CN107326401A - A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites - Google Patents
A kind of preparation method of CNTs/Cu composite granules and CNTs/Cu composites Download PDFInfo
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- CN107326401A CN107326401A CN201710364458.9A CN201710364458A CN107326401A CN 107326401 A CN107326401 A CN 107326401A CN 201710364458 A CN201710364458 A CN 201710364458A CN 107326401 A CN107326401 A CN 107326401A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 178
- 239000002131 composite material Substances 0.000 title claims abstract description 128
- 239000008187 granular material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 121
- 238000004070 electrodeposition Methods 0.000 claims abstract description 34
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- 238000012545 processing Methods 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000006396 nitration reaction Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
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- 238000001556 precipitation Methods 0.000 description 4
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- 239000002109 single walled nanotube Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000009700 powder processing Methods 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical group CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- -1 polyethylene pyrrole Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- B22F1/0003—
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Abstract
The present invention relates to the preparation method of a kind of copper-based CNTs/Cu composite granules of CNT and CNTs/Cu composites, belong to new material and metallic composite preparing technical field.First by CNT（CNTs）Processing is heated to reflux with mixed acid；The CNTs that nitration mixture is handled is added in the aqueous solution containing surface dispersant, batch (-type) ultrasonic disperse, is centrifugally separating to obtain upper strata CNTs stable dispersions；Obtained CNTs stable dispersions are added in acid copper sulfate basal liquid and carry out ultrasonic disperse, CuSO in acid copper sulfate basal liquid4Concentration is 5~50g/L, H2SO4Concentration is 50~200g/L；Then on negative electrode electrochemical deposition prepare network structure CNT it is copper-based（CNTs/Cu）Composite granule, powder is scraped in electrodeposition process using periodicity.CNTs/Cu composite granules vacuum heating-press sintering, cold-rolling deformation are obtained to the high-strength highly-conductive CNTs/Cu composites of network in-line arrangement structure.The tensile strength for the composite that the present invention is obtained is 520MPa, and electrical conductivity is more than 91%IACS.
Description
Technical field
The present invention relates to the preparation method of a kind of CNTs/Cu composite granules and CNTs/Cu composites, belong to new material
With metallic composite preparing technical field.
Background technology
Prepare CNTs/Cu composites firstly the need of the key issue of solution be CNTs in Cu matrixes it is dispersed with
And the interface cohesion problem with metallic matrix.CNTs is due to very high specific surface area and Van der Waals force stronger each other
Effect, and be fiber shape, it is easy to mutually it is intertwined, so that cause CNTs to be difficult to be uniformly distributed in the base, and
Effective interface cohesion is formed between the two.In numerous preparation methods, most of powder metallurgic method is prepared using high-energy ball milling
CNTs/Cu composite granules, this method improves CNTs degree of scatter, but CNTs structures in mechanical milling process to a certain extent
Destruction is inevitable, and substantial amounts of defect, such as dislocation and internal stress can be produced in matrix, and it is excellent that these are unfavorable for performance CNTs
Physical and mechanical property, so as to cause the intensity decreases of composite, especially electrical conductivity to strongly reduce.
