CN109877336A - A kind of preparation method of flake copper powder - Google Patents
A kind of preparation method of flake copper powder Download PDFInfo
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- CN109877336A CN109877336A CN201910135153.XA CN201910135153A CN109877336A CN 109877336 A CN109877336 A CN 109877336A CN 201910135153 A CN201910135153 A CN 201910135153A CN 109877336 A CN109877336 A CN 109877336A
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Abstract
The invention discloses a kind of preparation methods of flake copper powder, this method is with water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt, sublimable flaky compound crystallization template or contains acid compound crystallization template or the crystallization template of alkali compounds containing sheet, and reducing agent is raw material, using the method for chemical plating, template surface copper facing is crystallized in compound, until copper ion fully reacting, after reaction, through separating-purifying and Treatment technique for processing process, without ball milling, flake copper powder 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; high production efficiency; 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 powder technique, industrialization prospect is good.
Description
Technical field
The invention belongs to the preparation technical fields of metal powder material, are related to a kind of preparation method of flake copper powder.
Background technique
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 properties, 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.
Currently, 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 contact, 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 of flaky metal powder needed for flaky metal powder particle forms 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 significant
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 obviously than globular metallic powder and graininess
The large specific surface area of metal powder shows excellent catalytic performance, electromagnetic shielding performance and reflection of radar wave performance.Therefore,
The technology of preparing of flaky metal powder is concerned.
The technical report that chemical method prepares flaky metal powder is many, but these technology poor repeatabilities, can be used for industry
That changes is few.Currently, the flaky metal powder product of commercial type, is mostly with globular metallic powder or granular metal powder
End is obtained through ball milling under given conditions, due to generally requiring inert gas shielding when ball milling, and must be added to lubrication appropriate
Agent and dispersing agent ball milling are then classified, the modification of surface polishing and surface to required granularity, finally 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, energy consumption height,
High production cost；And the obtained flaky metal powder product purity of ball milling is not often high, partial 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 that one kind can be in the processing technique of the surfaces of various materials formation coat of metal, 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
The method that a variety of materials surface forms coating is deposited at metal.
It is mostly in metallic conductor and non-metallic isolator material surface currently, having chemical plating reported in the literature
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 mentioned 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.
Summary of the invention
Goal of the invention: the deficiencies in the prior art are directed to, the object of the present invention is to provide a kind of systems of flake copper powder
Preparation Method, with low energy consumption, environmental pollution is small, simple production process, production process route is short, large-scale production investment is small, produces
Product purity is high and the high feature of yield.
Technical solution: in order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A kind of preparation method of flake copper powder, steps are as follows:
1) preparation sheet acid compound crystallization template or alkali compounds containing sheet crystallize template；
2) mixture containing sublimable flaky compound crystallization template and mantoquita is prepared；Or configuration acidification containing sheet is closed
The acidic mixture of object crystallization template and mantoquita；Or the alkalinity mixing of configuration alkali compounds containing sheet crystallization template and mantoquita
Object；
3) ratio for being 0.1%~30.0%: 70.0%~99.9% according to the mass percent of reducing agent and water, by water
It is mixed with reducing agent, after stirring and dissolving is complete, makes reducing agent aqueous solution；
4) by mixture, acidic mixture or the alkaline mixt in step 2), step 3) preparation of flake copper powder: is added
In reducing agent aqueous solution, copper ion is reduced into metallic copper and chemical plating is plated to crystallization template surface, until copper ion react
Completely；When reactant is mixture, repetition is washed and filtered after washing several times again to reaction product through filtering resulting solid matter
Operation obtains copper-plated sublimable flaky compound crystallization, and the material is within the temperature range of 70~150 DEG C, through decompression heat
Processing makes the crystallization distillation of sublimable flaky compound, is sublimated recycling after sublimable flaky compound crystallization distillation with cold-trap
And can be recycled, until the crystallization of sublimable flaky compound obtains copper sheet after eliminating, gained copper sheet is again through adding dehydrated alcohol
Be dispersed with stirring, ultrasonic echography crush 1~6h, filtering and drying technical process；When reactant is acidic mixture or alkalinity
When mixture, reaction product is heated to boiling, so that flaky compound crystallization template is dissolved in boiling water, it is thick that copper sheet is obtained by filtration while hot
Product, gained copper sheet crude product is after multiple 50% ethanol water washs and filters repetitive operation purification, then warp plus anhydrous second
Alcohol is dispersed with stirring, ultrasonic echography crushes the technical process of 1~6h, filtering and drying；It is final obtain average grain diameter be 1.0~
5.0 μm and the average flake copper powder with a thickness of 10~40nm；
In step 1), sheet acid compound crystallize template preparation: according to surfactant, acid compound crystallization and
The mass percent of water is (0.1%~30.0%): (0.1%-30.0%): the ratio of (55.0%~95.0%), first by water
It is mixed with surfactant, arrives aqueous surfactant solution after stirring and dissolving is complete；Aqueous surfactant solution is heated
To boiling, acid compound crystallization stirring is added to abundant dissolution, the saturated solution of acid compound crystallization is obtained by filtration while hot；
The saturated solution that acid compound crystallizes is placed in temperature control crystallisation by cooling in 50 DEG C of insulating box, when temperature of charge drops to 50 DEG C
Afterwards, material is taken out from insulating box, then allows material cooled to room temperature, keeps crystallization complete；Material filtering obtains sheet acidity
Compound crystallizes crude product, filters mother liquid obtained recycling, and sheet acid compound crystallization crude product is pressed its quality again, separately taken
Crystallization is obtained by filtration in 0~5 DEG C of cold water wash crystallization 2~3 times of 1~10 times of crystalline quality, and crystallization, which is dried, obtains sheet acid
Property compound crystallize template.
