CN104120458A - Method for preparation of carbon nanotube-copper composite powder by anode dissolving - Google Patents
Method for preparation of carbon nanotube-copper composite powder by anode dissolving Download PDFInfo
- Publication number
- CN104120458A CN104120458A CN201410321915.2A CN201410321915A CN104120458A CN 104120458 A CN104120458 A CN 104120458A CN 201410321915 A CN201410321915 A CN 201410321915A CN 104120458 A CN104120458 A CN 104120458A
- Authority
- CN
- China
- Prior art keywords
- copper
- acid
- carbon nanotube
- carbon nano
- composite granule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000010949 copper Substances 0.000 title claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 150000001879 copper Chemical class 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 25
- 239000000956 alloy Substances 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- -1 depolarizer Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 3
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 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
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910000838 Al alloy Inorganic materials 0.000 abstract 2
- 229910000861 Mg alloy Inorganic materials 0.000 abstract 2
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract 2
- 229910001297 Zn alloy Inorganic materials 0.000 abstract 2
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 230000002999 depolarising effect Effects 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000003717 electrochemical co-deposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000004913 activation 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- QVLQKWQNKGVECJ-UHFFFAOYSA-N copper;propanoic acid Chemical compound [Cu].CCC(O)=O QVLQKWQNKGVECJ-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention relates to a method for preparation of carbon nanotube-copper composite powder by anode dissolving, and belongs to the technical field of the preparation of new materials. The method is as follows: preparation of a copper salt solution, to be more specific, first, a copper salt, carbon nanotubes, a depolarizing agent, a dispersing agent and water are evenly mixed for preparation of a solution; and preparation of the carbon nanotube-copper composite powder, to be more specific, one of magnesium and magnesium alloy, zinc and zinc alloy, and aluminum and aluminum alloy is put in the prepared copper salt solution for electric reaction for 0.1-12h at the temperature of 0 to 100 DEG C, under the conditions of ultrasonic or mechanical stirring to prepare the carbon nanotube-copper composite powder. According to the method, in a certain copper salt solution, the magnesium and magnesium alloy, zinc and zinc alloy, or aluminum and aluminum alloy as a dissolving anode is put in the copper salt solution, copper ions in the copper salt solution are reduced to copper powder, while the formation of the copper powder, the carbon nanotubes dispersed in the solution are used as crystal nucleus for realizing codeposition to prepare the carbon nanotube-copper composite powder.
Description
Technical field
The present invention relates to a kind of anode dissolution and prepare the method for carbon nano tube-copper composite granule, belong to technical field of new material preparation.
Background technology
Copper powder is widely used in electromechanical components and the electronics aviation fields such as powder metallurgy, electrical carbon product, electronic material, metallic paint, chemical catalyst, strainer, radiating pipe.The composite granule obtaining after copper and carbon nanotube are compound improves a lot compared with copper powder on mechanics and thermal property.At present, the method for preparing copper and carbon nano-tube composite powder mainly contains chemical codeposition method, electrochemical co-deposition method and ball milled etc.
Patent publication No. is that CN101716677A is by after carbon nanotube oxide treatment, through sensitization and activation, in the plating solution of 15 ~ 25 ℃, supersound process is carried out electroless copper, finally in carbon nano tube surface, obtain continuous copper oxide coating, adopt hydrogen reducing copper oxide, obtain copper-carbon nano-tube composite powder.Patent publication No. is that CN101069928A proposition gelatin carries out further functionalization to the carbon nanotube after being oxidized, in copper solutions, (copper sulfate, glucose and polyglycol solution) adopts the method for electroless plating to prepare carbon nano tube-copper oxide composite powder, then in hydrogen atmosphere, the Reduction of Oxide of copper become to copper.Patent publication No. is that CN102628115A adopts high-energy ball milling to prepare carbon nanotube reinforced copper-base composite granule, carbon nanotube, copper powder and auxiliary agent are put into high energy ball mill and carry out ball milling, ball-milling medium is Stainless Steel Ball, select argon gas as milling atmosphere, dry method one-step synthesis CNTs/Cu composite granule.Patent US2007/0036978A1(2007), US7651766B2 and 2010US2010/0122910A1(2010) in copper sulfate electroplate liquid, utilize electrochemical co-deposition method to prepare Cu-CNTs composite granule.
Above-mentioned copper and the carbon nano-tube composite powder technology prepared exists technical process comparatively complicated, the problem of products production controllability deficiency, as, while adopting chemical plating technology to prepare carbon nano tube-copper composite granule, processing technological flow is long, and operation is comparatively complicated, and cost is more high.
