CN104711568B - A kind of preparation method and its device for wrapping up carbon nanomaterial on the metal filament - Google Patents
A kind of preparation method and its device for wrapping up carbon nanomaterial on the metal filament Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and its device for wrapping up carbon nanomaterial on the metal filament, this method is that wire proper alignment is got well and bundled to form capillary, then it is impregnated into the suspension containing carbon nanomaterial, pass through evaporation drying after taking-up again, and this operation is repeated, then the wire being bundled into together separately can obtain to the wire of carbon nanomaterial parcel.Proper alignment is got well and bundle by CNT wrap up wire be impregnated into again in graphene suspension, the wire being bundled into together separately then be can obtain into CNT, the wire that graphene wraps up successively.Wire proper alignment is got well and bundled and is impregnated into CNT and graphene mixing suspension, then by evaporation drying, and can be repeated several times, then the wire being bundled into together separately can obtain to the wire of CNT and the compound parcel of graphene.This method and its industrialized production that is simply easy to, have in fields such as electromagnetic shielding, conductive cable, flexible electronic device, intelligent textile, solar device, energy-storage battery, line style ultracapacitors and be extremely widely applied prospect.
Description
Technical field
The present invention relates to wire paint-on technique, is related specifically to a kind of preparation side for wrapping up carbon nano material on the metal filament
Method and its device.
Background technology
CNT and graphene with its unique crystal structure, make it have carrier mobility is high, specific surface area is big,
Metal or semiconductive, quantum hall effect, mechanical strength and the high performance of elasticity, these excellent performances cause it various
Field has a wide range of applications, as Flied emission field, sensor field, electrochemical field, fuel cell catalyst.Although carbon
The nanostructured performance of nanotube and graphene protrudes, but still faced one difficult processing, high processing costs and performance during conduct coating
The outstanding problem such as be hard to keep.When especially wrapping up wire, traditional spraying coating process causes substantial amounts of raw material losses,
And low production efficiency.Therefore, existing multiple research units are expanded in terms of wrapping up CNT and graphene on the metal filament
Research.Such as：Shanghai Silicate Inst., Chinese Academy of Sciences is to be led to using metal wire or wire as catalysts template within 2012
Cross graphene/gold that chemical vapour deposition technique makes carbon source directly generate graphene coating in the outer surface of the metal wire and formed
Belong to line or metal wire composite structure (publication number：CN102560415A).This method needs to carry out under 700 DEG C of high temperature above,
The catalytic growth of graphene is required to the species of metal wire, and the thickness of graphene layer is influenceed also enter line width by growth mechanism
The regulation and control of scope.University Of Ji'nan in 2012 develops prepares the micro- extraction of LBL self-assembly graphite ene coatings solid phase in wire carrier
The method for taking fiber, wire carry out chemical silvering, then the method using LBL self-assembly to its surface, with gold as carrier
Nano particle is as linking arm, by (publication number on mercapto-functionalized graphene LBL self assembly to silver plated metals silk：
CN102553553A).This method needs to be attached with other nano-particles or organic molecule, and step is complicated；And graphene
It is spaced between layer, weakens interlaminar action power.Seminar of Tsing-Hua University, which utilizes to be electrochemically-deposited on metal wire, deposited stone
Black alkene is used for electrode of super capacitor (Chemical Communications, 2013,49,291).Electrochemical deposition energy consumption is big,
The non-laminar stacked arrangement of graphene deposited, poor adhesion.In addition, while CNT and graphene fiber is prepared,
Using twisted method can CNT and graphene parcel on the metal filament (Nature communications, 2014,
4:1970；ACS Nano,2014,8,4571).But this method preparation technology is complicated, it is difficult to realizes long length and batch production.
And the present invention can solve the problems, such as above well.
The content of the invention
It is an object of the invention to provide a kind of new method for wrapping up carbon nanomaterial on the metal filament, this method is according to capillary
Principle, additional evaporation drying, the wire of prepared carbon nanomaterial parcel is in electromagnetic shielding, conductive cable, flexible electronic
The fields such as device, intelligent textile, solar device, energy-storage battery, line style ultracapacitor have a wide range of applications.