Electrochemical deposition technique has the advantages that technique is simple, operate controllable, multipurpose, is widely used in electronics and vapour
The industrial circles such as car.At present, the preparation that the technology is applied to CNTs/Cu composites has been studied, mainly using electrochemistry
Deposition prepares CNTs/Cu composite coatings or film, and CNTs/Cu compound wires, and these materials will be mainly used in electronics material
Micro-dimension or the small size fields such as material interconnecting pins, compound wire, battery electrode, electrochemical sensor.Patent publication No. is
CN1929110A prepares CNTs/Cu composite deposites using electrochemical deposition.The CNTs after purifying, High Temperature Disperse processing is matched somebody with somebody first
CNTs-Cu composite plating baths are made, CNTs/Cu composite deposites are prepared using electrochemical deposition, and combine micro-structural plating, photoetching and are carved
Erosion, lift-off technology, form micro- interconnecting pins structure of electronic circuit.Patent publication No. is CN101976594A using plating or changed
Be plated in CNTs fiber surfaces plating Cu coating, obtains a kind of lightweight, the CNTs compound wires of high-strength highly-conductive, but its electrical conductivity is most
A height of 20.69%IACS.Patent publication No. be CN103022450A first by CNTs chemical nickel platings, using foam copper as collector, first
Plating Cu- (CNTs-Ni) composite deposites and Sn- (CNTs-Ni) composite deposite, are finally thermally treated resulting in tin cupro-nickel-CNTs three afterwards
Tie up composite network alloys for anode materials of Li-ion battery.Patent publication No. is that the CNTs that CN101069928A is first handled nitration mixture is carried out
Gelatin is coated, then the CNTs after cladding is added in copper solution（Copper sulphate, glucose, polyethylene glycol）Electroless copper, finally
Cu oxide is reduced into copper at 200-700 DEG C in hydrogen atmosphere, CNTs is obtained and inlays in particle and in network distribution
Spherical composite pellets.In addition, document（Electrochemistry Communications, 2003,5,797-799）Report is adopted
Carbon nano-fiber (CNF)/copper laminated film, a diameter of 100-200nm of CNF used are prepared for electrochemical deposition, length is 20 μ
m.Compared to CNTs, CNF intensity and electric conductivity are easier on larger-diameter CNF to realize electrodeposit metals all not as good as CNTs
Coating.Some documents are prepared for single-walled carbon nanotube (SWCNTs)/Cu composite coatings using electrochemical deposition（Materials
Letters, 2008,62,47-50）, SWCNTs films/Cu layered composite films（Advanced Functional Materials,
2012,22,5209-5215）And obtain composite fibre in CNTs fiber surface deposited cu layer（Nanoscale, 2011,3,
4215–4219）.In above-mentioned technology, CNTs/Cu composites have although been obtained using electrochemical techniques, but using special
SWCNTs, CNTs film or fiber, cost are higher, and obtained product, which is generally, leads to line, coating, film or fiber, limits it
Using being rarely reported and prepared using electrochemical deposition with tensile strength and electric property excellent composite.The present invention
A kind of electro-deposition preparation method of CNTs/Cu composite granules is disclosed before people（Publication number CN104233379）.First to CNTs
Surface carries out mechanical activation with disperseing, and the CNTs of processing directly is added into electrochemical deposition in electrolyte and prepares composite granule.
Activated using mechanical mill and disperse CNTs, improve dispersive propertys of the CNTs in electrolyte and composite granule really, but by
It is fiber-like nanostructures in CNTs, with higher surface energy and the characteristic easily reunited, its surface modification and dispersiveness are still
It is a significant challenge for preparing CNTs/Cu composites.Therefore, the present invention proposes one kind on this basis prepares uniform point
Dissipate and the CNTs stable dispersions of belt surface electric charge new dispersing technology, and optimize solution composition and electro-deposition operating condition,
Greatly the uniformly dispersed and interface cohesions of CNTs in the base, the block of acquisition are improved by scraping powder processing in electrodeposition process
Composite material forms network in-line arrangement structure, the characteristics of with high-strength highly-conductive, has in contact material field and well should
With potentiality, while also providing beneficial enlightenment for the preparation of other metals/CNTs/ graphene composite materials.