Summary of the invention
The problem and the deficiency that for above-mentioned prior art, exist, the invention provides a kind of method that anode dissolution is prepared carbon nano tube-copper composite granule.The method is in specific copper salt solution, magnesium and alloy, zinc and alloy thereof or aluminium and alloy thereof are placed in to copper salt solution as dissolving anode, cupric ion in copper salt solution is reduced to copper powder, in the copper powder forming, the carbon nanotube being dispersed in solution of take is nucleus, realize codeposition, obtain copper-carbon nano-tube composite powder, the present invention is achieved through the following technical solutions.
Anode dissolution is prepared a method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: be configured to solution after first mantoquita, carbon nanotube, depolarizer, dispersion agent and water being mixed, wherein in solution, the mass percent of mantoquita is 1 ~ 30%, the mass percent of carbon nanotube is 0.0001 ~ 10%, the mass percent of depolarizer is 0.001 ~ 10%, the mass percent of dispersion agent is 0.001 ~ 5%, and residual mass per-cent is water;
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:1 ~ 100 are placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 0.1 ~ 12h under 0 ~ 100 ℃, ultrasonic or mechanical stirring condition, can prepare carbon nano tube-copper composite granule.
Mantoquita in described step (1) is the organic salt forming with the organic acid of formic acid, acetic acid or propionic acid, with the inorganic salt that sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid form, one or more the arbitrary proportion mixing mantoquitas in the salt forming with methyl-phosphorous acid and derivative thereof.
Before carbon nanotube configuration in described step (1), first through the acidifying of sulfuric acid, nitric acid and hydrochloric acid or these sour mixtures, carbon nanotube is one or both arbitrary proportion mixtures in multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
Described step (1) depolarizer is one or more the arbitrary proportion mixtures in hydrochloric acid, acetic acid, sodium acetate, formic acid, citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA).
Described dispersion agent is one or more the arbitrary proportion mixtures in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, gelatin, polyvinyl alcohol, polyoxyethylene glycol, octadecanoic acid, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, alkyl fatty polyoxyethylenated alcohol, aliphatic amine polyoxyethylene ether, alkylol amide polyoxy ethane ether, block polyoxyethylene polyoxypropylene ether, alkylol amide.
If specifically do not mention concentration in mentioned reagent, it is all analytical reagent.
The invention has the beneficial effects as follows: (1) present method technological operation is simple, copper-carbon nano-tube composite powder can form through a codeposition; (2) dispersion of carbon nanotube in composite granule is comparatively even, and does not introduce other metallic impurity; (3) present method environmental friendliness, raw material used in the present invention is little to environmental influence, and the element in the waste liquid obtaining is easy to be recycled.
Accompanying drawing explanation
Fig. 1 is the carbon nano tube-copper composite granule scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares;
Fig. 2 is the carbon nano tube-copper composite granule size distribution figure that the embodiment of the present invention 1 prepares.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: be configured to solution after first mantoquita, carbon nanotube, depolarizer, dispersion agent and water being mixed, wherein in solution, the mass percent of mantoquita is 5%, mantoquita is copper sulfate, the mass percent of carbon nanotube is 0.001%, and carbon nanotube is Single Walled Carbon Nanotube, and the mass percent of depolarizer is 0.05%, depolarizer is hydrochloric acid, the mass percent of dispersion agent is 0.5%, and dispersion agent is sodium lauryl sulphate, and residual mass per-cent is water;
(2) prepare carbon nano tube-copper composite granule: using aluminium as anode, according to solid-to-liquid ratio, be that 1:40 is placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 4h under 25 ℃, ultrasound condition, can prepare carbon nano tube-copper composite granule, carbon nano tube-copper composite granule microscopic appearance as shown in Figure 1, Fig. 2 is the particle size distribution figure of this composite granule of recording of laser particle analyzer, and the mean particle size of composite granule is about 27.5um.
Embodiment 2
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: be configured to solution after first mantoquita, carbon nanotube, depolarizer, dispersion agent and water being mixed, wherein in solution, the mass percent of mantoquita is 10%, mantoquita is venus crystals, the mass percent of carbon nanotube is 0.01%, carbon nanotube is multi-walled carbon nano-tubes, the mass percent of depolarizer is 0.05%, depolarizer is tartrate, the mass percent of dispersion agent is 0.1%, dispersion agent is block polyoxyethylene polyoxypropylene ether, and residual mass per-cent is water;
(2) prepare carbon nano tube-copper composite granule: using aluminium and be that 1:20 is placed in the copper salt solution that step (1) configures as anode according to solid-to-liquid ratio, in temperature, be electricity reaction 2h under 55 ℃, mechanical stirring condition, can prepare carbon nano tube-copper composite granule.