In step 1), sheet alkali compounds crystallize template preparation: according to surfactant, alkali compounds crystallization and
The mass percent of water is (0.1%~30.0%): (0.1%~30.0%): the ratio of (55.0%~95.0%), first by water
It is mixed with surfactant, arrives aqueous surfactant solution after stirring and dissolving is complete；Aqueous surfactant solution is heated
To boiling, alkali compounds crystallization stirring is added to abundant dissolution, the saturated solution of alkali compounds crystallization is obtained by filtration while hot；
The saturated solution that alkali compounds crystallizes is placed in temperature control crystallisation by cooling in 50 DEG C of insulating box, when temperature of charge drops to 50 DEG C
Afterwards, material is taken out from insulating box, then allows material cooled to room temperature, keeps crystallization complete；Material filtering obtains sheet alkalinity
Compound crystallizes crude product, filters mother liquid obtained recycling, and sheet alkali compounds crystallization crude product is pressed its quality again, separately taken
Crystallization is obtained by filtration in 0~5 DEG C of cold water wash crystallization 2~3 times of 1~10 times of crystalline quality, and crystallization, which is dried, obtains sheet alkali
Property compound crystallize template.
In step 2): preparing the method for crystallizing the mixture of template and mantoquita containing sublimable flaky compound are as follows: according to
Water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and sublimable flaky compound crystallize template
Mass percent 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%): the ratio of (0.1~30.0%)
Example first mixes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant and nickel salt, stirs complete to all materials
Dissolution adds sublimable flaky compound crystallization template, stirs and handle 1~60min with ultrasonic echography, can distil
Flaky compound crystallization template to be ground into partial size with ultrasonic echography be after 0.5~20.0 μm of flaky crystal to get to containing
The mixture of sublimable flaky compound crystallization template and mantoquita.
In step 2): the method for the acidic mixture of configuration acid compound containing sheet crystallization template and mantoquita are as follows: according to
The matter of water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt, acid and sheet acid compound crystallization template
Measuring percentage 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%): (0.1~
30.0%) ratio first closes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and acid-mixed, stirring
Be completely dissolved to all materials, 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 partial size is 0.5~20.0 μm with ultrasonic echography by 60min
Afterwards to get the acidic mixture for crystallizing template and mantoquita to acid compound containing sheet.
In step 2): the method for the alkaline mixt of configuration alkali compounds containing sheet crystallization template and mantoquita are as follows: according to
The matter of water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt, alkali and sheet alkali compounds crystallization template
Measuring percentage 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%): (0.1~
30.0%) ratio first mixes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and alkali, stirring
Be completely dissolved to all materials, add sheet alkali compounds crystallization template, stir and with ultrasonic echography processing 1~
Sheet alkali compounds crystallization template is ground into the flaky crystal that partial size is 0.5~20.0 μm with ultrasonic echography by 60min
Afterwards to get the alkaline mixt for crystallizing template and mantoquita to alkali compounds containing sheet.
The preparation method of the flake copper powder, acid used be 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 and maleic acid are any one or more of.
The preparation method of the flake copper powder, alkali used are ammonia, ammonium hydroxide, ethylenediamine, n-butylamine, n-amylamine, diethyl
Alkene triamine, triethylene tetramine and tetraethylenepentamine are any one or more of.
The preparation method of the flake copper powder, sublimable flaky compound crystallization template used is borneol, benzene first
Any one of acid, naphthalene and anthracene.
The preparation method of the flake copper powder, sheet acid compound crystallization template used be 4- metoxyphenol,
Any one of benzoic acid, boric acid, 2,6- xylenol and decanedioic acid.
The preparation method of the flake copper powder, sheet alkali compounds crystallization template used is antifebrin, to first
Aniline, naphthalidine and 2- naphthylamines are any one or more of.
The preparation method of the flake copper powder, mantoquita used be copper citrate, copper sulphate, copper nitrate, cupric tartrate,
Copper chloride and copper acetate are any one or more of.
The preparation method of the flake copper powder, nickel salt used are nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, lemon
Sour nickel and tartaric acid nickel are any one or more of.
The preparation method of the flake copper powder, antioxidant used are benzotriazole, mercapto benzothiazole, amino
Mercaptan, 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, uncle
In the pure and mild phenethyl mercaptan of lauryl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, Stearyl mercaptan, dibenzylsulfide
It is any one or more.
The preparation method of the flake copper powder, complexing agent used are N-hydroxyethyl-ethylenediamine triacetic acid, N- ethoxy
Ethylenediamine triacetic acid trisodium, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, citric acid,
Sodium citrate, potassium citrate, ammonium citrate, tartaric acid, sodium tartrate, potassium tartrate, sodium potassium tartrate tetrahydrate, glycerol, triethanolamine,
Potassium antimony tartrate and ammonium tartrate are any one or more of.
The preparation method of the flake copper powder, copper brightener used are 2- aminoothyl mercaptan, thiocarbamide, two thio ammonia
Base sodium formate, sodium polydithio-dipropyl sulfonate, 2-mercaptobenzimidazole and 1,2- ethylene thiourea are any one or more of.
The preparation method of the flake copper powder, dispersing agent used are polyvinylpyrrolidone, carboxymethyl cellulose, carboxylic
Sodium carboxymethylcellulose pyce, methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gelatin, polyacrylic acid,
Any one of Sodium Polyacrylate, ammonium polyacrylate, polyacrylic acid potassium, polyvinyl alcohol, gum arabic and polyethylene glycol are more
Kind.
The preparation method of the flake copper powder, reducing agent are formaldehyde, ortho phosphorous acid, sodium hypophosphite, sodium borohydride, boron
Hydrofining, hydrazine, hydrazine sulfate, dimethylamino borine, glyoxalic acid and pyroracemic aldehyde are any one or more of.