The content of the invention
The problem of existing for above-mentioned prior art and deficiency, the present invention provide a kind of CNTs/Cu composite granules and
The preparation method of CNTs/Cu composites.The present invention prepares CNTs/Cu composite granules using electrochemical deposition.Electro-deposition it
Before, first using the original CNTs of nitration mixture purification process, selective oxidation removes wherein impurity, and in the oxygen-containing official of carbon pipe surface grafting
Can group；Using ultrasonic wave it is dispersed and centrifuge to greatest extent reduce CNTs aggregates, obtain CNTs stable dispersions；
CNTs surface functional groups produce Coulomb repulsion effect due to negatively charged, reduce CNTs and mutually reunite in the electrolytic solution, together
When Cu2+Ion effectively absorption in electronegative functional group's active site, electrodeposition process by constantly reducing, crystal nucleation and
Crystal is grown up, and CNTs is combined or is embedded into Cu matrixes, and is not only coated on matrix surface, realizes that CNTs and Cu are coprecipitated
Product；Scrape powder processing to further reduce CNTs and mutually wind, so that it is multiple to obtain good and network structure the CNTs/Cu of interface cohesion
Close powder；Composite granule is after common hot pressed sintering and cold-rolling treatment, and the final CNTs/Cu for obtaining network in-line arrangement structure is combined
Material.The present invention is achieved through the following technical solutions.
A kind of preparation method of CNTs/Cu composite granules, it is comprised the following steps that：
（1）It is 3 first by CNTs and volume ratio:1 concentrated nitric acid and the mixed acid of the concentrated sulfuric acid are heated back at a temperature of 50~80 DEG C
2~10h of stream obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs be added in the aqueous solution containing surface dispersant, using probe type
Supersonic generator 30~120min of batch (-type) ultrasonic disperse under 400~700W power, then in 1000~4000r/ of rotating speed
10~70min is centrifuged under min and obtains upper strata CNTs stable dispersions；
（3）By step（2）Obtained CNTs stable dispersions, which are added in acid copper sulfate basal liquid, carries out ultrasonic disperse, acid
CuSO in copper sulphate basal liquid4Concentration is 5~50g/L, H2SO4Concentration is 50~200g/L；Then with metallic copper（Purity is
99.99wt%）For anode, stainless steel is negative electrode, and cathode-current density is 100~300mA/cm2, constant current electro-deposition at room temperature
120~300min and mechanical agitation or ultrasonic vibration simultaneously, electrochemical deposition prepares the CNTs/ of network structure on negative electrode
Cu composite granules, using periodically powder is scraped in electrodeposition process, scrape powder interval time for 5~40min, powder are scraped every time by negative electrode
Upper all composite granules are scraped.
The step（1）Middle CNTs is multi-walled carbon nanotube, and external diameter is 8~50nm, and length is 0.5~30 μm.
The step（2）Middle surface dispersant is lauryl sodium sulfate（SLS）, neopelex（SDBS）、
Hexadecyltrimethylammonium chloride（CTAC）, cetyl trimethylammonium bromide（CTAB）, polyethylene glycol（PEG）, polyethylene pyrrole
Pyrrolidone（PVP）In one kind or any two kinds of scalemic thereofs.
Above-mentioned concentrated nitric acid and the concentrated sulfuric acid are the pure concentrated nitric acid of analysis and the concentrated sulfuric acid.
A kind of method that above-mentioned CNTs/Cu composite granules prepare CNTs/Cu composites, it is comprised the following steps that：
（1）By the CNTs/Cu composite granule vacuum heating-press sinterings prepared, 6.67 × 10-3Under Pa vacuum conditions, in temperature
Degree is 500~800 DEG C, pressure is 30~150min of hot pressed sintering under 40~80MPa, obtains CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites carry out the cold rolling high-strength highly-conductive CNTs/ for obtaining network in-line arrangement structure
Cu composites.
The step（2）In it is cold rolling for large deformation processing, deflection be 50~90%.
The beneficial effects of the invention are as follows：
（1）The dispersivenesses of CNTs in the electrolytic solution greatly improve, and are provided by CNTs surface modifications, ultrasonic disperse and centrifugation
A kind of method for preparing stable CNTs dispersion liquids；
（2）CNTs/Cu composite granules only need to obtain by once-combined electro-deposition, are not required to hydrogen reducing, and composite granule
Particle diameter is adjustable, and purity is high, the Cu with height preferred orientation（111）Face, advantageously forms the twin of certain density（twin）, carry
The high intensity of matrix, also improves the electric property of material；
（3）CNTs forms network in-line arrangement structure and high interfacial bonding strength in the base, not only increases the power of composite
Performance is learned, and new passage is provided for electric transmission, the tensile strength of gained composite is 520MPa, and electrical conductivity is more than
91%IACS；
（4）Electrodeposition technology is simple and easy to apply, composite electrolyte reusable edible used, it is only necessary to regular replenishment, environment-friendly, is combined
The processing technology of material has stronger compatibility with existing process, contributes to the lifting and popularization and application of technology and product.