The present invention is achieved through the following technical solutions：Wire surface is cleaned up；Single metal wire is wound on
Get well and bundle on axis or 2 and above wire proper alignment；Proper alignment or the wire wound are soaked
Stain is into the mixture suspension containing carbon nanomaterial；Pass through evaporation drying；Repeat aforesaid operations；The gold that will be bundled
The wire that category silk is separated or untied on axis can obtain the wire that carbon nanomaterial wraps up.
Wire used is normal temperature solid-state elemental metals silk or alloying metal silk, for preparing carbon nanomaterial parcel
Wire includes spun gold, filamentary silver, copper wire, iron wire, nickel wire, cobalt silk, aluminium wire, zinc silk, magnesium silk, titanium silk, bismuth silk, chromium silk, manganese silk, tantalum
Silk, tungsten filament, molybdenum filament, platinum filament, rhodium silk, ruthenium silk, palladium silk, rhenium silk or iridium wire or their B alloy wire.
For prepare wire carbon nanomaterial include single-walled carbon nanotube, few-wall carbon nanotube, multi-walled carbon nanotube,
Graphene oxide, redox graphene, graphene or graphite nano plate or their mixture.
Suspension used includes carbon nanomaterial, solvent, dispersant and binding agent.Wherein, solvent include water, methanol,
Ethanol, isopropanol, ethylene glycol, methyl ether, ether, ethyl methyl ether, acetone, butanone, MEK, chloroform, carbon tetrachloride, benzene, toluene, four
Hydrogen furans, dimethylformamide, dimethyl sulfoxide (DMSO), acetic acid, methyl formate and its mixture；Dispersant includes：Dodecyl sulphur
Sour sodium, cetyl trimethylammonium bromide, polyvinyl alcohol, polyethylene glycol, PVP, span 80, Triton
X-100；Binding agent agent includes：Cellulose, chitosan, Nafion, epoxy resin, phenolic resin, polyaminoacid methyl esters.
Wire is successively impregnated into containing in different carbon nanomaterial suspension, by impregnating, after drying, wire divides again
Open the wire that can obtain different carbon nanomaterial parcels.
Present invention also offers a kind of device for wrapping up carbon nanomaterial on the metal filament, the device includes：Stainless steel gold
Belong to rod (1), stainless steel disk (2), article carrying platform (3), cavity (4), motor (5), wire (6), axle (10), including speed to show
Shield the speed control system (7) of (8) and speed control knob (9)；Stainless steel bar (1) is vertically fixed in stainless steel disk (2),
The axle (10) of stainless steel disk (2) is connected with motor (5), and speed control system (7) is connected by wire (6) with motor (5), no
The axle (10) of rust steel disk (2) can move axially perpendicular to cavity (4) and along cavity (4), and article carrying platform (3) hangs down with cavity (4)
Directly, the suspension containing carbon nanomaterial is placed on article carrying platform (3).
Beneficial effect：
1st, the method provided by the invention for preparing wire utilizes capillary principle, can carry out at normal temperatures, with chemical deposition
The methods of compare, simple, quick, safety is simultaneously readily produced.
2nd, the wire electric conductivity for the carbon nanomaterial parcel invented is fabulous, and has preferable mechanical performance and corrosion resistant
Performance, it is super in electromagnetic shielding, conductive cable, flexible electronic device, intelligent textile, solar device, energy-storage battery, line style
The fields such as capacitor have a wide range of applications.
3rd, assembling carbon nanomaterial utilizes the additional evaporation drying of capillary principle to the present invention on the metal filament, at normal temperatures
Carry out, safety and built-up time is extremely short operates convenient and swift, cost is cheap, beneficial to large-scale production.With LBL self-assembly
The method of graphene coating solid phase micro-extraction fiber is more compared to even more simple and fast, and free from admixture influences.
Brief description of the drawings
Fig. 1 is the structural representation of apparatus of the present invention；
Identifier declaration：1- stainless steel metal rods；2- stainless steel disks；3- article carrying platforms；4- cavitys；5- motors；6- wires；
7- speed control systems；8- speed display screens；9- speed control knobs；10- axles.