The preparation method of flake copper powder flake copper powder obtained, technical indicator are as follows: appearance: brown powder；
Purity: >=99.5%；Particle size range: 0.2~10.0 μm；Average grain diameter: 1.0~5.0 μm；Thickness range: 5~70nm；It is average
Thickness: 10~40nm；Apparent density: 1.9~2.9g/cm3；Tap density: 2.5~3.4g/cm3。
In step 4), the preparation of flake copper powder: the mixture for crystallizing template and mantoquita containing sublimable flaky compound exists
Under stirring condition, it is gradually added reducing agent aqueous solution, copper ion is reduced into metallic copper and chemical plating is plated to sublimable sheet
Compound crystallizes template surface, until copper ion fully reacting；Reaction product passes through multiple water through filtering resulting solid matter again
Washing and filtering repetitive operation obtain copper-plated sublimable flaky compound crystallization, temperature model of the material at 70~150 DEG C
It in enclosing, is heat-treated through decompression, makes sublimable flaky compound crystallization distillation, used after sublimable flaky compound crystallization distillation
Cold-trap, which is sublimated, to be recycled and can be recycled, until the crystallization of sublimable flaky compound obtains copper sheet after eliminating, gained copper sheet is again
Absolute ethyl alcohol and stirring dispersion, ultrasonic echography is added to crush 1~6h, filtering and the technical process of drying to get average grain diameter is arrived
For 1.0~5.0 μm and averagely with a thickness of the flake copper powder of 10~40nm.
In step 4), the preparation of flake copper powder: by the acidic mixture of the crystallization template and mantoquita of acid compound containing sheet
It is cooling with room temperature cold bath, so that reaction system is maintained room temperature, under stirring condition, be gradually added reducing agent aqueous solution, by copper from
Son is reduced into metallic copper and chemical plating is plated to sheet acid compound crystallization template surface, until copper ion fully reacting；Due to
Sheet acid compound crystallization template is only very slightly soluble in cold water, but is dissolved in hot water and boiling water, therefore, reaction product is heated to boiling
It rises, sheet acid compound crystallization template is made to be dissolved in boiling water, copper sheet crude product is obtained by filtration while hot, gained copper sheet crude product is through more
After secondary 50% ethanol water washing and filtering repetitive operation purification, then added absolute ethyl alcohol and stirring dispersion, ultrasonic echography powder
Broken 1~6h, filtering and the technical process of drying are to get for 1.0~5.0 μm and average with a thickness of 10~40nm's to average grain diameter
Flake copper powder.
In step 4), the preparation of flake copper powder: by the alkaline mixt of the crystallization template and mantoquita of alkali compounds containing sheet
It is cooling with room temperature cold bath, so that reaction system is maintained room temperature, under stirring condition, be gradually added reducing agent aqueous solution, by copper from
Son is reduced into metallic copper and chemical plating is plated to sheet alkali compounds crystallization template surface, until copper ion fully reacting；Due to
Sheet alkali compounds crystallization template is only very slightly soluble in cold water, but is dissolved in hot water and boiling water, therefore, reaction product is heated to boiling
It rises, sheet alkali compounds crystallization template is made to be dissolved in boiling water, copper sheet crude product is obtained by filtration while hot, gained copper sheet crude product is through more
After secondary 50% ethanol water washing and filtering repetitive operation purification, then added absolute ethyl alcohol and stirring dispersion, ultrasonic echography powder
Broken 1~6h, filtering and the technical process of drying are to get for 1.0~5.0 μm and average with a thickness of 10~40nm's to average grain diameter
Flake copper powder.
The preparation method of the flake copper powder, water used are in distilled water, deionized water, ultrapure water and high purity water
It is any；
The preparation method of the flake copper powder, ultrasonic wave used be frequency be 20KHz~1MHz, power be 30W~
The ultrasonic wave of 15KW.
The utility model has the advantages that compared with prior art, the preparation method of flake copper powder provided by the invention has following significant
Advantage:
1) sublimable flaky compound crystallization is selected to make template, it is therefore an objective to make chemical plating obtained solid product through multiple water
After washing and filtering repetitive operation remove water-solubility impurity, the method that can directly adopt distillation removes template, and template is easily removed
It goes, purifying technique very simple, quickly and efficiently is conducive to the flake copper powder that high-purity is prepared, copper powder purity is reachable
99.5% or more, product purity is high.
2) in the case that mantoquita dosage determines, the dosage of template is crystallized by changing sublimable flaky compound, is adjusted
The ratio of mantoquita and sublimable flaky compound crystallization template, can effectively control the thickness of flake copper powder；It is super with ultrasonic wave
Sound crushes the sheet of copper that sublimable flaky compound crystallization template and chemical plating obtain, and adjusts ultrasonic echography grinding time,
The partial size of flake copper powder can be effectively controlled, size controlling method is simple and effective；Therefore, flake copper powder both can be effectively controlled in the present invention
Thickness, and the partial size of flake copper powder can be effectively controlled, the flake copper powder of high-specific surface area can be prepared, specific surface area is
3~10 times of grain copper powder,
3) in the preparation process of flake copper powder, the purpose of copper brightener is added, is to keep chemical plating copper layer light flat
It is whole, improve the flatness and finish of flake copper powder particle surface；In the preparation process of flake copper powder, the mesh of complexing agent is added
, be the dynamic equilibrium in order to form free copper ion Yu 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 it is
Keep chemical plating copper layer light smooth, can also effectively improve the flatness and finish of flake copper powder particle surface；This is all advantageous
In improving the intergranular contact area of flake copper powder, the electric conductivity with the product of flake copper powder particle formulation is improved, and is not added
The flake copper powder for adding copper brightener to prepare with complexing agent is compared, and the electric conductivity of flake copper powder prepared by the present invention can be improved
35% or so, improvement effect is obvious.
4) in the preparation process of flake copper powder, the purpose of dispersing agent is added, is particle agglomeration in order to prevent, improves sheet of copper
The dispersibility of powder particles, so that flake copper powder is easily dispersed when preparing product with flake copper powder, user is easy to use, improves piece
The service performance of shape copper powder.