Brief description of the drawings
Fig. 1 is that electrochemical deposition of the present invention prepares CNTs/Cu composite granule schematic diagrames；
Fig. 2 is the CNTs/Cu composite granule scanning electron microscope (SEM) photographs that the embodiment of the present invention 1 is prepared；
Fig. 3 is the CNTs/Cu composite granule transmission electron microscope pictures that the embodiment of the present invention 1 is prepared；
Fig. 4 be the embodiment of the present invention 2 prepare it is cold rolling after CNTs/Cu composite transmission electron microscope pictures；
Fig. 5 be the embodiment of the present invention 2 prepare it is cold rolling after CNTs/Cu fracture of composite materials surface scanning electron microscope (SEM) photograph；
Fig. 6 be the embodiment of the present invention 2 prepare it is cold rolling after CNTs/Cu composites and anode industrial pure copper plate should
Force-strain curve figure；
Fig. 7 be the embodiment of the present invention 2 prepare it is cold rolling after CNTs/Cu composites and anode industrial pure copper plate property
Can comparison diagram.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The preparation method of the CNTs/Cu composite granules, it is comprised the following steps that：
（1）First by CNTs（External diameter is 8~20nm, and length is 2~10 μm）It is 3 with volume ratio:1 concentrated nitric acid（Mass fraction
For 67%）And the concentrated sulfuric acid（Mass fraction is 98%）Mixed acid be heated to reflux 2h at a temperature of 80 DEG C, make its surface graft oxygen-containing
Functional group, obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs（1.83g）It is added to containing surface dispersant（Mass ratio is 1:1
SDBS and PVP, gross mass is 1g）The aqueous solution（200mL）In, using probe type supersonic generator under 500W power interval
Formula ultrasonic disperse 60min（Per 5~8min of ultrasonic disperse 10min intervals）, then centrifuged under rotating speed 2000r/min
30min, precipitation quality is 0.23g, obtains upper strata CNTs stable dispersions（Concentration is 8g/L）；
（3）By step（2）Obtained CNTs stable dispersions（40mL）It is added to acid copper sulfate basal liquid（800mL）It is middle to carry out
CuSO in ultrasonic disperse 30min, acid copper sulfate basal liquid4Concentration is 15g/L, H2SO4Concentration is 100g/L；Then with metal
Copper（Purity is 99.99wt%）For anode, stainless steel is negative electrode, and cathode-current density is 170mA/cm2, constant current is electric at room temperature
240min and simultaneously mechanical agitation are deposited, electrochemical deposition prepares the CNTs/Cu composite granules of network structure on negative electrode
（CNTs volume fractions in powder are 2.5%, and composite granule particle diameter is 0.50 μm）, scraped in electrodeposition process using periodicity
Powder, scrapes powder interval time for 5min, powder is scraped every time and scrapes composite granule all on negative electrode.
Above-mentioned electrochemical deposition prepares CNTs/Cu composite granules schematic diagram as shown in figure 1, Fig. 2 and Fig. 3 are respectively electro-deposition
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of gained CNTs/Cu composite granules, as can be seen that gained composite granule from Fig. 2 and Fig. 3
Pattern is substantially spherical in shape, uniform particle sizes, in CNTs insertion Cu matrixes, is connected to different Cu particles, and in network distribution, with matrix
With high interfacial bonding strength.