Fig. 2 is the scanning electron microscope diagram of original Ni silks.
Fig. 3 is assembling graphene oxide Ni silk scanning electron microscope diagrams.
Embodiment
The present invention relates to a kind of preparation method for wrapping up carbon nanomaterial on the metal filament, the carbon in the embodiment of the present invention
Nano material is by taking CNT and graphene as an example.Wire surface is cleaned up, proper alignment is got well and bundled, and is surpassed
Long wire, it can be bundled by coil mode, be wrapped on the stainless steel metal rod of experimental provision, be then impregnated into
In carbon nano tube suspension, regulation rotating speed makes its uniform rotation in carbon nano tube suspension, after evaporation drying, and it is repeatable more
It is secondary, then the wire that proper alignment is got well and bundled separately can obtain CNT parcel wire.Or bundle
The wire for the CNT parcel being held together is wrapped on the stainless steel metal rod of experimental provision, is impregnated into graphene suspension
In liquid, regulation rotating speed makes its uniform rotation in graphene suspension, then by evaporation drying, and can be repeated several times, then will be whole
The neat wire for arranging and bundling separately can obtain the wire that CNT and graphene wrap up successively.Or will
Wire surface is cleaned up, and proper alignment is got well and bundles and be wrapped on the stainless steel metal rod of experimental provision, so
After be impregnated into CNT and graphene mixture suspension, regulation rotating speed it is hanged in CNT and graphene mixture
Uniform rotation is again by evaporation drying in supernatant liquid, and can be repeated several times, then the wire that proper alignment is got well and bundled
It separately can obtain the wire of CNT and graphene mixture parcel.Wire used include but is not limited to spun gold,
Filamentary silver, copper wire, iron wire, nickel wire, cobalt silk, aluminium wire, zinc silk, magnesium silk, titanium silk, bismuth silk, chromium silk, manganese silk, tantalum wire, tungsten filament, molybdenum filament, platinum
Silk, rhodium silk, ruthenium silk, palladium silk, rhenium silk or iridium wire or their alloying metal silk；Carbon nanomaterial used includes but is not limited to：
Single-walled carbon nanotube, few-wall carbon nanotube, multi-walled carbon nanotube, graphene oxide, redox graphene, graphene, graphite
Nanometer sheet and its mixture.
Preparation method is as follows：
(1) N (N of equal length are chosen>1, and be integer) section spun gold, filamentary silver, copper wire, iron wire, nickel wire, cobalt silk, aluminium wire, zinc
Silk, magnesium silk, titanium silk, bismuth silk, chromium silk, manganese silk, tantalum wire, tungsten filament, molybdenum filament, platinum filament, rhodium silk, ruthenium silk, palladium silk, rhenium silk or iridium wire or it
B alloy wire titanium, bismuth, chromium, manganese, tantalum, tungsten, molybdenum, platinum, rhodium, ruthenium, palladium, rhenium, iridium and its alloying metal silk.
(2) by the wire of selection clean up and it is neat be bundled into together, be then impregnated into carbon nano tube suspension
In, drying or drying after taking-up, and can be repeated several times, prepare the wire of CNT parcel.
(3) carbon nano tube suspension includes CNT, solvent, dispersant and binding agent.
(4) wire includes but is not limited to spun gold, filamentary silver, copper wire, iron wire, nickel wire, cobalt silk, aluminium wire, zinc silk, magnesium silk, titanium
Silk, bismuth silk, chromium silk, manganese silk, tantalum wire, tungsten filament, molybdenum filament, platinum filament, rhodium silk, ruthenium silk, palladium silk, rhenium silk or iridium wire or their alloy
Silk, titanium, bismuth, chromium, manganese, tantalum, tungsten, molybdenum, platinum, rhodium, ruthenium, palladium, rhenium, iridium and its alloying metal silk.
