CN103273056A - Flake-shaped copper powder and preparing method thereof - Google Patents
Flake-shaped copper powder and preparing method thereof Download PDFInfo
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- CN103273056A CN103273056A CN2013102014150A CN201310201415A CN103273056A CN 103273056 A CN103273056 A CN 103273056A CN 2013102014150 A CN2013102014150 A CN 2013102014150A CN 201310201415 A CN201310201415 A CN 201310201415A CN 103273056 A CN103273056 A CN 103273056A
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Abstract
The invention relates to flake-shaped copper powder and a preparing method of the flake-shaped copper powder. Conductive carbon materials are mixed in the flake-shaped copper powder. The method includes the steps of using copper powder as row materials, adding the conductive carbon materials as a dispersing agent, conducting ball milling, and preparing the flake-shaped copper powder. The conductive carbon materials are added and used as the dispersing agent in the preparing process of the flake-shaped copper powder, the problem that in the prior art, conductive performance of the flake-shaped copper powder is passivated due to the fact that a surface active agent is used as the dispersing agent is solved, preprocessing processes of the flake-shaped copper powder are reduced, the process is simple, the condition is moderate, the operation is simple and convenient to conduct, large-scale production is easy to achieve, the conductive performance of the obtained flake-shaped copper powder is high, the resistance is little, and the flake-shaped copper powder very suits to be used as conductive fillings.
Description
Technical field
The present invention relates to a kind of flake copper and preparation method thereof, be specifically related to a kind of flake copper that possesses big radius-thickness ratio and preparation method thereof, described flake copper has good electrical conductivity, can be used as conductive filler, be widely used in the fields such as conducting resinl, polymer paste, electrically-conducting paint, electromagnetic shielding.
Background technology
Copper and copper alloy powder have many good performances, and be good as cheap, electrical and thermal conductivity performance, to be easy to casting, corrosion resisting property good etc., therefore is widely used in electric and electronic industry and energy petrochemical industry etc.Copper powder is during as conductive filler, its pattern is bigger to the electric conductivity influence of conductive material with granularity: because multiform becomes point to contact between Ball-type packing, face contact between the laminal filter of two dimension is conducive to increase contact area, is easy to realize the conduction of electric charge, improves the electric conductivity of material.Therefore, preparation sheet, ganoid copper powder become the research focus of electricity field.
Flake copper is fish scale sheet or flat, can adopt the method for liquid-phase reduction or mechanical force ball milling to be prepared.
Technical Colleges Of Guilin discloses a kind of chemical preparation process of flake copper in CN1315604C, the employing ethylenediamine tetra-acetic acid is chelating agent, is reducing agent with the ascorbic acid, and the method by liquid-phase reduction makes ganoid ultrafine flake copper powder; Product yield is lower in this method, and large-scale production is difficulty comparatively.
Kunming University of Science and Technology discloses a kind of horizontal agitation grinding method and has prepared ultra-fine sheet of copper Zinc alloy powder in CN102151835A; in the protective atmosphere of inert gas; adopting surfactants such as palmitic acid, polyethylene glycol, neopelex is dispersant, grinds through mechanical force to have prepared the sheet alloyed powder.
The spherical copper powder that Jinchuan group discloses in CN101524760A with 1～2 micron is raw material, and adopting stearic acid is that dispersant prepares the sheet footpath less than the method for 20 microns flake copper.Because the prolonging-delay characteristics of copper powder self, often need to add 2～5% surfactant material in the mechanical force ball-milling method as dispersant and cold welding agent; Related surfactant material mostly is electrically non-conductive material, prepared flake copper is further often needing through preliminary treatment such as solvent refluxings in the process, remove the surfactant that these influence electric conductivity, complicated operation, the cost height, and surface checking takes place easily, the copper powder size distribution forms broadening.