Embodiment 2
The method that the CNTs/Cu composite granules prepare CNTs/Cu composites, it is comprised the following steps that：
（1）The CNTs/Cu composite granule vacuum heating-press sinterings that embodiment 1 is prepared, 6.67 × 10-3Pa vacuum conditions
Under, temperature be 700 DEG C, pressure be hot pressed sintering 120min under 60MPa, obtain CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites progress is cold rolling, and cold rolling reduction is 65%（Thickness reduces 65%）, change
The arragement directions of kind CNTs in the base, obtain the high-strength highly-conductive CNTs/Cu composites of network in-line arrangement structure.
CNTs/Cu composites transmission electron microscope picture after cold rolling is as shown in figure 4, the CNTs/Cu composites after cold rolling break
Split the scanning electron microscope (SEM) photograph on surface as shown in figure 5, CNTs/Cu composites after cold rolling and anode industrial pure copper plate stress-
Strain curve figure is as shown in fig. 6, the performance comparison figure such as figure of the CNTs/Cu composites and anode industrial pure copper plate after cold rolling
Shown in 7；Figure 4, it is seen that hot pressed sintering CNTs/Cu composites are after cold-rolling treatment, CNTs orientation is with rolling
Direction processed is substantially parallel, is distributed in the base in in-line arrangement, from figure 5 it can be seen that composite has ductile rupture structure,
CNTs is extracted from matrix, is firmly combined with network in-line arrangement structure, and with basal body interface, from fig. 6 it can be seen that composite wood
The tensile strength of material is plastically deformed apparently higher than anode industrial pure copper plate, and with preferable, it can be seen from figure 7 that phase
Than fine copper plate, the tensile strength of composite is significantly improved, and electrical conductivity is slightly reduced, and shows that the composite material combination property is good
It is good.
Embodiment 3
The preparation method of the CNTs/Cu composite granules, it is comprised the following steps that：
（1）First by CNTs（External diameter is 20~30nm, and length is 0.5~2 μm）It is 3 with volume ratio:1 concentrated nitric acid（Quality point
Number is 67%）And the concentrated sulfuric acid（Mass fraction is 98%）Mixed acid be heated to reflux 5h at a temperature of 70 DEG C, contain its surface graft
Oxygen functional group, obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs（1.94g）It is added to containing surface dispersant（PEG, quality is 1g）
The aqueous solution（200mL）In, using probe type supersonic generator under 600W power batch (-type) ultrasonic disperse 30min（Often surpass
Sound disperses 5~8min of 10min intervals）, 10min is then centrifuged under rotating speed 1000r/min, precipitation quality is 0.54g, is obtained
To upper strata CNTs stable dispersions（Concentration is 7g/L）；
（3）By step（2）Obtained CNTs stable dispersions（40mL）It is added to acid copper sulfate basal liquid（800mL）It is middle to carry out
CuSO in ultrasonic disperse 30min, acid copper sulfate basal liquid4Concentration is 30g/L, H2SO4Concentration is 150g/L；Then with metal
Copper（Purity is 99.99wt%）For anode, stainless steel is negative electrode, and cathode-current density is 240mA/cm2, constant current is electric at room temperature
180min and ultrasonic vibration simultaneously are deposited, electrochemical deposition prepares the CNTs/Cu composite granules of network structure on negative electrode
（CNTs volume fractions in powder are 4%, and composite granule particle diameter is 0.88 μm）, powder is scraped using periodicity in electrodeposition process,
Powder interval time is scraped for 15min, powder is scraped every time and scrapes composite granule all on negative electrode.
Embodiment 4
The method that the CNTs/Cu composite granules prepare CNTs/Cu composites, it is comprised the following steps that：
（1）The CNTs/Cu composite granule vacuum heating-press sinterings that embodiment 3 is prepared, 6.67 × 10-3Pa vacuum conditions
Under, temperature be 800 DEG C, pressure be hot pressed sintering 30min under 50MPa, obtain CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites progress is cold rolling, and cold rolling reduction is 75%（Thickness reduces 75%）, change
The arragement directions of kind CNTs in the base, obtain the high-strength highly-conductive CNTs/Cu composites of network in-line arrangement structure.Gained composite wood
The tensile strength of material is 520MPa, and electrical conductivity is more than 91%IACS.
