saturated solution for closing object crystallization is placed in temperature control crystallisation by cooling in 50 DEG C of insulating box, after temperature of charge drops to 50 DEG C, from perseverance Material is taken out in incubator, then allows material cooled to room temperature, makes crystallization complete；Material filtering obtains sheet acid compound knot Brilliant crude product, filters mother liquid obtained recycling, and sheet acid compound crystallization crude product separately takes 1~10 times again by its quality In 0~5 DEG C of cold water wash crystallization 2~3 times of crystalline quality, crystallization is obtained by filtration, crystallization, which is dried, obtains sheet acidity chemical combination Object crystallizes template；
2. acid compound containing sheet crystallizes the preparation of the acidic mixture of template and mantoquita：According to water, mantoquita, complexing agent, plating The mass percent that copper brightener, dispersant, antioxidant, nickel salt, acid and sheet acid compound crystallize template is (35.0% ~95.0%): (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%): the ratio of (0.1~30.0%) first will Water, mantoquita, complexing agent, copper brightener, dispersant, antioxidant, nickel salt and acid mixing, are stirred completely molten to all materials Solution adds sheet acid compound crystallization template, stirs and handle 1~60min with ultrasonic echography, by sheet acidity chemical combination It is to get to acidification containing sheet after 0.5~20.0 μm of flaky crystal that object, which crystallizes template and is ground into grain size with ultrasonic echography, Close the acidic mixture of object crystallization template and mantoquita；
3. the preparation of reducing agent aqueous solution：It is (0.1%~30.0%) according to the mass percent of reducing agent and water: (70.0% ~99.9%) ratio mixes water with reducing agent, to get to reducing agent aqueous solution after stirring and dissolving is complete；
4. the preparation of flake copper：Acid compound containing sheet is crystallized to the acidic mixture room temperature cold bath of template and mantoquita Cooling makes reaction system maintain room temperature, under stirring condition, is gradually added reducing agent aqueous solution, copper ion is reduced into metal Copper and chemical plating are plated to sheet acid compound crystallization template surface, and up to copper ion, the reaction was complete；Due to sheet acidity chemical combination Object crystallization template is only very slightly soluble in cold water, but be dissolved in hot water and boiling water, therefore, reaction product is heated to boiling, and makes sheet acid Compound crystallization template is dissolved in boiling water, copper sheet crude product is obtained by filtration while hot, gained copper sheet crude product is through multiple 50% ethanol water After solution washs and filters repetitive operation purification, then through adding absolute ethyl alcohol and stirring dispersion, 1~6h of ultrasonic echography crushing, filtering With dry technical process to get the flake copper for being 1.0~5.0 μm to average grain diameter and average thickness is 10~40nm；
Wherein, water used is any one of distilled water, deionized water, ultra-pure water and high purity water；
Wherein, ultrasonic wave used is the ultrasonic wave that frequency is 20KHz~1MHz, power is 30W~15KW.
2. preparation method described in claim 1, it is characterised in that the technical indicator of the flake copper of preparation is：
1) appearance：Brown powder；
2) purity：>=99.5%；
3) particle size range：0.2~10.0 μm；
4) average grain diameter：1.0~5.0 μm；
5) thickness range：5~70nm；
6) average thickness：10~40nm；
7) apparent density：1.9~2.9g/cm3；
8) tap density：2.5~3.4g/cm3。
3. preparation method described in claim 1, it is characterised in that ultrasonic wave used is that frequency is 20KHz~1MHz, power Ultrasonic wave for 30W~15KW.
