CN104233379A - Electro-deposition preparation method of carbon nano tube-copper base composite powder - Google Patents
Electro-deposition preparation method of carbon nano tube-copper base composite powder Download PDFInfo
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- CN104233379A CN104233379A CN201410450868.1A CN201410450868A CN104233379A CN 104233379 A CN104233379 A CN 104233379A CN 201410450868 A CN201410450868 A CN 201410450868A CN 104233379 A CN104233379 A CN 104233379A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 38
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 67
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 67
- 239000006185 dispersion Substances 0.000 claims abstract description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006557 surface reaction Methods 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000008151 electrolyte solution Substances 0.000 claims description 21
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000004137 mechanical activation Methods 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003701 mechanical milling Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 108010010803 Gelatin Proteins 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 5
- 229920000159 gelatin Polymers 0.000 claims description 5
- 239000008273 gelatin Substances 0.000 claims description 5
- 235000019322 gelatine Nutrition 0.000 claims description 5
- 235000011852 gelatine desserts Nutrition 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 238000010297 mechanical methods and process Methods 0.000 abstract description 2
- 230000005226 mechanical processes and functions Effects 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Metals (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to an electro-deposition preparation method of carbon nano tube-copper base composite powder, and belongs to the technical field of new material and metal powder preparation. The electro-deposition preparation method comprises the following steps: firstly, carrying out surface functionalization and dispersion on a carbon nano tube; preparing composite electro-deposition liquor, namely uniformly mixing copper sulfate, sulfuric acid, treated carbon nano tube, an additive and water to prepare electrolyte; a composite powder electro-deposition process, namely by taking metal copper as an anode and taking metal titanium as a cathode, carrying out electro-deposition in prepared electrolyte for 20-200 minutes under conditions of controlling the temperature of the electrolyte to 20-120 DEG C and cathode current density to 50-300mA/cm<2>to obtain carbon nano tube-copper base composite powder on the cathode. According to the electro-deposition preparation method disclosed by the invention, an inert carbon-carbon bond on the surface of the carbon nano tube is opened by virtue of a mechanical process to form an active functional group, so that the interface repulsive force between the carbon nano tube and the electrolyte is lowered, and the uniform distribution of the carbon nano tube in copper particles is realized.
Description
Technical field
The present invention relates to a kind of electro-deposition preparation method of carbon nano tube-copper based composite powder, belong to novel material and metal-powder preparing technical field.
Background technology
Carbon nano tube-copper based composite powder is the main raw material that powder metallurgic method prepares carbon nano tube-copper based composites, because the surfactivity of carbon nanotube is very low, very poor with the wettability of metallic matrix, this just makes carbon nanotube be difficult to form firmly interface cohesion with metallic matrix, causes the especially very difficult raising of mechanical property of the performance of matrix material.In order to give full play to the premium properties of carbon nanotube, the key issue first solved is needed to be the dispersed of carbon nanotube and the Problem of Wettability with metallic matrix.For solving the dispersed problem of carbon pipe, patent publication No. is that CN101716677A proposes to adopt chemical codeposition legal system for copper-base composite particles of internal carbon-inlaid nano pipe, first the mixed acid solution utilizing certain proportion to be made up of the vitriol oil and concentrated nitric acid carries out purification process to carbon nanotube, gelatin is adopted to carry out further functionalization to carbon nanotube, in copper solutions (copper sulfate, glucose and polyglycol solution), form copper oxide particle on the carbon nanotubes, and carbon nanotube is inlayed wherein.Then in hydrogen atmosphere, the Reduction of Oxide of copper is become copper.Patent publication No. is that CN102628115A adopts high-energy ball milling to prepare carbon nanotube reinforced copper-base composite granule, by the carbon nanotube of 0.5 ~ 10wt%, the copper powder of 85 ~ 99.4% and the auxiliary agent of 0.1 ~ 5wt% are put into high energy ball mill and are carried out ball milling, ball-milling medium is Stainless Steel Ball, ball material mass ratio is 5 ~ 50:1, drum's speed of rotation is 200 ~ 1000r/min, Ball-milling Time is 1 ~ 10h, select argon gas as milling atmosphere to prevent powder oxidation in process, the composite granule obtained obtains the carbon nanotube reinforced copper-base composite material of high strength and high hardness through reduced anneal → press forming → vacuum sintering.Patent publication No. is that CN103170627A adopts the method screening rotating electrophoresis to obtain the carbon nanotube of length-to-diameter ratio distribution gradient, then increase in gradient by length-to-diameter ratio and mix through ball mill with copper alloy powder respectively, after chemical nickel plating, obtain copper base composite powder.Number of patent application is the method that a kind of anode dissolution of 2014103219152 proposition prepares carbon nano tube-copper composite granule, first copper salt solution is configured to after mantoquita, carbon nanotube, depolarizer, dispersion agent and water that sour purifying is good being mixed, then a kind of in magnesium and alloy, zinc and alloy thereof, Aluminum-aluminum alloy is placed in as dissolving anode the copper salt solution configured, temperature be 0 ~ 100 DEG C, electricity reaction 0.1 ~ 12h under ultrasonic or mechanical agitation, prepare carbon nano tube-copper composite granule.Although in above-mentioned technology, obtain carbon nano tube-copper based composite powder, still come with some shortcomings, e.g., process operations is comparatively complicated, and cost is higher, and products production controllability is not enough.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of electro-deposition preparation method of carbon nano tube-copper based composite powder.First the inertia carbon-carbon bond of carbon nano tube surface is opened the functional group forming activity by the present invention by mechanical process, to reduce carbon nanotube and electrolyte interface repulsion, then utilize the electronegativity of the functional group of carbon nano tube surface and electropositive Cu
2+in conjunction with, at cathode codeposition, and realize carbon nanotube being uniformly distributed in copper particle, the present invention is achieved through the following technical solutions.