Embodiment 5
The preparation method of the CNTs/Cu composite granules, it is comprised the following steps that：
（1）First by CNTs（External diameter is 40~50nm, and length is 10~30 μm）It is 3 with volume ratio:1 concentrated nitric acid（Quality point
Number is 67%）And the concentrated sulfuric acid（Mass fraction is 98%）Mixed acid be heated to reflux 8h at a temperature of 60 DEG C, contain its surface graft
Oxygen functional group, obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs（1.34g）It is added to containing surface dispersant（Mass ratio is 1:1
SLS and CTAC, gross mass is 1g）The aqueous solution（200mL）In, using probe type supersonic generator under 400W power interval
Formula ultrasonic disperse 120min（Per 5~8min of ultrasonic disperse 10min intervals）, then centrifuged under rotating speed 4000r/min
70min, precipitation quality is 0.14g, obtains upper strata CNTs stable dispersions（Concentration is 6g/L）；
（3）By step（2）Obtained CNTs stable dispersions（40mL）It is added to acid copper sulfate basal liquid（800mL）It is middle to carry out
CuSO in ultrasonic disperse 30min, acid copper sulfate basal liquid4Concentration is 5g/L, H2SO4Concentration is 50g/L；Then with metallic copper
（Purity is 99.99wt%）For anode, stainless steel is negative electrode, and cathode-current density is 100mA/cm2, constant current electricity is heavy at room temperature
Product 300min and simultaneously mechanical agitation, electrochemical deposition prepares the CNTs/Cu composite granules of network structure on negative electrode
（CNTs volume fractions in powder are 1.5%, and composite granule particle diameter is 0.71 μm）, scraped in electrodeposition process using periodicity
Powder, scrapes powder interval time for 30min, powder is scraped every time and scrapes composite granule all on negative electrode.
Embodiment 6
The method that the CNTs/Cu composite granules prepare CNTs/Cu composites, it is comprised the following steps that：
（1）The CNTs/Cu composite granule vacuum heating-press sinterings that embodiment 5 is prepared, 6.67 × 10-3Pa vacuum conditions
Under, temperature be 600 DEG C, pressure be hot pressed sintering 60min under 40MPa, obtain CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites progress is cold rolling, and cold rolling reduction is 50%（Thickness reduces 50%）, change
The arragement directions of kind CNTs in the base, obtain the high-strength highly-conductive CNTs/Cu composites of network in-line arrangement structure.
Embodiment 7
The preparation method of the CNTs/Cu composite granules, it is comprised the following steps that：
（1）First by CNTs（External diameter is 30~40nm, and length is 10~20 μm）It is 3 with volume ratio:1 concentrated nitric acid（Quality point
Number is 67%）And the concentrated sulfuric acid（Mass fraction is 98%）Mixed acid be heated to reflux 10h at a temperature of 50 DEG C, contain its surface graft
Oxygen functional group, obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs（1.16g）It is added to containing surface dispersant（CTAB, quality is
1g）The aqueous solution（200mL）In, using probe type supersonic generator under 700W power batch (-type) ultrasonic disperse 90min（Often
5~8min of ultrasonic disperse 10min intervals）, 50min is then centrifuged under rotating speed 3000r/min, precipitation quality is 0.16g,
Obtain upper strata CNTs stable dispersions（Concentration is 5g/L）；
（3）By step（2）Obtained CNTs stable dispersions（40mL）It is added to acid copper sulfate basal liquid（800mL）It is middle to carry out
CuSO in ultrasonic disperse 30min, acid copper sulfate basal liquid4Concentration is 50g/L, H2SO4Concentration is 200g/L；Then with metal
Copper（Purity is 99.99wt%）For anode, stainless steel is negative electrode, and cathode-current density is 300mA/cm2, constant current is electric at room temperature
120min and mechanical agitation or ultrasonic vibration simultaneously are deposited, electrochemical deposition prepares the CNTs/ of network structure on negative electrode
Cu composite granules（CNTs volume fractions in powder are 0.6%, and composite granule particle diameter is 1 μm）, using week in electrodeposition process
Phase property scrapes powder, scrapes powder interval time for 40min, powder is scraped every time and scrapes composite granule all on negative electrode.