5) it compared with the thick product for using spherical copper powder to prepare, is prepared using flake copper powder produced by the invention viscous
Thick shape product, such as conductive adhesive, electrocondution slurry, conductive coating and electrically conductive ink, since flake copper powder is in sticky system
With thixotropic property, the sedimentation stability of product and storage stability is set to improve 50% or so, the stability of product is good.
6) copper belongs to soft metal, copper powder particle be pressurized or be impacted can be laminated it is agglomerating, therefore, ball mill grinding and grinding
Crushing is laminated agglomerating and reunites between will lead to copper powder particle, and the present invention is crushed copper sheet using ultrasonic echography comminuting method
It is 1.0~5.0 μm of flake copper powders at average grain diameter, copper powder particle reunion can be effectively prevented.
7) after the fully reacting for preparing flake copper powder, reaction product filtering obtained solid product is washed and is filtered after washing several times
After repetitive operation removes water-solubility impurity, copper-plated sublimable flaky compound crystallization is obtained, the material is at 70~150 DEG C
It in temperature range, is heat-treated through decompression, makes sublimable flaky compound crystallization distillation, sublimable flaky compound crystallization rises
The recycling of sublimating of Hua Houyong cold-trap can be recycled, and therefore, not only saved template resource and reduced production cost, but also reduced
The discharge of pollutant, improves economic benefit and environmental benefit.
8) technique that reported mantle plate method prepares flake copper powder requires high, severe reaction conditions, and control is improper often
What is obtained is graininess copper powder rather than flake copper powder, and therefore, the technique repetition stability that mantle plate method prepares flake copper powder is poor,
Unstable product quality, or even cannot get flake copper powder, production success rate is not high；Reported dura mater plate method prepares sheet
The technology of copper powder exist again template be difficult to remove, complex process and the processing cost height that even can not remove or remove template etc.
Problem, such as copper powder is prepared using titanium dioxide, porous aluminas substance as template, 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 powder；Biological template prepares flake copper powder operating procedure complexity, and control difficulty is high, and reaction process is slower, production
Low efficiency.The success rate that technical solution of the present invention prepares flake copper powder is 100%, and template easily removes, and product purity exists
99.5% or more, production cost is low, high production efficiency.
9) preparing during flake copper powder using the purpose of antioxidant is to form layer protecting film in copper coating surface,
To prevent the copper coating of sublimable flaky compound crystallization template surface to be oxidized.
10) nickel salt is used during preparing flake copper powder, is had using redox reaction of the nickel salt to electroless copper
There is very strong catalytic action, goes on smoothly the electroless copper reaction of sublimable flaky compound crystallization template surface.
11) technical solution of the present invention have low energy consumption, environmental pollution is small, and simple production process, process route is brief,
Large-scale production equipment investment is small, and high production efficiency, production cost is low, the dispersion performance of product and conduct electricity very well it is a series of excellent
Point, is suitable for large-scale production, solves the problems, such as that existing ball-milling method and template prepare flake copper powder technique, industry
Change promise well.
12) when preparation 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 keep the flaky crystal to be formed more regular；The sheet acid compound that material filtering obtains crystallizes crude product,
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 be flaky crystal, with sheet acid compound crystallize for 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.
13) 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 washing and filtering repetitive operation, 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 the flake copper powder that high-purity is prepared, copper powder purity
Up to 99.5% or more, product purity is high.
14) firstly, since the sheet acid compound crystallization template selected is slightly soluble in cold water, it is dissolved in hot water and boiling water, 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 because of dissolution, and the amount that sheet acid compound crystallizes template is just stable, to flake copper powder 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 in environment because of acid-base neutralization reaction, in this way, the amount of sheet acid compound crystallization template is just stable, to flake copper powder 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, can effectively control the thickness of flake copper powder；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 partial size of flake copper powder can be effectively controlled, size controlling method is simple and effective；In short, sheet both can be effectively controlled in the present invention
The thickness of copper powder, and the partial size of flake copper powder can be effectively controlled, the flake copper powder of high-specific surface area, specific surface area can be prepared
It is 3~10 times of particle copper powder.
15) after the fully reacting for preparing flake copper powder, when reaction product is heated to boiling, due to sheet acid compound
Crystallization template is slightly soluble in cold water, but is dissolved in hot water and boiling water, therefore, after filtering to take out copper sheet while hot, sheet acid compound knot
Crystal template stays in the resulting mother liquor of filtering, and after mother liquor is 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 be recycled for crystallization, therefore, both be saved
Template resource and production cost is reduced, and reduce the discharge of pollutant, improves economic benefit and environmental benefit.
16) when preparation sheet alkali compounds crystallization template, the saturated solution that alkali compounds 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 keep the flaky crystal to be formed more regular；The sheet alkali compounds that material filtering obtains crystallizes crude product,
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 alkalinity chemical combination
The loss of object crystallization improves the preparation efficiency of sheet alkali compounds crystallization template；The crystallization of sheet alkali compounds refers to the alkali
Property compound crystal shape be flaky crystal, with sheet alkali compounds crystallize for template, copper is plated to sheet by chemical plating
Alkali compounds crystallization template surface can form sheet of copper, and the preparation process of sheet of copper is simple.
17) the sheet alkali compounds 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 alkali compounds crystallization template is made to be dissolved in boiling water, after filtering while hot, then through multiple
50% ethanol water washing and filtering repetitive operation, can remove impurity and sheet alkali compounds crystallization template, impurity and
Template is easy to remove, and purifying technique simply, quickly and efficiently, is conducive to the flake copper powder that high-purity is prepared, copper powder purity
Up to 99.5% or more, product purity is high.