4. preparation method described in claim 1, it is characterised in that surfactant used is lauryl sodium sulfate, 12 Alkylsurfuric acid ammonium, dodecyl sulphate potassium, dodecyl sulphate monoethanolamine, dodecyl sulphate diethanol amine, dodecyl Sulfuric acid triethanolamine, sodium hexadecyl sulfate, hexadecyl hydrosulfate ammonium, hexadecyl hydrosulfate potassium, hexadecyl hydrosulfate monoethanol Amine, hexadecyl hydrosulfate diethanol amine, hexadecyl hydrosulfate triethanolamine, dodecyl polyoxyethylene ether sodium sulphate, dodecane Base polyoxyethylene ether ammonium sulfate, dodecyl polyoxyethylene ether potassium sulfate, dodecyl polyoxyethylene ether diethanolamine, ten Dialkyl group laureth sulfate, dodecyl polyoxyethylene ether sulfuric acid triethanolamine, sodium cetanesulfonate, ten Six alkyl sulfonic acid ammoniums, cetyl potassium sulfonate, cetyl sulfonic acid monoethanolamine, cetyl sulfonic acid diethanol amine, hexadecane Base sulfonic acid triethanolamine, neopelex, dodecyl benzene sulfonic acid ammonium, Potassium dodecylbenzenesulfonate, detergent alkylate Sulfonic acid monoethanolamine, dodecyl benzene sulfonic acid diethanol amine, dodecyl benzene sulfonic acid triethanolamine, nonylphenol polyoxyethylene ether sulphur Sour sodium, nonylphenol polyoxyethylene ether ammonium sulfate, nonylphenol polyoxyethylene ether potassium sulfate, nonylphenol polyoxyethylene ether sulfuric acid monoethanol Amine, nonylphenol polyoxyethylene ether sulfate, nonylphenol polyoxyethylene ether sulfuric acid triethanolamine, coconut oil alkanolamide, Lauroylamidopropyl betaine, Cocoamidopropyl betaine, soyamide propyl betaine, octadecyl dimethyl amine oxide It is any one or more with dodecyldimethylamine oxide etc..
5. preparation method described in claim 1, it is characterised in that：
1. sheet acid compound crystallization template used be 4- metoxyphenols, benzoic acid, boric acid, 2,6- xylenols and Any one of decanedioic acid；
2. mantoquita used be any one of copper citrate, copper sulphate, copper nitrate, cupric tartrate, copper chloride and copper acetate or It is a variety of；
3. antioxidant used for benzotriazole, mercapto benzothiazole, amineothiot, n-propyl mercaptan, isopropyl mercaptan, Tert-butyl mercaptan, sec-butyl mercaptan, iso-butyl mercaptan, butyl mercaptan, tertiary butyl mercaptan, isoamyl mercaptan, n-amylmercaptane, N-hexyl mercaptan, n octylmercaptan, n-nonyl mercaptan, n-dodecyl mercaptan, tert-dodecylmercaotan, tetradecyl mercaptan, Any one or more ofs such as hexadecyl mercaptan, Stearyl mercaptan, benzyl mercaptan and phenethyl mercaptan；
4. nickel salt used be any one of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, citric acid nickel and tartaric acid nickel or It is a variety of.
6. preparation method described in claim 1, it is characterised in that complexing agent used is N-hydroxyethyl-ethylenediamine triacetic acid, N- Trisodium hydroxyethylene diamine triacetate, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, lemon Lemon acid, sodium citrate, potassium citrate, ammonium citrate, tartaric acid, sodium tartrate, potassium tartrate, sodium potassium tartrate tetrahydrate, glycerine, three second Hydramine, potassium antimony tartrate and ammonium tartrate any one or more of.
7. preparation method described in claim 1, it is characterised in that copper brightener used be 2- aminoothyl mercaptans, thiocarbamide, Any one of nabam, sodium polydithio-dipropyl sulfonate, 2-mercaptobenzimidazole and 1,2- ethylene thiourea It is or a variety of.
8. preparation method described in claim 1, it is characterised in that dispersant used is polyvinylpyrrolidone, carboxymethyl fibre It ties up element, sodium carboxymethylcellulose, methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gelatin, gather Any in acrylic acid, Sodium Polyacrylate, ammonium polyacrylate, polyacrylic acid potassium, polyvinyl alcohol, gum arabic and polyethylene glycol Kind is a variety of.
9. preparation method described in claim 1, it is characterised in that acid used is benzene sulfonic acid, p-methyl benzenesulfonic acid, formic acid, second Any one of acid, propionic acid, citric acid, tartaric acid, lactic acid, nitric acid, sulfuric acid, hydrochloric acid, fumaric acid and maleic acid etc. It is or a variety of.
10. preparation method described in claim 1, it is characterised in that reducing agent used is ortho phosphorous acid, sodium hypophosphite, boron Any one or more ofs such as sodium hydride, potassium borohydride, hydrazine, hydrazine sulfate, dimethylamino borine, glyoxalic acid and pyroracemic aldehyde.
CN201810237826.8A 2018-03-16 2018-03-16 The preparation method of flake copper in a kind of acid medium Withdrawn CN108188411A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201810237826.8A CN108188411A (en) 2018-03-16 2018-03-16 The preparation method of flake copper in a kind of acid medium
CN201910135153.XA CN109877336B (en) 2018-03-16 2019-02-21 Preparation method of flaky copper powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810237826.8A CN108188411A (en) 2018-03-16 2018-03-16 The preparation method of flake copper in a kind of acid medium