Embodiment 8
The method that the CNTs/Cu composite granules prepare CNTs/Cu composites, it is comprised the following steps that：
（1）Embodiment 7 is prepared into CNTs/Cu composite granule vacuum heating-press sinterings.6.67 × 10-3Under Pa vacuum conditions,
Temperature be 500 DEG C, pressure be hot pressed sintering 150min under 80MPa, obtain CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites progress is cold rolling, and cold rolling reduction is 90%（Thickness reduces 90%）, change
The arragement directions of kind CNTs in the base, obtain the high-strength highly-conductive CNTs/Cu composites of network in-line arrangement structure.
Above in association with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can also be before present inventive concept not be departed from the knowledge that those of ordinary skill in the art possess
Put that various changes can be made.
Claims (5)
1. a kind of preparation method of CNTs/Cu composite granules, it is characterised in that comprise the following steps that：
（1）It is 3 first by CNTs and volume ratio:1 concentrated nitric acid and the mixed acid of the concentrated sulfuric acid are heated back at a temperature of 50~80 DEG C
2~10h of stream obtains the CNTs of nitration mixture processing；
（2）By step（1）In obtain nitration mixture processing CNTs be added in the aqueous solution containing surface dispersant, using probe type
Supersonic generator 30~120min of batch (-type) ultrasonic disperse under 400~700W power, then in 1000~4000r/ of rotating speed
10~70min is centrifuged under min and obtains upper strata CNTs stable dispersions；
（3）By step（2）Obtained CNTs stable dispersions, which are added in acid copper sulfate basal liquid, carries out ultrasonic disperse, acid
CuSO in copper sulphate basal liquid4Concentration is 5~50g/L, H2SO4Concentration is 50~200g/L；Then using metallic copper as anode, no
Rust steel is negative electrode, and cathode-current density is 100~300mA/cm2, 120~300min of constant current electro-deposition and same opportunity at room temperature
Tool is stirred or ultrasonic vibration, and electrochemical deposition prepares the CNTs/Cu composite granules of network structure on negative electrode, in electro-deposition
During using periodically powder is scraped, scrape powder interval time for 5~40min, powder scraped every time and scrapes composite granule all on negative electrode
Under.
2. the preparation method of CNTs/Cu composite granules according to claim 1, it is characterised in that：The step（1）In
CNTs is multi-walled carbon nanotube, and external diameter is 8~50nm, and length is 0.5~30 μm.
3. the preparation method of CNTs/Cu composite granules according to claim 1, it is characterised in that：The step（2）Middle table
Face dispersant is lauryl sodium sulfate, neopelex, hexadecyltrimethylammonium chloride, cetyl trimethyl
One kind or any two kinds of scalemic thereofs in ammonium bromide, polyethylene glycol, polyvinylpyrrolidone.
4. a kind of method that CNTs/Cu composites are prepared according to any described CNTs/Cu composite granules of claims 1 to 3,
It is characterized in that comprising the following steps that：
（1）By the CNTs/Cu composite granule vacuum heating-press sinterings prepared, 6.67 × 10-3Under Pa vacuum conditions, in temperature
It is 30~150min of hot pressed sintering under 40~80MPa for 500~800 DEG C, pressure, obtains CNTs/Cu composites；
（2）By step（1）Obtained CNTs/Cu composites carry out the cold rolling high-strength highly-conductive CNTs/ for obtaining network in-line arrangement structure
Cu composites.
5. the method that CNTs/Cu composite granules according to claim 4 prepare CNTs/Cu composites, it is characterised in that：
The step（2）In it is cold rolling for large deformation processing, deflection be 50~90%.
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