An electro-deposition preparation method for carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 13 ~ 20:1 adds dispersion agent by carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, carries out surperficial mechanical activation and dispersion in oxidizing atmosphere;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 20 ~ 200g/L, sulfuric acid concentration is 50 ~ 300g/L, carbon nanotube concentration is 0.1 ~ 1.0g/L, additive concentration is 0.5 ~ 10g/L, remaining as water;
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 20 ~ 120 DEG C, cathode current density is 50 ~ 300mA/cm
2under condition, galvanic deposit 20 ~ 200min in the electrolytic solution that step (2) configures, can obtain carbon nanotube copper based composite powder at negative electrode.
Surperficial mechanical activation in described step (1) be separated into mechanical milling process, Ball-milling Time is 20 ~ 150min.
Additive in dispersion agent in described step (1) and step (2) is one or more the arbitrary proportion mixtures in polyvinylpyrrolidone, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Cetyltrimethylammonium bromide, hexadecyl trimethyl ammonium bromide, gelatin, polyvinyl alcohol, polyoxyethylene glycol.
The mixed gas of to be mass ratio be 5 ~ 20:1 oxygen and the air of the oxidizing atmosphere in described step (1).
The invention has the beneficial effects as follows: (1) technological operation is simple, and carbon nano tube-copper based composite powder only needs can be formed through once-combined galvanic deposit, and the consumption of technique agents useful for same is very low, only need to regularly replace anode; (2) carbon nanotube is coated by copper uniform particles; (3) present method environmental friendliness, operating environment improves, and is easy to industrialization.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram in the embodiment of the present invention 1 after carbon nanotube activation;
Fig. 2 is the scanning electron microscope (SEM) photograph A of the carbon nano tube-copper based composite powder prepared in the embodiment of the present invention 1;
Fig. 3 is the scanning electron microscope (SEM) photograph B of the carbon nano tube-copper based composite powder prepared in the embodiment of the present invention 1;
Fig. 4 is the transmission electron microscope picture of the carbon nano tube-copper based composite powder prepared in the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
The electro-deposition preparation method of this carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 20:1 adds dispersion agent by 10g carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, surperficial mechanical activation and dispersion is carried out in oxidizing atmosphere, wherein surperficial mechanical activation be separated into mechanical milling process, ball-milling medium steel ball 200g, Ball-milling Time is 30min, dispersion agent is polyvinylpyrrolidone (PVP), the mixed gas of oxidizing atmosphere to be mass ratio be 5:1 oxygen and air, the infrared spectra through the carbon nanotube of surperficial mechanical activation and dispersion is illustrated in Fig. 1;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 20g/L, sulfuric acid concentration is 50g/L, carbon nanotube concentration is 0.1g/L, additive concentration is 1g/L, remaining as water, wherein additive is 0.5g/L polyvinylpyrrolidone and 0.5g/L sodium lauryl sulphate;
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 20 DEG C, cathode current density is 50mA/cm
2under condition, galvanic deposit 20min in the electrolytic solution that step (2) configures, can obtain mean particle size at negative electrode is 42.5 μm of carbon nanotube copper based composite powders.
Fig. 2 and 3 is scanning electron microscope (SEM) photographs of the different amplification of carbon nano tube-copper based composite powder, and Fig. 4 is the transmission electron microscope picture of carbon nano tube-copper based composite powder.