(5) solvent includes water, methanol, ethanol, isopropanol, ethylene glycol, methyl ether, ether, ethyl methyl ether, acetone, butanone, first and second
Ketone, chloroform, carbon tetrachloride, benzene, toluene, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide (DMSO), acetic acid, methyl formate and its mixed
Compound.
(6) dispersant includes lauryl sodium sulfate, cetyl trimethylammonium bromide, polyvinyl alcohol, polyethylene glycol, poly-
Vinyl pyrrolidone, span 80, Triton X-100.
(7) binding agent includes cellulose, chitosan, Nafion, epoxy resin, phenolic resin, polyaminoacid methyl esters.
(8) wire of proper alignment and the CNT parcel bundled is immersed in graphene suspension,
Drying or drying after taking-up, and can be repeated several times, preparing CNT, the wire that graphene wraps up successively.
(9) CNT or graphene suspension include CNT or graphene, and (same to step 5), dispersant are (same for solvent
Step 6) and binding agent (same to step 7).
(10) wire that metal nano wire prepared by step 2 wraps up is operated according to step 8, obtains carbon nanometer
The wire that pipe, graphene wrap up successively.
(11) proper alignment and the wire that has bundled are immersed in CNT and graphene mixing suspension, taken out
Drying or drying afterwards, and can be repeated several times, preparing the conductive wire of CNT and graphene mixing parcel.
Carbon nanomaterial includes but is not limited to, single-walled carbon nanotube, few-wall carbon nanotube, multi-walled carbon nanotube, oxidation stone
Black alkene, redox graphene, graphene, graphite nano plate and its mixture, in above-mentioned preparation method and example below
Carbon nanomaterial use CNT and graphene.
Embodiment 1
(1) N (N are chosen>2, and be integer) the copper metal silk of section equal length, is cleaned up, and the wire of selection is neat
Arrange and bundle, be wrapped in experimental provision relevant position.
(2) 0.02-0.5 grams of single-walled carbon nanotube is added to the water and isopropanol mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of cellulose are added, single-walled carbon nanotube suspension is made
Liquid.
(3) the copper metal silk wound is immersed in single-walled carbon nanotube suspension, regulation rotating speed makes it be received in single wall carbon
Uniform rotation in mitron suspension, then taking out and dried at 1-200 DEG C, this process can be carried out repeatedly, then by proper alignment
The wire got well and bundled separates, and prepares the copper metal silk of highly conductive single-walled carbon nanotube parcel.
Embodiment 2
(1) the copper metal silk of the single-walled carbon nanotube parcel bundled in one section of embodiment 1 is chosen, is wrapped in experimental provision
Relevant position.
(2) 0.02-0.5 grams of graphene is added in the water and isopropanol mixing suspension that volume ratio is 0.1-10, then
0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of cellulose are added, graphene suspension is made.
(3) the copper metal silk that the single-walled carbon nanotube wound wraps up is placed in graphene suspension, regulation rotating speed makes
It takes out in graphene suspension after uniform rotation is dried at 1-200 DEG C, and this process can be carried out repeatedly, then will neatly be arranged
Arrange wire that is good and bundling to separate, prepare single-walled carbon nanotube, the copper metal silk that graphene wraps up successively.
Embodiment 3
(1) N (N are chosen>2, and be integer) the nickel wire of section equal length cleans up, by wire proper alignment well simultaneously
Bundle, be wrapped in experimental provision relevant position.
(2) 0.02-0.5 grams of single-walled carbon nanotube is added in tetrahydrofuran suspension, adds 0.001-0.1 grams and gather
Vinyl alcohol and 0.0001-0.001 grams of epoxy resin, are made single-walled carbon nanotube suspension.
(3) the nickel wire wound is immersed in single-walled carbon nanotube suspension, regulation rotating speed makes it in single wall carbon
Uniform rotation in nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, then will neatly be arranged
Arrange nickel wire that is good and bundling to separate, prepare the highly conductive nickel wire of single-walled carbon nanotube parcel.
Embodiment 4
(1) the nickel wire of the single-walled carbon nanotube parcel bundled in one section of embodiment 3 is chosen, is wrapped in experiment
Device relevant position.