Because copper powder is very active, serious gathering, oxidative phenomena take place easily in the preparation flake copper process, can not directly use.How preventing that the flake copper material is oxidized in preparation process, is a difficult problem of preparation flake copper.
This area need be developed a kind of simple to operate, and electric conductivity is good, and radius-thickness ratio is big, and can effectively prevent the preparation method of the flake copper that copper powder is oxidized.
Summary of the invention
The present invention is directed to existing flake copper and remove the complicated operation of dispersant, and residual dispersant influences flake copper electric conductivity, technical problems such as the easy oxidation of preparation process copper powder, a kind of preparation method of flake copper simple to operate is proposed, the radius-thickness ratio of the flake copper that this method prepares is big, and electric conductivity is good.
The invention provides a kind of flake copper, be doped with conductive carbon material in the described flake copper.
Add conductive carbon material in the flake copper of the present invention as dispersant, replace nonconducting surfactant-based dispersant in the traditional preparation process method, improved the electric conductivity of flake copper, guaranteed fully mixing of copper powder raw material and dispersant simultaneously.Flake copper of the present invention has good electrical conductivity, and its coating specific insulation of making can reach 0.20 * 10
-3Ω cm.Can be used as conductive filler, be widely used in the fields such as conducting resinl, polymer paste, electrically-conducting paint, electromagnetic shielding.
In the flake copper provided by the invention, conductive carbon material is the combination of any a kind or at least 2 kinds in carbon black, carbon fiber, Graphene or the CNT, and described combination is carbon black/carbon fiber, Graphene/CNT, carbon fiber/graphite alkene/CNT etc. for example.
The sheet footpath of flake copper provided by the invention≤100 microns, for example 3 microns, 13 microns, 25 microns, 34 microns, 46 microns, 57 microns, 73 microns, 88 microns, 94 microns etc., thickness is about 0.02 micron to about 1 micron, radius-thickness ratio is on average about 20 to about 100, and for example 25,29,32,40,48,55,68,79,88,92 etc.
The present invention also provides the preparation method of aforementioned flake copper, and described method is: be raw material with the copper powder, add conductive carbon material as dispersant, carry out ball milling, make flake copper.
Described method has been added conductive carbon material as dispersant in the raw material copper powder, obtained the aforementioned flake copper that is doped with conductive carbon material through behind the ball milling.Conductive carbon material plays conduction simultaneously and disperses in flake copper effect has improved the electric conductivity of flake copper, and has guaranteed the dispersing uniformity of each component in the copper powder.
Wherein, content 〉=99% of copper in the described raw material copper powder; Preferred described copper powder is electrolytic copper powder or atomized copper powder.
Blister copper (cupric 99%) is made slab in advance as anode, and fine copper is laminated and is made negative electrode, with sulfuric acid (H
2SO
4) and copper sulphate (CuSO
4) mixed liquid as electrolyte.After the energising, copper becomes copper ion (Cu) to move to negative electrode from anodic solution, arrives electron gain behind the negative electrode and claims cathode copper at the fine copper that negative electrode is separated out.The Powdered electrolytic copper powder that is of cathode copper.Atomized copper powder is further processed by cathode copper, is shallow rare mangrove dendritic powder, and easily oxidation in moist empty institute can be dissolved in hot sulfuric acid or nitric acid.
Electrolytic copper powder of the present invention and atomized copper powder all can be by commercially available.
The interpolation mass ratio of conductive carbon material of the present invention and raw material copper powder is 1:20～1:5000, for example 1:22,1:43,1:67,1:80,1:105,1:136,1:175,1:230,1:286,1:322,1:440,1:498,1:565,1:637,1:952,1:1520,1:1789,1:2350,1:2685,1:3058,1:3650,1:4850,1:4980 etc., preferred 1:50～1:2500.
Wherein, described conductive carbon material is the combination of any a kind or at least 2 kinds in carbon black, carbon fiber, Graphene or the CNT.