Embodiment 3
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: be configured to solution after first mantoquita, carbon nanotube, depolarizer, dispersion agent and water being mixed, wherein in solution, the mass percent of mantoquita is 30%, mantoquita is the Tubercuprose of mass ratio 1:1 and the mixture of propionic acid copper, the mass percent of carbon nanotube is 0.0001%, carbon nanotube is multi-walled carbon nano-tubes, the mass percent of depolarizer is 0.001%, depolarizer is acetic acid, the mass percent of dispersion agent is 0.001%, dispersion agent is Sodium dodecylbenzene sulfonate, and residual mass per-cent is water;
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:80 is placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 12h under 0 ℃, ultrasound condition, can prepare carbon nano tube-copper composite granule.
Embodiment 4
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: first by mantoquita, carbon nanotube, depolarizer, after mixing, dispersion agent and water is configured to solution, wherein in solution, the mass percent of mantoquita is 1%, mantoquita is the cupric chloride of mass ratio 1:1:1, cupric nitrate, the mixing mantoquita of cupric phosphate, the mass percent of carbon nanotube is 10%, carbon nanotube is multi-walled carbon nano-tubes, the mass percent of depolarizer is 10%, depolarizer is the sodium acetate of quality 1:1:1:1, formic acid, citric acid, tartaric mixture, the mass percent of dispersion agent is 5%, dispersion agent is the cetyl trimethylammonium bromide of mass ratio 1:1:1:1:1, gelatin, polyvinyl alcohol, the mixture of polyoxyethylene glycol and octadecanoic acid, residual mass per-cent is water,
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:1 is placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 0.1h under 100 ℃, ultrasound condition, can prepare carbon nano tube-copper composite granule.
Embodiment 5
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: first by mantoquita, carbon nanotube, depolarizer, after mixing, dispersion agent and water is configured to solution, wherein in solution, the mass percent of mantoquita is 20%, mantoquita is methyl-phosphorous acid copper, the mass percent of carbon nanotube is 8%, carbon nanotube is multi-walled carbon nano-tubes, the mass percent of depolarizer is 0.2%, depolarizer is ethylenediamine tetraacetic acid (EDTA), the mass percent of dispersion agent is 0.08%, dispersion agent is the polyoxyethylene nonylphenol ether of quality 1:1:1, polyoxyethylene octylphenol ether and alkyl fatty polyoxyethylenated alcohol mixture, residual mass per-cent is water,
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:100 is placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 8h under 90 ℃, ultrasound condition, can prepare carbon nano tube-copper composite granule.
Embodiment 6
This anode dissolution is prepared the method for carbon nano tube-copper composite granule, and its concrete steps are as follows:
(1) configuration copper salt solution: first by mantoquita, carbon nanotube, depolarizer, after mixing, dispersion agent and water is configured to solution, wherein in solution, the mass percent of mantoquita is 28%, mantoquita is the mantoquita of methyl-phosphorous acid derivative, the mass percent of carbon nanotube is 0.02%, carbon nanotube is Single Walled Carbon Nanotube, the mass percent of depolarizer is 0.001%, depolarizer is hydrochloric acid, the mass percent of dispersion agent is 0.05%, dispersion agent is the alkyl fatty polyoxyethylenated alcohol of quality 1:1:1, aliphatic amine polyoxyethylene ether and alkylol amide polyoxy ethane ether mixture, residual mass per-cent is water,
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:10 is placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 8h under 80 ℃, mechanical stirring condition, can prepare carbon nano tube-copper composite granule.
Claims (5)
1. anode dissolution is prepared a method for carbon nano tube-copper composite granule, it is characterized in that concrete steps are as follows:
(1) configuration copper salt solution: be configured to solution after first mantoquita, carbon nanotube, depolarizer, dispersion agent and water being mixed, wherein in solution, the mass percent of mantoquita is 1 ~ 30%, the mass percent of carbon nanotube is 0.0001 ~ 10%, the mass percent of depolarizer is 0.001 ~ 10%, the mass percent of dispersion agent is 0.001 ~ 5%, and residual mass per-cent is water;
(2) prepare carbon nano tube-copper composite granule: using a kind of in magnesium and alloy, zinc and alloy thereof, aluminium and alloy thereof, as anode, according to solid-to-liquid ratio, be that 1:1 ~ 100 are placed in the copper salt solution that step (1) configures, in temperature, be electricity reaction 0.1 ~ 12h under 0 ~ 100 ℃, ultrasonic or mechanical stirring condition, can prepare carbon nano tube-copper composite granule.