(2) 0.02-0.5 grams of graphene is added in the water and isopropanol mixing suspension that volume ratio is 0.1-10, then
0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of chitosan are added, graphene suspension is made.
(3) the nickel wire that the single-walled carbon nanotube wound wraps up is placed in graphene suspension, regulation rotating speed makes
Its uniform rotation in graphene suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, then should
The nickel wire bundled separates, and prepares CNT, the nickel wire that graphene wraps up successively.
Embodiment 5
(1) N (N are chosen>2, and be integer) the golden wire of section equal length, is cleaned up, and the wire of selection is neat
Arrange and bundle, be wrapped in experimental provision relevant position.
(2) 0.02-0.5 grams of single-walled carbon nanotube is added to the water and isopropanol mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of Nafion are added, single-walled carbon nanotube suspension is made
Liquid.
(3) the golden wire wound is immersed in single-walled carbon nanotube suspension, regulation rotating speed makes it in single wall carbon
Uniform rotation in nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, and will be bundled in
Wire together separates, and prepares the golden wire of highly conductive single-walled carbon nanotube parcel.
Embodiment 6
(1) the golden wire of the single-walled carbon nanotube parcel neatly bundled in one section of embodiment 5 is chosen, is wrapped in
Experimental provision relevant position.
(2) 0.02-0.5 grams of graphene is added in the water and isopropanol mixing suspension that volume ratio is 0.1-10, then
0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of epoxy resin are added, graphene suspension is made.
(3) the golden wire that the single-walled carbon nanotube wound wraps up is placed in graphene suspension, regulation rotating speed makes
Its uniform rotation in graphene suspension, then take out and dried at 1-200 DEG C, this process can carry out repeatedly, bundling
Golden wire together separates, and prepares single-walled carbon nanotube, the golden wire that graphene wraps up successively.
Embodiment 7
(1) N (N are chosen>2, and be integer) the silver metal silk of section equal length, is cleaned up, and the wire of selection is whole
Arrange and bundle together, be wrapped in the relevant position of experimental provision.
(2) 0.02-0.5 grams of double-walled carbon nano-tube is added to the water and ethanol mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of cetyl trimethylammonium bromide and 0.0001-0.001 grams of phenolic resin are added, double-walled carbon is made and receives
Mitron suspension.(3) the silver metal silk wound is immersed in double-walled carbon nano-tube suspension, regulation rotating speed makes it in double-walled
Uniform rotation in carbon nano tube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, and will binding
Wire together separates, and prepares the silver metal silk of highly conductive double-walled carbon nano-tube parcel.
Embodiment 8
(1) the silver metal silk of proper alignment in one section of embodiment 7 and the double-walled carbon nano-tube parcel bundled is chosen,
It is wrapped in the relevant position of experimental provision.
(2) 0.02-0.5 grams of graphene nanometer sheet is added to the water and ethylene glycol mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of polyvinyl alcohol and 0.0001-0.001 grams of polyaminoacid methyl esters are added, graphene nanometer sheet suspension is made
Liquid.
(3) the silver metal silk that the double-walled carbon nano-tube wound wraps up is placed in graphene nanometer sheet suspension, controlled
Rotating speed makes its uniform rotation in graphene nanometer sheet suspension, then takes out and is dried at 1-200 DEG C, and this process can be carried out
Repeatedly, then by this wire bundled separates, and prepares double-walled carbon nano-tube, the silver gold that graphene nanometer sheet wraps up successively
Belong to silk.
Embodiment 9
(1) N (N are chosen>2, and be integer) the aluminum metal silk of section equal length, is cleaned up, and the wire of selection is neat
Arrange and bundle, be wrapped in the relevant position of experimental provision.
(2) 0.02-0.5 grams of multi-walled carbon nanotube is added to the water and ethanol mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of PVP and 0.0001-0.001 grams of cellulose are added, multi-walled carbon nanotube is made and hangs
Supernatant liquid.