Ball milling is to utilize abrading-ball to roll in the tubular grinding machine, hit, and makes material become the technology of fine powder, is divided into dry grinding and wet-milling.The dry grinding energy consumption is big, and environmental pollution is little; And wet-milling grinding efficiency height, operating condition is better than dry grinding.All in all, the production technology of ball milling is simple, and small investment, cost are low, remarkable in economical benefits, environmental pollution are little.The present invention is applied to ball milling to have reduced preparation technology's difficulty in the production process of flake copper, has reduced production cost.Ball milling of the present invention can select dry mill process also can select wet-grinding technology and relative device.
Preferably, among the preparation method of flake copper provided by the invention, the mill pearl of described ball milling is zirconia ball, and preferred diameter is the zirconia ball of 1～10mm, and further preferred diameter is the zirconia ball of 6～8mm.
The diameter of described zirconia ball can be 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm etc.
Preferably, in the described mechanical milling process, the mill pearl of ball milling and the mass ratio of copper powder raw material are 10:1～40:1, for example 12:1,16:1,19:1,21:1,24:1,28:1,33:1,36:1,39:1 etc., preferably 20:1～30:1.
Preferably, described mechanical milling process adopts agitated ball mill or horizontal agitating ball mill.
Preferably, the described ball milling time is 1～20h, for example 2h, 7h, 13h, 15h, 17h, 19h etc., preferred 2～10h.
Preferably, the atmosphere of described mechanical milling process is in air, nitrogen, argon gas or the helium any a kind.
As optimal technical scheme, ball milling of the present invention is wet-milling, and described wet-milling process adds grinding aid, and described grinding aid is preferably any a kind in water, absolute ethyl alcohol or the acetone.
When carrying out the wet-milling ball milling, addition the present invention of grinding aid does not do concrete restriction, can be 4:1～7:1,5:1,6.2:1 etc. as the interpolation mass ratio of grinding aid and raw material copper powder.
The content of conductive carbon material in the described flake copper, and the pattern of flake copper is determined by its preparation method.The preparation method of described flake copper is the preparation method of the aforesaid flake copper of the present invention.Among the preparation method of described flake copper, conductive carbon material and raw material copper powder so that the mass ratio of 1:20～1:5000 adds through behind the ball milling, obtain the flake copper that conductive carbon material is fixed.
The present invention also provides a kind of purposes of aforementioned flake copper, and described flake copper is as conductive filler;
Preferably, described flake copper is applied to the conductive filler in the fields such as conducting resinl, polymer paste, electrically-conducting paint or electromagnetic shielding.
Flake copper provided by the invention has bigger radius-thickness ratio, and smooth surface, gloss are bright, the sheet footpath of described sheet copper sheet usually≤100 microns, thickness usually between about 0.01 micron to about 1 micron, radius-thickness ratio on average about 50 to about 100; Owing to adopt in the preparation process material with carbon element (as carbon black, carbon fiber, Graphene, CNT etc.) of high conduction performance to replace in the traditional preparation process method nonconducting surfactant material as dispersant, the flake copper that makes has good electrical conductivity, can be used as conductive filler, be widely used in the fields such as conducting resinl, polymer paste, electrically-conducting paint, electromagnetic shielding.
During as pigment, flake copper provided by the invention is owing to have good electrochemical, can strengthen the anti-corrosion capability of coating, in the coating of coating, be horizontal distribution, can satisfy industrial coating to the specific (special) requirements of pigment, as durability, fast light and fastness to weathering, high tinctorial strength and glossiness etc.Because flake copper provided by the invention has the big planar structure of radius-thickness ratio, can be evenly distributed in the organic coating, thereby can prepare the uniform high quality printing printing ink of color.
During as conductive paste, flake copper energy formation face contacts with face, have the advantages of good caking property energy, and electric conductivity is good, can be used as conductive paste.
Flake copper provided by the invention has added enough dispersants (conductive carbon material), has overcome in preparation process that copper powder is assembled easily, the problem of oxidation, can directly be used as conductive coating paint and conductive paste.