2. anode dissolution according to claim 1 is prepared the method for carbon nano tube-copper composite granule, it is characterized in that: the organic salt that the mantoquita in described step (1) forms for the organic acid with formic acid, acetic acid or propionic acid, with the inorganic salt that sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid form, one or more the arbitrary proportion mixing mantoquitas in the salt forming with methyl-phosphorous acid and derivative thereof.
3. anode dissolution according to claim 1 is prepared the method for carbon nano tube-copper composite granule, it is characterized in that: before the carbon nanotube configuration in described step (1), first through the acidifying of sulfuric acid, nitric acid and hydrochloric acid or these sour mixtures, carbon nanotube is one or both arbitrary proportion mixtures in multi-walled carbon nano-tubes or Single Walled Carbon Nanotube.
4. anode dissolution according to claim 1 is prepared the method for carbon nano tube-copper composite granule, it is characterized in that: described step (1) depolarizer is one or more the arbitrary proportion mixtures in hydrochloric acid, acetic acid, sodium acetate, formic acid, citric acid, tartrate, ethylenediamine tetraacetic acid (EDTA).
5. anode dissolution according to claim 1 is prepared the method for carbon nano tube-copper composite granule, it is characterized in that: described dispersion agent is one or more the arbitrary proportion mixtures in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, gelatin, polyvinyl alcohol, polyoxyethylene glycol, octadecanoic acid, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, alkyl fatty polyoxyethylenated alcohol, aliphatic amine polyoxyethylene ether, alkylol amide polyoxy ethane ether, block polyoxyethylene polyoxypropylene ether, alkylol amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410321915.2A CN104120458A (en) | 2014-07-08 | 2014-07-08 | Method for preparation of carbon nanotube-copper composite powder by anode dissolving |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410321915.2A CN104120458A (en) | 2014-07-08 | 2014-07-08 | Method for preparation of carbon nanotube-copper composite powder by anode dissolving |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104120458A true CN104120458A (en) | 2014-10-29 |
Family
ID=51766079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410321915.2A Pending CN104120458A (en) | 2014-07-08 | 2014-07-08 | Method for preparation of carbon nanotube-copper composite powder by anode dissolving |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104120458A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109261155A (en) * | 2018-09-25 | 2019-01-25 | 中南大学 | A kind of carbon nano tube/copper zinc alloy composites and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070036978A1 (en) * | 2005-05-20 | 2007-02-15 | University Of Central Florida | Carbon nanotube reinforced metal composites |
| US20100122910A1 (en) * | 2005-05-20 | 2010-05-20 | University Of Central Florida Research Foundation, Inc. | Electrochemical-codeposition methods for forming carbon nanotube reinforced metal composites |
| CN102528038A (en) * | 2011-12-31 | 2012-07-04 | 浙江工业大学 | Preparation method of copper/carbon nanotube composite superhydrophobic material |
-
2014
- 2014-07-08 CN CN201410321915.2A patent/CN104120458A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070036978A1 (en) * | 2005-05-20 | 2007-02-15 | University Of Central Florida | Carbon nanotube reinforced metal composites |
| US20100122910A1 (en) * | 2005-05-20 | 2010-05-20 | University Of Central Florida Research Foundation, Inc. | Electrochemical-codeposition methods for forming carbon nanotube reinforced metal composites |
| CN102528038A (en) * | 2011-12-31 | 2012-07-04 | 浙江工业大学 | Preparation method of copper/carbon nanotube composite superhydrophobic material |
Non-Patent Citations (14)
| Title |
|---|
| A sensitive nonenzymatic glucose sensor in alkaline media with a copper nanocluster/multiwall carbon nanotube-modified glassy carbon electrode;Xinhuang Kang et al.,;《ANALYTICAL BIOCHEMISTRY》;20070108;第363卷;第143-150页 * |