(3) the aluminum metal silk wound is immersed in multi-walled carbon nanotube suspension, regulation rotating speed makes it in more wall carbon
Uniform rotation in nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, then this is bundled
Good wire separates, and prepares the aluminum metal silk of highly conductive multi-walled carbon nanotube parcel.
Embodiment 10
(1) the aluminum metal silk of the multi-walled carbon nanotube parcel bundled in one section of embodiment 9 is chosen, is wrapped in experiment
On the relevant position of device.
(2) 0.02-0.5 grams of redox graphene is added to the water and ethylene glycol mix suspending that volume ratio is 0.1-10
In liquid, 0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of chitosan are added, redox graphene is made
Suspension.
(3) the aluminum metal silk that the multi-walled carbon nanotube wound wraps up is placed in redox graphene suspension, adjusted
Section rotating speed makes its uniform rotation in redox graphene suspension, then takes out and is dried at 1-200 DEG C, and this process can be with
Carry out repeatedly, then the wire bundled is separated, prepare multi-walled carbon nanotube, the aluminium that redox graphene wraps up successively
Wire.
Embodiment 11
(1) N (N are chosen>2, and be integer) the copper metal silk of section equal length, is cleaned up, and the copper metal silk of selection is whole
Arrange and bundle together, be wrapped on the relevant position of experimental provision.
(2) 0.02-0.5 grams of multi-walled carbon nanotube is added to volume ratio and mixed for 0.1-10 water and dimethyl sulfoxide (DMSO) and hanged
In supernatant liquid, 0.001-0.1 grams of lauryl sodium sulfate and 0.0001-0.001 grams of chitosan are added, multi-walled carbon nanotube is made
Suspension.
(3) the copper metal silk wound is immersed in multi-walled carbon nanotube suspension, regulation rotating speed makes it be received in more wall carbon
Uniform rotation in mitron suspension, then take out and dried at 1-200 DEG C, this process can carry out repeatedly, preparing highly conductive
Multi-walled carbon nanotube parcel copper metal silk.
Embodiment 12
(1) the copper metal silk of the multi-walled carbon nanotube parcel bundled in one section of embodiment 11 is chosen, is wrapped in reality
The relevant position of experiment device.
(2) 0.02-0.5 grams of graphene nanometer sheet is added to the water and methyl ether mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of cetyl trimethylammonium bromide and 0.0001-0.001 grams of Nafion are added, graphene nano is made
Piece suspension.
(3) the copper metal silk that the multi-walled carbon nanotube wound wraps up is placed in graphene nanometer sheet suspension, regulation turns
Speed makes its uniform rotation in graphene nanometer sheet suspension, then takes out and is dried at 1-200 DEG C, and this process can carry out more
It is secondary, then the wire bundled is separated, prepare multi-walled carbon nanotube, the copper metal silk that graphene nanometer sheet wraps up successively.
Embodiment 13
(1) N (N are chosen>2, and be integer) the copper metal silk of section equal length, cleans up, it is corresponding to be wrapped in experimental provision
Position.
(2) 0.02-0.5 grams of few-wall carbon nanotube is added to the water and ethyl methyl ether mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of cetyl trimethylammonium bromide and 0.0001-0.001 grams of epoxy resin are added, few wall carbon is made and receives
Mitron suspension.
(3) the copper metal silk wound is immersed in few-wall carbon nanotube suspension, regulation rotating speed makes it in few wall carbon
In nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, by the wire bundled point
Open, prepare the copper metal silk of highly conductive few-wall carbon nanotube parcel.
Embodiment 14
(1) the copper metal silk of the few-wall carbon nanotube parcel bundled in one section of embodiment 13 is chosen, is wrapped in experiment dress
Put relevant position.
(2) 0.02-0.5 grams of graphene oxide is added in the water and methyl ether mixing suspension that volume ratio is 0.1-10,
0.001-0.1 grams of polyvinyl alcohol and 0.0001-0.001 grams of phenolic resin are added, graphene oxide suspension is made.
(3) the copper metal silk that the few-wall carbon nanotube wound wraps up is placed in graphene oxide suspension, regulation dress
Putting makes its uniform rotation in graphene oxide suspension, then takes out and is dried at 1-200 DEG C, and this process can carry out more
It is secondary, the wire bundled is separated, prepares few-wall carbon nanotube, the copper metal silk that graphene oxide wraps up successively.