Embodiment 2
The electro-deposition preparation method of this carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 13:1 adds dispersion agent by 20g carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, surperficial mechanical activation and dispersion is carried out in oxidizing atmosphere, wherein surperficial mechanical activation be separated into mechanical milling process, ball-milling medium steel ball 400g, Ball-milling Time is 50min, dispersion agent is hexadecyl trimethyl ammonium bromide (CTAB), the mixed gas of oxidizing atmosphere to be mass ratio be 10:1 oxygen and air;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 100g/L, sulfuric acid concentration is 180g/L, carbon nanotube concentration is 0.5g/L, additive concentration is 5g/L, remaining as water, additive is 2.5g/L sodium lauryl sulphate and 2.5g/L polyoxyethylene glycol;
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 50 DEG C, cathode current density is 150mA/cm
2under condition, galvanic deposit 50min in the electrolytic solution that step (2) configures, can obtain at negative electrode the carbon nanotube copper based composite powder that mean particle size is 34.7 μm.
Embodiment 3
The electro-deposition preparation method of this carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 15:1 adds dispersion agent by 30g carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, surperficial mechanical activation and dispersion is carried out in oxidizing atmosphere, wherein surperficial mechanical activation be separated into mechanical milling process, ball-milling medium steel ball 600g, Ball-milling Time is 20min, dispersion agent is polyvinyl alcohol, the mixed gas of oxidizing atmosphere to be mass ratio be 15:1 oxygen and air;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 150g/L, sulfuric acid concentration is 200g/L, carbon nanotube concentration is 0.8g/L, additive concentration is 7g/L, remaining as water, additive is 5g/L polyoxyethylene glycol and 2g/L Cetyltrimethylammonium bromide (OTAB);
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 70 DEG C, cathode current density is 200mA/cm
2under condition, galvanic deposit 100min in the electrolytic solution that step (2) configures, can obtain at negative electrode the carbon nanotube copper based composite powder that mean particle size is 25.0 μm.
Embodiment 4
The electro-deposition preparation method of this carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 18:1 adds dispersion agent by 40g carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, surperficial mechanical activation and dispersion is carried out in oxidizing atmosphere, wherein surperficial mechanical activation be separated into mechanical milling process, ball-milling medium steel ball 800g, Ball-milling Time is 150min, dispersion agent is sodium lauryl sulphate, the mixed gas of oxidizing atmosphere to be mass ratio be 20:1 oxygen and air;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 200g/L, sulfuric acid concentration is 300g/L, carbon nanotube concentration is 1.0g/L, additive concentration is 10g/L, remaining as water, additive is 7g/L gelatin and 3g/L Cetyltrimethylammonium bromide (OTAB);
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 120 DEG C, cathode current density is 300mA/cm
2under condition, galvanic deposit 200min in the electrolytic solution that step (2) configures, can obtain at negative electrode the carbon nanotube copper based composite powder that mean particle size is 15.0 μm.
Embodiment 5
The electro-deposition preparation method of this carbon nano tube-copper based composite powder, its concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 17:1 adds dispersion agent by 40g carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, surperficial mechanical activation and dispersion is carried out in oxidizing atmosphere, wherein surperficial mechanical activation be separated into mechanical milling process, ball-milling medium steel ball 800g, Ball-milling Time is 90min, dispersion agent is Sodium dodecylbenzene sulfonate, the mixed gas of oxidizing atmosphere to be mass ratio be 15:1 oxygen and air;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 118g/L, sulfuric acid concentration is 245g/L, carbon nanotube concentration is 0.8g/L, additive concentration is 0.5g/L, remaining as water, additive is gelatin;
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 85 DEG C, cathode current density is 80mA/cm
2under condition, galvanic deposit 116min in the electrolytic solution that step (2) configures, can obtain carbon nanotube copper based composite powder at negative electrode.
By reference to the accompanying drawings the specific embodiment of the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment, in the ken that those of ordinary skill in the art possess, various change can also be made under the prerequisite not departing from present inventive concept.
Claims (4)
1. an electro-deposition preparation method for carbon nano tube-copper based composite powder, is characterized in that concrete steps are as follows:
(1) carbon nano tube surface functionalization and dispersion: be that 13 ~ 20:1 adds dispersion agent by carbon nanotube with according to carbon nanotube and dispersion agent mass ratio, carries out surperficial mechanical activation and dispersion in oxidizing atmosphere;
(2) composite electrodeposition liquid is configured: after first copper sulfate, sulfuric acid, carbon nanotube, additive and water after step (1) process being mixed, be configured to electrolytic solution, wherein in electrolytic solution, concentration of copper sulfate is 20 ~ 200g/L, sulfuric acid concentration is 50 ~ 300g/L, carbon nanotube concentration is 0.1 ~ 1.0g/L, additive concentration is 0.5 ~ 10g/L, remaining as water;
(3) composite granule electrodeposition process: take metallic copper as anode, metal titanium is negative electrode, control electrolyte temperature be 20 ~ 120 DEG C, cathode current density is 50 ~ 300mA/cm
2under condition, galvanic deposit 20 ~ 200min in the electrolytic solution that step (2) configures, can obtain carbon nanotube copper based composite powder at negative electrode.