| Electrochemical detection of carbohydrates using copper nanoparticles and carbon nanotubes;K.B. Male et al.,;《Analytica Chimica Acta》;20040518;第516卷;第35-41页 * |
| G.S. CHO ET AL.,: "DECORATION OF CARBON NANOTUBES WITH COPPER PARTICLES BY METAL DISPLACEMENT REACTION", 《18TH INTERNATIONAL CONFERENCE ON COMPOSITE MATERIALS》 * |
| GUE-SERB CHO ET AL.,: "Cu Particles Deposition onto MWCNTs by Chemical Reaction", 《MATERIALS SCIENCE FORUM》 * |
| K.B. MALE ET AL.,: "Electrochemical detection of carbohydrates using copper nanoparticles and carbon nanotubes", 《ANALYTICA CHIMICA ACTA》 * |
| XINHUANG KANG ET AL.,: "A sensitive nonenzymatic glucose sensor in alkaline media with a copper nanocluster/multiwall carbon nanotube-modified glassy carbon electrode", 《ANALYTICAL BIOCHEMISTRY》 * |
| 余泉茂: "铁粉法与甲醛法在石墨粉表面化学镀铜的工艺对比", 《机械工程材料》 * |
| 冯立明 等: "《电镀工艺学》", 30 September 2010 * |
| 可溶阳极和不溶阳极;龚竹青;《理论电化学导论》;中南工业大学出版社;19880630;440-447 * |
| ***等: "碳纳米管/铜纳米结构电极材料在葡萄糖检测中的应用", 《高等学校化学学报》 * |
| 碳纳米管/铜纳米结构电极材料在葡萄糖检测中的应用;***等;《高等学校化学学报》;20120331;第33卷(第3期);第458-463页 * |
| 碳纳米管-超细铜粉复合粉体的制备;许龙山等;《无机材料学报》;20060331;第21卷(第2期);第309-314页 * |
| 许龙山等: "碳纳米管-超细铜粉复合粉体的制备", 《无机材料学报》 * |
| 龚竹青: "《理论电化学导论》", 30 June 1988, 中南工业大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109261155A (en) * | 2018-09-25 | 2019-01-25 | 中南大学 | A kind of carbon nano tube/copper zinc alloy composites and its preparation method and application |
| CN109261155B (en) * | 2018-09-25 | 2021-05-07 | 中南大学 | Carbon nanotube/copper-zinc alloy composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| LIU et al. | Preparation of Cu nanoparticles with NaBH4 by aqueous reduction method | |
| Zhang et al. | Preparation of copper nanoparticles by chemical reduction method using potassium borohydride | |
| Xu et al. | Catalytic reduction of 4-nitrophenol over graphene supported Cu@ Ni bimetallic nanowires | |
| CN106694904A (en) | Preparation method of highly dispersed micron order flake silver powder with large radius-thickness ratio | |
| CN109108303B (en) | Preparation method of high-dispersity Pt-Cu alloy nanoparticles | |
| CN102125853B (en) | Nano zinc ferrite-graphene composite photocatalyst of visible light response and preparation method thereof | |
| CN101972855B (en) | Method for preparing silver micro-powder for high-temperature sintering silver pastes | |
| CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
| CN108213456B (en) | Preparation method of cubic nanometer copper powder | |
| CN103466611B (en) | The preparation method of graphene load nano silver-nickel alloy composite powder material | |
| CN103456969B (en) | Preparation method of Pt-Co/C-single-layer graphene for fuel cell | |
| CN105271170B (en) | Preparation method of nano carbon and composite material of nano carbon | |
| CN106784897B (en) | A kind of preparation method of anode of fuel cell Pd/CNTs nanocatalyst | |
| CN106903324A (en) | A kind of preparation method of Graphene-nano silver dispersion | |
| CN103447549B (en) | Preparation method of cobalt nanosphere | |
| CN109304478B (en) | Method for preparing graphene/copper composite powder by one-step method | |
| CN105458292A (en) | Preparation method of carbon nano tube/copper powder | |
| CN110698903A (en) | Preparation method of three-dimensional graphene/carbon nanotube composite material for water-based electromagnetic shielding coating | |
| CN103084194A (en) | Tungsten carbide/graphene nano composite material and preparation method thereof | |
| CN110923679A (en) | Graphene-loaded nano copper particle composite material and preparation method thereof | |
| CN102886525B (en) | Cobalt powder with large grain size and preparation method thereof | |
| CN103721750B (en) | A kind of Large Diameter Pipeline carbon nano-tube catalyst and preparation method thereof | |
| Muxi et al. | Research progress on preparation technology of graphene-reinforced aluminum matrix composites | |
| Zhang et al. | Preparation, characterization and catalytic property of CuO nano/microspheres via thermal decomposition of cathode-plasma generating Cu2 (OH) 3NO3 nano/microspheres | |
| CN102718209A (en) | Method for preparing graphene based on reduction of divalent iron ion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141029 |