Embodiment 15
(1) N (N are chosen>2, and be integer) the nickel wire of section equal length, cleans up, it is corresponding to be wrapped in experimental provision
Position.
(2) 0.02-0.5 grams of multi-walled carbon nanotube is added to the water and toluene mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of polyvinyl alcohol and 0.0001-0.001 grams of polyaminoacid methyl esters are added, multi-walled carbon nanotube suspension is made
Liquid.
(3) the nickel wire wound is immersed in multi-walled carbon nanotube suspension, regulation rotating speed makes it in more wall carbon
Uniform rotation in nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, by what is bundled
Wire separates, and prepares the nickel wire after highly conductive multi-walled carbon nanotube parcel.
Embodiment 16
(1) the nickel wire after the multi-walled carbon nanotube parcel bundled in one section of embodiment 15 is chosen, is wrapped in experiment
Device relevant position.
(2) 0.02-0.5 grams of graphene oxide is added in the water and ethanol mixing suspension that volume ratio is 0.1-10,
0.001-0.1 grams of polyvinyl alcohol and 0.0001-0.001 grams of span 80 are added, graphene oxide suspension is made.
(3) the nickel wire that the multi-walled carbon nanotube wound wraps is placed in graphene oxide suspension, adjusted
Rotating speed makes its uniform rotation in graphene oxide suspension, then takes out and is dried at 1-200 DEG C, and this process can carry out more
It is secondary, the wire bundled is separated, prepares multi-walled carbon nanotube, the wire that graphene oxide wraps up successively.
Embodiment 17
(1) N (N are chosen>2, and be integer) the corronil wire of section equal length, is cleaned up, by the cupro-nickel of selection
Alloying metal silk proper alignment is got well and bundled, and is wrapped in the relevant position of experimental provision.
(2) 0.02-0.5 grams of single-walled carbon nanotube is added to the water and chloroform mixing suspension that volume ratio is 0.1-10
In, 0.001-0.1 grams of polyethylene glycol and 0.0001-0.001 grams of cellulose are added, single-walled carbon nanotube suspension is made.
(3) the corronil wire wound is immersed in single-walled carbon nanotube suspension, regulation rotating speed makes it
The uniform rotation in single-walled carbon nanotube suspension, then take out and dried at 1-200 DEG C, this process can be carried out repeatedly, will
The wire bundled separates, and prepares the corronil wire of highly conductive single-walled carbon nanotube parcel.
Embodiment 18
(1) the corronil wire of the single-walled carbon nanotube parcel bundled in one section of embodiment 17 is chosen, is twined
It is wound on experimental provision relevant position.
(2) 0.02-0.5 grams of graphene oxide is added in the water and ethanol mixing suspension that volume ratio is 0.1-10,
0.001-0.1 grams of polyvinyl alcohol and 0.0001-0.001 grams of chitosan are added, graphene oxide suspension is made.
(3) the corronil wire that the single-walled carbon nanotube wound wraps up is placed in graphene oxide suspension,
Regulation rotating speed makes its uniform rotation in graphene oxide suspension, then takes out and is dried at 1-200 DEG C, this process can be entered
Row is multiple, prepares single-walled carbon nanotube, the corronil wire that graphene oxide wraps up successively.
Although the radical that wire is referred in implementation is N (N>1, and be integer), wire in a particular embodiment
Radical be (N>2, and be integer), from the principle of the present invention, utilize capillary principle assemble nanometer layer, the radical of metal
Can be 1, i.e. will be on an axis around upper wire, as long as space be present between adjacent metal wire coil, can also be through
Cross the wire that the uniform rotation in carbon nanomaterial forms carbon nanomaterial cladding.