Publications (1)

Publication Number Publication Date
CN108188411A true CN108188411A (en) 2018-06-22

Family

ID=62595660

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810237826.8A Withdrawn CN108188411A (en) 2018-03-16 2018-03-16 The preparation method of flake copper in a kind of acid medium

Country Status (1)

Country Link
CN (1) CN108188411A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109877336A (en) * 2018-03-16 2019-06-14 南京林业大学 A kind of preparation method of flake copper powder
CN111922360A (en) * 2020-10-19 2020-11-13 西安宏星电子浆料科技股份有限公司 Preparation method of nano copper powder

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109877336A (en) * 2018-03-16 2019-06-14 南京林业大学 A kind of preparation method of flake copper powder
CN111922360A (en) * 2020-10-19 2020-11-13 西安宏星电子浆料科技股份有限公司 Preparation method of nano copper powder

Similar Documents

Publication Publication Date Title
CN108356282A (en) The preparation method of flake silver powder in a kind of acid medium
CN108580920A (en) A kind of preparation method of flake silver powder
CN101834004B (en) Silver powder for conductive silver paste of solar battery electrode and preparation method thereof
CN102234116B (en) Method for preparing nano white carbon black by utilizing iron tailings
CN103962570B (en) A kind of preparation method of nano-nickel powder
WO2016155313A1 (en) High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor
CN108356281A (en) A kind of preparation method of Nickel Powder
CN101274847A (en) Spinel type ferrite magnetic hollow microsphere and preparation thereof
CN102205422A (en) Nano copper powder for electronic paste and preparation process
CN109877336A (en) A kind of preparation method of flake copper powder
CN109663932A (en) A kind of preparation method of flake silver powder
CN108188411A (en) The preparation method of flake copper in a kind of acid medium
CN111717938B (en) Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof
CN110407238A (en) A kind of method that crystal seed method prepares flaky alpha-alumina crystals
CN103227322A (en) Quaternary lithium-ion battery positive electrode material and preparation method thereof
CN106169580B (en) A kind of preparation method of battery-grade iron phosphate/graphene composite material
CN111600010A (en) Preparation method of single crystal large particles of ternary material
CN108356283A (en) The preparation method of sheet cobalt powder in a kind of acid medium
CN108500287A (en) The preparation method of Nickel Powder in a kind of acid medium
CN105731553A (en) Drusy ternary anode material precursor and preparation method thereof
CN105375078A (en) Method for circularly preparing spherical lithium nickel cobalt manganese oxide by lithium-ion battery positive plate
CN108500288A (en) A kind of preparation method of flake copper powder
CN108500289A (en) The preparation method of flake silver powder in a kind of alkaline medium
CN109671937B (en) In-situ synthesis method of transition metal oxide/graphene composite material
CN108405876A (en) The preparation method of flake copper powder in a kind of alkaline medium

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20180622