Compared with prior art, the present invention has following beneficial effect:
(1) added conductive carbon material as dispersant in the preparation process of flake copper provided by the invention, having solved in the prior art with the surfactant is the passivation influence to the flake copper electric conductivity that dispersant causes, economization the preprocessing process of flake copper.
(2) preparation method of flake copper provided by the invention, technology is simple, mild condition, easy and simple to handle, is easy to accomplish scale production.
(3) electric conductivity of flake copper provided by the invention is higher, and resistance is little, is suitable for being used as conductive filler.
Description of drawings
The SEM figure of the flake copper that Fig. 1 prepares for embodiment 1;
The SEM figure of the flake copper that Fig. 2 prepares for embodiment 2;
The SEM figure of the flake copper that Fig. 3 prepares for embodiment 3;
The SEM figure of the flake copper that Fig. 4 prepares for embodiment 4;
The particle size distribution figure of the flake copper that Fig. 5 prepares for embodiment 1～4;
The XRD figure of the flake copper that Fig. 6 prepares for embodiment 1～4.
The specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand that described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 50mL absolute ethyl alcohol and 0.05g carbon black disperser, and with the 300g diameter be that the zirconia mill pearl of 1mm is put into ball grinder simultaneously, ball milling 2h, the vacuum drying after filtering of resulting slurry obtains flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces).The SEM photo of the flake copper that Fig. 1 obtains for embodiment 1.Flake copper sheet footpath is about 80 microns as seen from Figure 1, and thickness is about 1 micron, and radius-thickness ratio on average is about 80.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 0.80 * 10
-3Ω cm.
Embodiment 2
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 50mL water and 0.5g CNT dispersant, and with the 300g diameter be that the zirconia mill pearl of 8mm is put into ball grinder simultaneously, ball milling 1h, the vacuum drying after filtering of resulting slurry obtains flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces).The SEM photo of the flake copper that Fig. 2 obtains for embodiment 2.Flake copper sheet footpath is about 40 microns as seen from Figure 2, and thickness is about 0.4 micron, and radius-thickness ratio on average is about 100.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 0.40 * 10
-3Ω cm.
Embodiment 3
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 50mL acetone and 0.025g carbon fiber dispersant, and with the 300g diameter be that the zirconia mill pearl of 2mm is put into ball grinder simultaneously, ball milling 3h, the vacuum drying after filtering of resulting slurry obtains flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces).The SEM photo of the flake copper that Fig. 3 obtains for embodiment 3.Flake copper sheet footpath is about 40 microns as seen from Figure 3, and thickness is about 0.8 micron, and radius-thickness ratio on average is about 50.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 0.60 * 10
-3Ω cm.
Embodiment 4
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 0.01g Graphene dispersant, and with the 300g diameter be that the zirconia mill pearl of 4mm is put into ball grinder simultaneously, in air dielectric, carry out dry ball milling 2h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces).The SEM photo of the flake copper that Fig. 4 obtains for embodiment 4.Flake copper sheet footpath is about 50 microns as seen from Figure 4, and thickness is about 1.0 microns, and radius-thickness ratio on average is about 50.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 0.20 * 10
-3Ω cm.
The flake copper of above-described embodiment 1～4 preparation is carried out granularmetric analysis at particles distribution instrument (Dandong Bai Te BT-9300Z laser particle size distribution instrument).Fig. 5 is the particle size distribution figure of the flake copper of embodiment 1～4 preparation, and the particle diameter of the flake copper that obtains of embodiment 1～4 is all less than 50 microns as can be seen, and wherein most of particle diameter is the 10-20 micron.
The flake copper of above-described embodiment 1～4 preparation is carried out XRD analysis on X-ray diffractometer (Dutch PANalytical, X'Pert PRO MPD type polycrystalline X-ray diffractometer).Fig. 6 is the XRD figure of the flake copper of embodiment 1～4 preparation, and the flake copper that obtains of embodiment 1～4 is pure phase as can be seen, all is copper.