Single metal wire is bundled into coiled type by more one metal wire strapped side by side, is impregnated into corresponding dispersion liquid, when extremely short
Between suspension can enter in the capillary between wire, pass through experiment, it has been found that dip time is a few minutes, several
Hour, several days etc. the purposes that may be implemented in wire over-assemble carbon nanomaterial, therefore it not is that the longer the better to impregnate, it is right
It is advisable in dip time a few minutes of suspension poor dispersion, can so avoids the solute in suspension as far as possible due to gravity
Deposition is on the metal filament.
Suspension concentration height can realize the purpose for assembling carbon nanomaterial on the metal filament.In general concentration low one
A little dipping times are more or the larger dipping time of concentration lacks some assemblings that can realize a certain specific thicknesses, if
Just hope CNT or graphene being assembled on wire and be not strict with, if expecting assembling effect ratio
Typically assembled if more uniform with low concentration.As long as also in other words the CNT in the suspension or graphene also or other
Material can be entered in the capillary between wire, and the material can be assembled on wire by evaporation.
For showing to assemble the result of carbon nanomaterial in wire, it is generally according to macroscopic observation wire surface color
It can determine whether, if allowing wire surface attachment is more general than relatively thin CNT or graphene only to need simply if just hoping
Dipping several times, impregnated if thick one layer of comparison to be intended to assembling tens times it is even more more.For material and metal
Silk color difference is larger, such as CNT is black and nickel wire is grey, and the nickel of grey is clearly can be appreciated that after dipping
Silk table face becomes the color of the CNT of black.Fig. 2 provides the scanning electron microscope diagram piece in nickel wire matrix material, figure
3 be scanning electron microscope diagram piece of the nickel wire after carbon nanomaterial is assembled.
Claims (9)
1. the preparation method of carbon nanomaterial is wrapped up on a kind of wire, it is characterised in that the preparation method comprises the following steps：
Wire surface is cleaned up；
Single metal wire is wound on axis using capillary principle or 2 and above wire proper alignment are got well and are bundled in
Together；
Proper alignment or the wire wound are impregnated into the suspension containing carbon nanomaterial；
Pass through evaporation drying；
Repeat aforesaid operations；
The wire that the wire bundled separates or unties on axis can obtain to the metal of carbon nanomaterial parcel
Silk.
2. preparation method according to claim 1, it is characterised in that：Described wire is normal temperature solid-state elemental metals silk
Or alloying metal silk.
3. preparation method according to claim 2, it is characterised in that：Described wire include spun gold, filamentary silver, copper wire,
Iron wire, nickel wire, cobalt silk, aluminium wire, zinc silk, magnesium silk, titanium silk, bismuth silk, chromium silk, manganese silk, tantalum wire, tungsten filament, molybdenum filament, platinum filament, rhodium silk, ruthenium
Silk, palladium silk, rhenium silk or iridium wire or their B alloy wire.
4. preparation method according to claim 1, it is characterised in that：Described carbon nanomaterial includes：Single
Pipe, few-wall carbon nanotube, multi-walled carbon nanotube, graphene oxide, redox graphene, graphene or graphite nano plate or it
Mixture.
5. preparation method according to claim 1, it is characterised in that：Described suspension includes carbon nanomaterial, solvent,
Dispersant and binding agent.
6. preparation method according to claim 5, it is characterised in that：Described solvent includes water, methanol, ethanol, isopropyl
Alcohol, ethylene glycol, methyl ether, ether, ethyl methyl ether, acetone, butanone, MEK, chloroform, carbon tetrachloride, benzene, toluene, tetrahydrofuran, two
NMF, dimethyl sulfoxide (DMSO), acetic acid, methyl formate and its mixture.
7. preparation method according to claim 5, it is characterised in that：Described dispersant include lauryl sodium sulfate,
Cetyl trimethylammonium bromide, polyvinyl alcohol, polyethylene glycol, PVP, span 80, Triton X-100.
8. preparation method according to claim 5, it is characterised in that：Described binding agent includes：Cellulose, chitosan,
Nafion, epoxy resin, phenolic resin, polyaminoacid methyl esters.
9. according to the preparation method described in claim any one of 1-8, it is characterised in that：Described evaporation drying step, can be with
Carry out at normal temperatures, can also heating evaporation drying.
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