18) firstly, since the sheet alkali compounds crystallization template selected is slightly soluble in cold water, it is dissolved in hot water and boiling water, 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 alkalization in this way
The amount for closing object crystallization template is not reduced because of dissolution, and the amount that sheet alkali compounds crystallizes template is just stable, to flake copper powder thickness
The controllability of degree is with regard to strong；Secondly as the sheet alkali compounds crystallization template selected belongs to alkaloid compound, reaction must be
It is carried out under alkaline environment, so, reactant must keep pH > 7, avoid the amount of sheet alkali compounds crystallization template in acidity
It is reduced in environment because of acid-base neutralization reaction, in this way, the amount of sheet alkali compounds crystallization template is just stable, to flake copper powder 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 alkali compounds for third
Amount adjusts the ratio of mantoquita and sheet alkali compounds crystallization template, can effectively control the thickness of flake copper powder；4th, it uses
Ultrasonic echography crushes the sheet of copper that sheet alkali compounds crystallization template and chemical plating obtain, when adjusting ultrasonic echography crushing
Between, the partial size of flake copper powder can be effectively controlled, size controlling method is simple and effective；In short, sheet both can be effectively controlled in the present invention
The thickness of copper powder, and the partial size of flake copper powder can be effectively controlled, the flake copper powder of high-specific surface area, specific surface area can be prepared
It is 3~10 times of particle copper powder.
19) after the fully reacting for preparing flake copper powder, when reaction product is heated to boiling, due to sheet alkali compounds
Crystallization template is slightly soluble in cold water, but is dissolved in hot water and boiling water, therefore, after filtering to take out copper sheet while hot, sheet alkali compounds knot
Crystal template stays in the resulting mother liquor of filtering, and after mother liquor is cooling, sheet alkali compounds crystallization template crystallizes precipitation again, precipitation
Again with after the method separating-purifying of recrystallization, sheet alkali compounds crystallization template can be recycled for crystallization, therefore, both be saved
Template resource and production cost is reduced, and reduce the discharge of pollutant, improves economic benefit and environmental benefit.
Specific embodiment
Below with reference to embodiment, present invention is further described in detail.In following embodiment, unless stated otherwise, own
Percentage all refer to mass percent.
Embodiment 1
A kind of preparation method of flake copper powder, the specific steps are as follows:
1) preparation of the mixture of template and mantoquita is crystallized containing sublimable flaky compound: according to product 1~8 in table 1
Water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and sublimable flaky compound crystallize template
Mass percent, first water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant and nickel salt are mixed, stirring is to institute
There is material to be completely dissolved, add sublimable flaky compound crystallization template, stir and with ultrasonic echography processing 1~
Sublimable flaky compound crystallization template is ground into the sheet knot that partial size is 0.5~20.0 μm with ultrasonic echography by 60min
After crystalline substance to get to containing sublimable flaky compound crystallization template and mantoquita mixture.
2) preparation of reducing agent aqueous solution: according to the reducing agent of product 1~8 in table 1 and the mass percent of water, by water with
Reducing agent mixing arrives reducing agent aqueous solution after stirring and dissolving is complete.
3) preparation of flake copper powder: the mixture of template and mantoquita is crystallized in stirring condition containing sublimable flaky compound
Under, it is gradually added reducing agent aqueous solution, copper ion is reduced into metallic copper and chemical plating is plated to sublimable flaky compound knot
Crystal template surface, until copper ion fully reacting；Reaction product after washing several times and filters again through the resulting solid matter of filtering
Repetitive operation obtains copper-plated sublimable flaky compound crystallization, and the material is within the temperature range of 70~150 DEG C, through subtracting
Autoclaving makes sublimable flaky compound crystallization distillation, is sublimated after sublimable flaky compound crystallization distillation with cold-trap
It recycles and can be recycled, until the crystallization of sublimable flaky compound obtains copper sheet after eliminating, gained copper sheet is added anhydrous again
Ethyl alcohol is dispersed with stirring, ultrasonic echography (frequency is 20KHz~1MHz, power is 30W~15KW) crushes 1~6h, filtering and does
Dry technical process is to get to average grain diameter for 1.0~5.0 μm and averagely with a thickness of the flake copper powder of 10~40nm；
Table 1,1~8 raw material of product and proportion
It infuses [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.
Embodiment 2
The preparation method of flake copper powder in a kind of acid medium, the specific steps are as follows:
1) preparation of sheet acid compound crystallization template: according to the surfactant of product 1~8, acid chemical combination in table 2
The mass percent of object crystallization and water, first mixes water with surfactant, arrives surfactant after stirring and dissolving is complete
Aqueous solution；Aqueous surfactant solution is heated to boiling, acid compound crystallization stirring is added to abundant dissolution, filters while hot
Obtain the saturated solution of acid compound crystallization；The saturated solution that acid compound crystallizes is placed in insulating box of the temperature control at 50 DEG C
Middle crystallisation by cooling takes out material after temperature of charge drops to 50 DEG C from insulating box, then allows material cooled to room temperature, makes
Crystallization is complete；Material filtering obtains sheet acid compound crystallization crude product, filters mother liquid obtained recycling, sheet acidification
It closes object crystallization crude product and presses its quality again, separately take 0~5 DEG C of cold water wash crystallization 2~3 times of 1~10 times of crystalline quality, filter
It is crystallized, crystallization, which is dried, obtains sheet acid compound crystallization template.
2) preparation of the acidic mixture of the crystallization template of acid compound containing sheet and mantoquita: according to product 1~8 in table 2
Middle water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt, acid and sheet acid compound crystallize template
Mass percent first closes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and acid-mixed, and stirring is extremely
All materials are completely dissolved, and are added sheet acid compound crystallization template, are stirred and handle 1~60min with ultrasonic echography,
By sheet acid compound crystallization template with ultrasonic echography be ground into partial size be after 0.5~20.0 μm of flaky crystal to get
To the acidic mixture of the crystallization template and mantoquita of acid compound containing sheet.
3) preparation of reducing agent aqueous solution:, 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, arrives reducing agent aqueous solution after stirring and dissolving is complete.
4) preparation of flake copper powder: the acidic mixture room temperature that acid compound containing sheet is crystallized 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, until copper ion fully reacting；Due to sheet acidity
Compound crystallization template is only very slightly soluble in cold water, but is 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 through plus absolute ethyl alcohol and stirring dispersion, (frequency is ultrasonic echography
20KHz~1MHz, power are 30W~15KW) crush 1~6h, the technical process of filtering and drying is to get to average grain diameter
1.0~5.0 μm and the average flake copper powder with a thickness of 10~40nm.