Embodiment 5
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding the 0.02g carbon black disperser, and with the 200g diameter be that the zirconia mill pearl of 10mm is put into ball grinder simultaneously, in nitrogen medium, carry out dry ball milling 5h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 30 microns of the flake copper sheet for preparing footpath, thickness is about 0.5 micron, and radius-thickness ratio on average is about 60.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.30 * 10
-3Ω cm.
Embodiment 6
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding the 0.08g carbon black disperser, and with the 100g diameter be that the zirconia mill pearl of 2mm is put into ball grinder simultaneously, in the helium medium, carry out dry ball milling 8h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 30 microns of the flake copper sheet for preparing footpath, thickness is about 1 micron, and radius-thickness ratio on average is about 30.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.40 * 10
-3Ω cm.
Embodiment 7
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding the 0.25g carbon black disperser, and with the 200g diameter be that the zirconia mill pearl of 6mm is put into ball grinder simultaneously, in argon medium, carry out dry ball milling 2h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 60 microns of the flake copper sheet for preparing footpath, thickness is about 0.8 micron, and radius-thickness ratio on average is about 75.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.10 * 10
-3Ω cm.
Embodiment 8
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding the 0.05g carbon black disperser, and with the 300g diameter be that the zirconia mill pearl of 1mm is put into ball grinder simultaneously, in air dielectric, carry out dry ball milling 10h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 30 microns of the flake copper sheet for preparing footpath, thickness is about 1 micron, and radius-thickness ratio on average is about 30.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.60 * 10
-3Ω cm.
Embodiment 9
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 50ml water and 0.0020g Graphene dispersant, and with the 400g diameter be that the zirconia mill pearl of 1mm is put into ball grinder simultaneously, ball milling 40h, resulting slurries filtration final vacuum drying obtains flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 20 microns of the flake copper sheet for preparing footpath, thickness is about 1 micron, and radius-thickness ratio on average is about 20.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.50 * 10
-3Ω cm.
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 0.005g Graphene dispersant, and with the 200g diameter be that the zirconia mill pearl of 10mm is put into ball grinder simultaneously, in nitrogen medium, carry out dry ball milling 5h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 40 microns of the flake copper sheet for preparing footpath, thickness is about 0.8 micron, and radius-thickness ratio on average is about 50.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.10 * 10
-3Ω cm.
Embodiment 11
A kind of preparation method of flake copper:
Take by weighing the 10.0g electrolytic copper powder, to wherein adding 0.015g Graphene dispersant, and with the 100g diameter be that the zirconia mill pearl of 2mm is put into ball grinder simultaneously, in argon medium, carry out dry ball milling 8h, obtain flake copper.
The flake copper for preparing is carried out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), about 30 microns of the flake copper sheet for preparing footpath, thickness is about 1 micron, and radius-thickness ratio on average is about 30.
The flake copper for preparing is mixed by weight 60:40 with resin, grind and obtain conducting resinl, become required pattern with 240 order serigraphys, solidify, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument.The resistivity of the flake copper that present embodiment prepares is 1.20 * 10
-3Ω cm.
Comparative Examples
A kind of preparation method of flake copper:
In the implementation case, the dispersant of the adding among the embodiment 1 is removed.The same with embodiment 1, take by weighing the 10.0g electrolytic copper powder, to wherein adding the 50mL absolute ethyl alcohol, and with the 300g diameter be that the zirconia mill pearl of 1mm is put into ball grinder simultaneously, ball milling 2h, the vacuum drying after filtering of resulting slurry obtains flake copper.
The flake copper that this Comparative Examples is prepared carries out the observation of surface topography in SEM (the JSM-6700F type that Japanese JEOL company produces), the big or small heterogeneity in flake copper sheet footpath for preparing, between the 20-100 micron, thickness is about 4 microns, and radius-thickness ratio is between the 5-25.