2. the electro-deposition preparation method of carbon nano tube-copper based composite powder according to claim 1, is characterized in that: the surperficial mechanical activation in described step (1) be separated into mechanical milling process, Ball-milling Time is 20 ~ 150min.
3. the electro-deposition preparation method of carbon nano tube-copper based composite powder according to claim 1, is characterized in that: the additive in the dispersion agent in described step (1) and step (2) is one or more the arbitrary proportion mixtures in polyvinylpyrrolidone, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Cetyltrimethylammonium bromide, hexadecyl trimethyl ammonium bromide, gelatin, polyvinyl alcohol, polyoxyethylene glycol.
4. the electro-deposition preparation method of carbon nano tube-copper based composite powder according to claim 1, is characterized in that: the mixed gas of to be mass ratio be 5 ~ 20:1 oxygen and the air of the oxidizing atmosphere in described step (1).
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Cited By (9)
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| CN105470524A (en) * | 2015-03-11 | 2016-04-06 | 万向A一二三系统有限公司 | Carbon nanotube coating aluminum foil for power battery and preparation method of carbon nanotube coating aluminum foil |
| RU2613553C2 (en) * | 2015-09-09 | 2017-03-17 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Method of making copper coatings with developed surface |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
| CN107338456A (en) * | 2017-07-11 | 2017-11-10 | 云南省核工业二0九地质大队 | A kind of method that ultrasonic wave added electro-deposition prepares lead/carbon nano-tube composite powder |
| CN107586981A (en) * | 2017-08-16 | 2018-01-16 | 昆明理工大学 | A kind of preparation method of carbon nanotube reinforced copper-base composite material |
| CN110327925A (en) * | 2019-07-29 | 2019-10-15 | 西安建筑科技大学 | Coal Quito pore catalyst and its preparation method and application of carbon monoxide in a kind of removing sintering flue gas |
| CN110548509A (en) * | 2019-08-02 | 2019-12-10 | 深圳大学 | copper-based carbon dioxide electrocatalytic material and preparation method thereof |
| CN110665510A (en) * | 2019-09-19 | 2020-01-10 | 西安工程大学 | Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas |
| CN113293417A (en) * | 2021-06-03 | 2021-08-24 | 常州大学 | Preparation method of bright high-conductivity graphene/copper composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470524A (en) * | 2015-03-11 | 2016-04-06 | 万向A一二三系统有限公司 | Carbon nanotube coating aluminum foil for power battery and preparation method of carbon nanotube coating aluminum foil |
| RU2613553C2 (en) * | 2015-09-09 | 2017-03-17 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Тольяттинский государственный университет" | Method of making copper coatings with developed surface |
| CN107326401A (en) * | 2017-05-22 | 2017-11-07 | 昆明理工大学 | A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites |
| CN107338456A (en) * | 2017-07-11 | 2017-11-10 | 云南省核工业二0九地质大队 | A kind of method that ultrasonic wave added electro-deposition prepares lead/carbon nano-tube composite powder |
| CN107586981A (en) * | 2017-08-16 | 2018-01-16 | 昆明理工大学 | A kind of preparation method of carbon nanotube reinforced copper-base composite material |
| CN107586981B (en) * | 2017-08-16 | 2019-07-05 | 昆明理工大学 | A kind of preparation method of carbon nanotube reinforced copper-base composite material |
| CN110327925A (en) * | 2019-07-29 | 2019-10-15 | 西安建筑科技大学 | Coal Quito pore catalyst and its preparation method and application of carbon monoxide in a kind of removing sintering flue gas |
| CN110548509A (en) * | 2019-08-02 | 2019-12-10 | 深圳大学 | copper-based carbon dioxide electrocatalytic material and preparation method thereof |
| CN110665510A (en) * | 2019-09-19 | 2020-01-10 | 西安工程大学 | Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas |
| CN110665510B (en) * | 2019-09-19 | 2022-04-29 | 西安工程大学 | Preparation method of copper-cobalt-based catalyst for preparing low-carbon alcohol from synthesis gas |
| CN113293417A (en) * | 2021-06-03 | 2021-08-24 | 常州大学 | Preparation method of bright high-conductivity graphene/copper composite material |
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