Table 2,1~8 raw material of product and proportion
It infuses [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.
Embodiment 3
The preparation method of flake copper powder in a kind of acid medium, the specific steps are as follows:
1) preparation of sheet alkali compounds crystallization template: according to the surfactant of product 1~8, alkaline chemical combination in table 3
The mass percent of object crystallization and water, first mixes water with surfactant, arrives surfactant after stirring and dissolving is complete
Aqueous solution；Aqueous surfactant solution is heated to boiling, alkali compounds crystallization stirring is added to abundant dissolution, filters while hot
Obtain the saturated solution of alkali compounds crystallization；The saturated solution that alkali compounds crystallizes is placed in insulating box of the temperature control at 50 DEG C
Middle crystallisation by cooling takes out material after temperature of charge drops to 50 DEG C from insulating box, then allows material cooled to room temperature, makes
Crystallization is complete；Material filtering obtains sheet alkali compounds crystallization crude product, filters mother liquid obtained recycling, sheet alkalization
It closes object crystallization crude product and presses its quality again, separately take 0~5 DEG C of cold water wash crystallization 2~3 times of 1~10 times of crystalline quality, filter
It is crystallized, crystallization, which is dried, obtains sheet alkali compounds crystallization template；
2) preparation of the alkaline mixt of the crystallization template of alkali compounds containing sheet and mantoquita: according to product 1~8 in table 3
Middle water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt, alkali and sheet alkali compounds crystallize template
Mass percent first mixes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and alkali, and stirring is extremely
All materials are completely dissolved, and are added sheet alkali compounds crystallization template, are stirred and handle 1~60min with ultrasonic echography,
By sheet alkali compounds crystallization template with ultrasonic echography be ground into partial size be after 0.5~20.0 μm of flaky crystal to get
To the alkaline mixt of the crystallization template and mantoquita of alkali compounds containing sheet；
3) preparation of reducing agent aqueous solution:, 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, arrives reducing agent aqueous solution after stirring and dissolving is complete；
4) preparation of flake copper powder: the alkaline mixt room temperature that alkali compounds containing sheet is crystallized 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 alkali compounds crystallization template surface, until copper ion fully reacting；Due to sheet alkalinity
Compound crystallization template is only very slightly soluble in cold water, but is dissolved in hot water and boiling water, therefore, reaction product is heated to boiling, makes sheet
Alkali compounds 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 through plus absolute ethyl alcohol and stirring dispersion, (frequency is ultrasonic echography
20KHz~1MHz, power are 30W~15KW) crush 1~6h, the technical process of filtering and drying is to get to average grain diameter
1.0~5.0 μm and the average flake copper powder with a thickness of 10~40nm.
Table 3,1~8 raw material of product and proportion
It infuses [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.
Claims (10)
1. a kind of preparation method of flake copper powder, which is characterized in that steps are as follows:
1) preparation sheet acid compound crystallization template or alkali compounds containing sheet crystallize template；
2) mixture containing sublimable flaky compound crystallization template and mantoquita is prepared；Or the configuration knot of acid compound containing sheet
The acidic mixture of crystal template and mantoquita；Or the alkaline mixt of configuration alkali compounds containing sheet crystallization template and mantoquita；
3) ratio for being 0.1%~30.0%: 70.0%~99.9% according to the mass percent of reducing agent and water, by water and also
Former agent mixing, after stirring and dissolving is complete, makes reducing agent aqueous solution；
4) preparation of flake copper powder: mixture, acidic mixture or the alkaline mixt in step 2) are added in step 3)
Copper ion is reduced into metallic copper and chemical plating is plated to crystallization template surface by reducing agent aqueous solution, until copper ion fully reacting；
When reactant is mixture, repetitive operation is washed and filtered after washing several times again to reaction product through filtering resulting solid matter,
Copper-plated sublimable flaky compound crystallization is obtained, which is heat-treated within the temperature range of 70~150 DEG C through decompression,
Make sublimable flaky compound crystallization distillation, is sublimated after sublimable flaky compound crystallization distillation with cold-trap and recycle and can follow
Ring uses, until the crystallization of sublimable flaky compound obtains copper sheet after eliminating, gained copper sheet is again through adding absolute ethyl alcohol and stirring point
Scattered, ultrasonic echography crushes the technical process of 1~6h, filtering and drying；When reactant is acidic mixture or alkaline mixt
When, reaction product is heated to boiling, so that flaky compound crystallization template is dissolved in boiling water, copper sheet crude product is obtained by filtration while hot,
Gained copper sheet crude product is after multiple 50% ethanol water washs and filters repetitive operation purification, then warp plus absolute ethyl alcohol and stirring
Dispersion, ultrasonic echography crush the technical process of 1~6h, filtering and drying；It is final obtain average grain diameter be 1.0~5.0 μm and
Average thickness is the flake copper powder of 10~40nm.