The flake copper for preparing is mixed by weight 60:40 with resin, grinding obtains conducting resinl, becomes required pattern with 240 order serigraphys, solidifies, at room temperature measure the resistivity of conducting resinl with RTS-8 type four point probe resistance instrument, the resistivity of the sheet of copper for preparing is 3.94 * 10
-5Ω cm.
Applicant's statement, the present invention illustrates detailed process equipment of the present invention and technological process by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a flake copper is characterized in that, is doped with conductive carbon material in the described flake copper.
2. flake copper as claimed in claim 1 is characterized in that, described conductive carbon material is the combination of any a kind or at least 2 kinds in carbon black, carbon fiber, Graphene or the CNT.
3. flake copper as claimed in claim 1 or 2 is characterized in that, the sheet of described flake copper footpath≤100 microns, and thickness is about 0.02 micron to about 1 micron, radius-thickness ratio on average about 20 to about 100.
4. the preparation method as the described flake copper of one of claim 1～3 is characterized in that, described method is: be raw material with the copper powder, add conductive carbon material as dispersant, carry out ball milling, make flake copper.
5. preparation method as claimed in claim 4 is characterized in that, content 〉=99% of copper in the described raw material copper powder; Preferred described raw material copper powder is electrolytic copper powder or atomized copper powder.
6. as claim 4 or 5 described preparation methods, it is characterized in that the interpolation mass ratio of described conductive carbon material and raw material copper powder is 1:20～1:5000, preferred 1:50～1:2500;
Preferably, described conductive carbon material is the combination of any a kind or at least 2 kinds in carbon black, carbon fiber, Graphene or the CNT.
7. as the described preparation method of one of claim 4～6, it is characterized in that the mill pearl of described ball milling is zirconia ball, preferred diameter is the zirconia ball of 1～10mm, and further preferred diameter is the zirconia ball of 6～8mm;
Preferably, in the described mechanical milling process, the mill pearl of ball milling and the mass ratio of copper powder raw material are 10:1～40:1, preferred 20:1～30:1.
8. as the described preparation method of one of claim 4～7, it is characterized in that described mechanical milling process adopts agitated ball mill or horizontal agitating ball mill;
Preferably, the described ball milling time is 1～20h, preferred 2～10h;
Preferably, the atmosphere of described mechanical milling process is in air, nitrogen, argon gas or the helium any a kind.
9. as the described preparation method of one of claim 4～8, it is characterized in that described ball milling is wet-milling, described wet-milling process adds grinding aid, and described grinding aid is preferably any a kind in water, absolute ethyl alcohol or the acetone.
10. the purposes as flake copper as described in one of claim 1～3 is characterized in that, described flake copper is as conductive filler;
Preferably, described flake copper is applied to the conductive filler in the fields such as conducting resinl, polymer paste, electrically-conducting paint or electromagnetic shielding.
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| CN103949649A (en) * | 2014-05-13 | 2014-07-30 | 中南大学 | Method for preparing flaky copper in aqueous system |
| CN106270535A (en) * | 2016-08-15 | 2017-01-04 | 华北理工大学 | The mechanical crushing method of metal-air battery negative pole (Mg, Al, Zn, Fe) micro Nano material that a kind of graphenic surface bag is attached |
| CN106457404A (en) * | 2014-04-23 | 2017-02-22 | 阿尔法金属公司 | Method for manufacturing metal powder |
| CN107433328A (en) * | 2017-09-21 | 2017-12-05 | 上海交通大学 | A kind of flake copper for carrying nanometer copper crystal and preparation method thereof |
| CN109763128A (en) * | 2019-03-23 | 2019-05-17 | 昆明理工大学 | A kind of method that alloy corrosion method prepares ultra-fine flakey copper powder |
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