2. the preparation method of flake copper powder according to claim 1, which is characterized in that in step 1), sheet acidity chemical combination
Object crystallization template preparation: according to surfactant, acid compound crystallization and water mass percent be (0.1%~
30.0%): (0.1%~30.0%): the ratio of (55.0%~95.0%) first mixes water with surfactant, stirs molten
Solution completely after to get arrive aqueous surfactant solution；Aqueous surfactant solution is heated to boiling, acid compound knot is added
The saturated solution of acid compound crystallization is obtained by filtration to abundant dissolution in crystalline substance stirring while hot；The saturation that acid compound is crystallized
Solution is placed in temperature control crystallisation by cooling in 50 DEG C of insulating box and takes out material from insulating box after temperature of charge drops to 50 DEG C,
It allows material cooled to room temperature again, keeps crystallization complete；Material filtering obtains sheet acid compound crystallization crude product, filters institute
It obtains Recycling Mother Solution to use, sheet acid compound crystallization crude product presses its quality again, separately takes the 0~5 of 1~10 times of crystalline quality
, crystallization is obtained by filtration, crystallization, which is dried, obtains sheet acid compound crystallization template DEG C cold water wash crystallization for 2~3 times；
The preparation of sheet alkali compounds crystallization template: according to surfactant, the quality percentage of alkali compounds crystallization and water
Than for (0.1%~30.0%): (0.1%~30.0%): the ratio of (55.0%~95.0%), first by water and surfactant
Mixing arrives aqueous surfactant solution after stirring and dissolving is complete；Aqueous surfactant solution is heated to boiling, is added
The saturated solution of alkali compounds crystallization is obtained by filtration to abundant dissolution in alkali compounds crystallization stirring while hot；By alkaline chemical combination
The saturated solution of 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 constant temperature
Material is taken out in case, then allows material cooled to room temperature, keeps crystallization complete；Material filtering obtains the crystallization of sheet alkali compounds
Crude product, filters mother liquid obtained recycling, and sheet alkali compounds crystallization crude product presses its quality again, separately takes 1~10 times
Crystallization is obtained by filtration in 0~5 DEG C of cold water wash crystallization 2~3 times of crystalline quality, and crystallization, which is dried, obtains sheet alkali compounds
Crystallize template.
3. the preparation method of flake copper powder according to claim 1, which is characterized in that in step 2): preparing and contain and can distil
Flaky compound crystallization template and mantoquita mixture method are as follows: according to water, mantoquita, complexing agent, copper brightener, dispersion
The mass percent that agent, antioxidant, nickel salt and sublimable flaky 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%): the ratio of (0.1~30.0%), first by water, mantoquita, complexing agent, copper brightener,
Dispersing agent, antioxidant and nickel salt mixing, stirring are completely dissolved to all materials, add sublimable flaky compound crystallization
Template, stirs and handles 1~60min with ultrasonic echography, and sublimable flaky compound is crystallized template ultrasonic echography
It is ground into after the flaky crystal that partial size is 0.5~20.0 μm and crystallizes template and mantoquita to get to containing sublimable flaky compound
Mixture；
The method for configuring the acidic mixture of the crystallization template of acid compound containing sheet and mantoquita are as follows: according to water, mantoquita, complexing
Agent, copper brightener, dispersing agent, 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%)
Example first closes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and acid-mixed, stirring to all materials
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 partial size with ultrasonic echography be after 0.5~20.0 μm of flaky crystal to get to containing sheet
The acidic mixture of acid compound crystallization template and mantoquita；
The method for configuring the alkaline mixt of the crystallization template of alkali compounds containing sheet and mantoquita are as follows: according to water, mantoquita, complexing
Agent, copper brightener, dispersing agent, antioxidant, nickel salt, alkali and sheet alkali compounds 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%)
Example first mixes water, mantoquita, complexing agent, copper brightener, dispersing agent, antioxidant, nickel salt and alkali, stirring to all materials
It is completely dissolved, adds sheet alkali compounds crystallization template, stir and handle 1~60min with ultrasonic echography, by sheet alkali
Property compound crystallization template to be ground into partial size with ultrasonic echography be after 0.5~20.0 μm of flaky crystal to get to containing sheet
The alkaline mixt of alkali compounds crystallization template and mantoquita.
4. the preparation method of flake copper powder according to claim 3, which is characterized in that acid used is benzene sulfonic acid, to first
Benzene sulfonic acid, formic acid, acetic acid, propionic acid, citric acid, tartaric acid, lactic acid, nitric acid, sulfuric acid, hydrochloric acid, fumaric acid and maleic two
Acid is any one or more of；Alkali used is ammonia, ammonium hydroxide, ethylenediamine, n-butylamine, n-amylamine, diethylenetriamine, triethylene four
Amine and tetraethylenepentamine are any one or more of.
5. the preparation method of flake copper powder according to claim 1, which is characterized in that sublimable sheet chemical combination used
It is any one of borneol, benzoic acid, naphthalene and anthracene that object, which crystallizes template,；Sheet acid compound crystallization template used is 4- methoxy
Any one of base phenol, benzoic acid, boric acid, 2,6- xylenol and decanedioic acid；Sheet alkali compounds crystallization used
Template is that antifebrin, para-totuidine, naphthalidine and 2- naphthylamines are any one or more of.
6. the preparation method of flake copper powder according to claim 1, which is characterized in that mantoquita used be copper citrate,
Copper sulphate, copper nitrate, cupric tartrate, copper chloride and copper acetate are any one or more of；Nickel salt used is nickel nitrate, sulfuric acid
Nickel, nickel chloride, nickel acetate, citric acid nickel and tartaric acid nickel are any one or more of.
7. the preparation method of flake copper powder according to claim 1, which is characterized in that antioxidant used is benzene a pair of horses going side by side three
Nitrogen azoles, mercapto benzothiazole, amineothiot, n-propyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, sec-butyl mercaptan, isobutyl group
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, hexadecyl mercaptan, Stearyl mercaptan, benzyl
Base mercaptan and phenethyl mercaptan are any one or more of；Complexing agent used is N-hydroxyethyl-ethylenediamine triacetic acid, N- hydroxyl second
Base ethylenediamine triacetic acid trisodium, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, lemon
Acid, sodium citrate, potassium citrate, ammonium citrate, tartaric acid, sodium tartrate, potassium tartrate, sodium potassium tartrate tetrahydrate, glycerol, three ethyl alcohol
Amine, potassium antimony tartrate and ammonium tartrate are any one or more of.
8. the preparation method of flake copper powder according to claim 1, which is characterized in that copper brightener used is 2- ammonia
Base ethyl mercaptan, thiocarbamide, nabam, sodium polydithio-dipropyl sulfonate, 2-mercaptobenzimidazole and 1,2- ethylidene
Thiocarbamide is any one or more of；Dispersing agent used is polyvinylpyrrolidone, carboxymethyl cellulose, carboxymethyl cellulose
Sodium, methylcellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, gelatin, polyacrylic acid, polyacrylic acid
Sodium, ammonium polyacrylate, polyacrylic acid potassium, polyvinyl alcohol, gum arabic and polyethylene glycol are any one or more of.
9. the preparation method of flake copper powder according to claim 1, which is characterized in that reducing agent be formaldehyde, ortho phosphorous acid,
Any one of sodium hypophosphite, sodium borohydride, potassium borohydride, hydrazine, hydrazine sulfate, dimethylamino borine, glyoxalic acid and pyroracemic aldehyde
Or it is a variety of.
10. the preparation method flake copper powder obtained of the described in any item flake copper powders of claim 1-9, technical indicator
Are as follows: appearance: brown powder；Purity: >=99.5%；Particle size range: 0.2~10.0 μm；Average grain diameter: 1.0~5.0 μm；Thickness
Range: 5~70nm；Average thickness: 10~40nm；Apparent density: 1.9~2.9g/cm3；Tap density: 2.5~3.4g/cm3。
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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 |
| CN201810237480.1A CN108500288A (en) | 2018-03-16 | 2018-03-16 | A kind of preparation method of flake copper powder |
| CN2018102374801 | 2018-03-16 | ||
| CN201810237826.8A CN108188411A (en) | 2018-03-16 | 2018-03-16 | The preparation method of flake copper in a kind of acid medium |
| CN2018102378268 | 2018-03-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111483194A (en) * | 2020-04-24 | 2020-08-04 | 台州大树信息技术有限公司 | Organic liquid covering film and preparation method and application thereof |
| 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 |
| WO2023138415A1 (en) * | 2022-01-24 | 2023-07-27 | 西安隆基乐叶光伏科技有限公司 | Modified copper powder, modification method therefor, and conductive slurry |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274368A (en) * | 2008-04-30 | 2008-10-01 | 武汉理工大学 | Method for preparing nano-Cu uniformly coated Zn4Sb3 powder |
| JP2009061580A (en) * | 2007-08-09 | 2009-03-26 | National Institute For Materials Science | Nano flake-like metal composite material, and manufacturing method of the same and surface enhanced raman scattering active substrate |
| CN102489318A (en) * | 2011-12-02 | 2012-06-13 | 南京林业大学 | Preparation method for porous nano p-CuS/n-CdS compound semiconductor photochemical catalyst |
| JP2012250890A (en) * | 2011-06-06 | 2012-12-20 | National Institute For Materials Science | Porous copper sulfide, method for manufacturing the same, and use of the same |
| CN104054138A (en) * | 2012-01-20 | 2014-09-17 | 东洋铝株式会社 | Conductive filler of flake form |
| CN104259472A (en) * | 2014-09-03 | 2015-01-07 | 江苏科技大学 | Organic composition of ultrafine sheet copper powder and preparation method of organic composition |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| KR20170093559A (en) * | 2016-02-05 | 2017-08-16 | 엘지전자 주식회사 | Nanoparticle containing hollow and method for producing the same |
| CN107398561A (en) * | 2017-06-29 | 2017-11-28 | 东北石油大学 | A kind of preparation method of the copper nanometer sheet with regular shape |
| CN108188411A (en) * | 2018-03-16 | 2018-06-22 | 南京林业大学 | The preparation method of flake copper in a kind of acid medium |
| 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 |
| CN108500288A (en) * | 2018-03-16 | 2018-09-07 | 南京林业大学 | A kind of preparation method of flake copper powder |
-
2019
- 2019-02-21 CN CN201910135153.XA patent/CN109877336B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009061580A (en) * | 2007-08-09 | 2009-03-26 | National Institute For Materials Science | Nano flake-like metal composite material, and manufacturing method of the same and surface enhanced raman scattering active substrate |
| CN101274368A (en) * | 2008-04-30 | 2008-10-01 | 武汉理工大学 | Method for preparing nano-Cu uniformly coated Zn4Sb3 powder |
| JP2012250890A (en) * | 2011-06-06 | 2012-12-20 | National Institute For Materials Science | Porous copper sulfide, method for manufacturing the same, and use of the same |
| CN102489318A (en) * | 2011-12-02 | 2012-06-13 | 南京林业大学 | Preparation method for porous nano p-CuS/n-CdS compound semiconductor photochemical catalyst |
| CN104054138A (en) * | 2012-01-20 | 2014-09-17 | 东洋铝株式会社 | Conductive filler of flake form |
| CN104259472A (en) * | 2014-09-03 | 2015-01-07 | 江苏科技大学 | Organic composition of ultrafine sheet copper powder and preparation method of organic composition |
| CN105529472A (en) * | 2015-12-09 | 2016-04-27 | 武汉理工大学 | Co-N double-doped flaky porous two-dimensional carbon material and preparation method thereof |
| KR20170093559A (en) * | 2016-02-05 | 2017-08-16 | 엘지전자 주식회사 | Nanoparticle containing hollow and method for producing the same |
| CN107398561A (en) * | 2017-06-29 | 2017-11-28 | 东北石油大学 | A kind of preparation method of the copper nanometer sheet with regular shape |
| CN108188411A (en) * | 2018-03-16 | 2018-06-22 | 南京林业大学 | The preparation method of flake copper in a kind of acid medium |
| 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 |
| CN108500288A (en) * | 2018-03-16 | 2018-09-07 | 南京林业大学 | A kind of preparation method of flake copper powder |
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| CN111483194A (en) * | 2020-04-24 | 2020-08-04 | 台州大树信息技术有限公司 | Organic liquid covering film and preparation method and application thereof |
| 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 |
| WO2023138415A1 (en) * | 2022-01-24 | 2023-07-27 | 西安隆基乐叶光伏科技有限公司 | Modified copper powder, modification method therefor, and conductive slurry |
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