CN102586869A - Three-dimensional grapheme tube and preparation method thereof - Google Patents

Three-dimensional grapheme tube and preparation method thereof Download PDF

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CN102586869A
CN102586869A CN2012100199016A CN201210019901A CN102586869A CN 102586869 A CN102586869 A CN 102586869A CN 2012100199016 A CN2012100199016 A CN 2012100199016A CN 201210019901 A CN201210019901 A CN 201210019901A CN 102586869 A CN102586869 A CN 102586869A
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graphene
metal wire
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CN102586869B (en
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黄富强
毕辉
林天全
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention aims at providing a three-dimensional grapheme tube and a preparation method of the three-dimensional grapheme tube. The diameter of the grapheme tube is 10nm to 5mm, the length is 50nm to 5mm, and the layer number of the grapheme is 1 to 100. The method comprises the following work procedures that: A, metal threads or metal wires are used as catalyst templates for directly generating grapheme/metal thread or metal wire composite structures through generating grapheme covering layers on the outer surfaces of the metal threads or metal wires through carbon sources by a chemical vapor deposition method; and B, the metal threads or the metal wires are removed through etching, and the three-dimensional grapheme tube is obtained. The grapheme tube provided by the invention has excellent conducting performance and corrosion resistance performance. The process provided by the invention is simple, and is easy to control, the conducting performance is excellent, and the preparation cost is low. The three-dimensional grapheme tube and the preparation method are applicable to the fields of solar devices, energy storage batteries, conductive composite materials and corrosion resistance.

Description

Three-dimensional Graphene pipe and preparation method thereof
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of three-dimensional Graphene pipe and preparation method thereof.
Background technology
Cellular lattice structure of the bidimensional that Graphene is made up of the carbon six-ring (2D) cycle, it is the soccerballene that makes up 0D, the elementary cell of the carbon nanotube of 1D and the carbon-based materials such as graphite of 3D.The unique crystalline structure of Graphene makes it have excellent properties; Like high heat conductance, high mechanical strength, peculiar electrical properties and optical property, therefore have important theoretical research and be worth, and its particular structure might make it obtain great practical application in a plurality of fields with excellent performance; For economy, the social development in future provides new strong growth point (K.S.Novoselov; Et al.Science 2004,306,666.).Graphene highly transparent from optical angle, visible-near-infrared being absorbed as~2.3% (R.Nair, et al.Science 2008,320,1308.); Graphene has avoided the conventional transparent conductive oxide near infrared photoabsorption, helps to utilize the near infrared sun power of 900-1200nm, realizes making full use of sun power.Say that from electronic transport carrier mobility is up to 20,000cm 2* V -1* s -1, be much better than common oxidic transparent conductive film (A.Geim, Nat.Mater.2007,6,183.); The carrier concentration of Graphene is well below conductive carbon pipe and graphite; The high mobility of Graphene and low carrier concentration help the electric charge fast transferring; Improve solar cell and collect the electric charge ability; Improve photoelectric transformation efficiency, thereby have broad application prospects at renewable energy source domains such as lithium ion battery, solar cells.Compare with the associated materials that extensively adopts at present in the above-mentioned application; Graphene has the low advantage of cost; Can be that raw material prepares by graphite cheap and easy to get, and film forming can realize through simple wet chemical method, thereby possess the incomparable price advantage of other materials.
At present; The researchist also prepares grapheme material through chemical stripping method, electric lonely electric discharge and chemical Vapor deposition process; And prepared graphene film and three-dimensional Graphene network structure through control growing condition and follow-up processing, have broad application prospects in solar device, energy-storage battery and conducing composite material field.[concrete visible document: K.S.Novoselov et al.Science, 2004,306:666.C.Lee, et al.Science, 2008,321:385.K.S.Kim; Et al.Nature, 2009,457:706.X.S.Li, et al.Science, 2009; 324:1312.S.Bae, et al.Nature Nanotechnology, 2010,5:574.X.Wang, et al.Nano Letters; 2008,8:323.L.G.D.Arco, et al.ACSNano, 2010,4:2865.].
Publication number CN102176338A discloses a kind of composite conducting material of a kind of confession, and said composite conducting material is Graphene and copper nano-wire to be composited and the composite conducting material that obtains by caking agent.In addition, have document openly to adopt Low Pressure Chemical Vapor Deposition, but the graphene-structured defective of said method preparation is many.Yet, do not have as yet at present under condition of normal pressure directly with metal wire or wire to make three-dimensional Graphene/metal wire or metal wire combined structure and then through removing the report that metal wire or wire prepare the Graphene tubular structure in metal wire or wire deposition as catalysts.
Summary of the invention
In the face of the problems referred to above that prior art exists, the inventor recognizes that employing metal wire or wire as catalytic templating, utilize chemical Vapor deposition process directly to deposit Graphene, obtains Graphene/metal wire or metal wire combined structure.And after utilizing etching liquid to remove metal wire or wire, can prepare the excellent three-dimensional Graphene pipe of electroconductibility and rotproofness.
At this, the present invention provides a kind of three-dimensional Graphene pipe, and the diameter of said Graphene pipe is 10nm~5mm, and length is 50nm~5mm, and the number of plies of said Graphene is 1~100.
Preferably, the diameter of three-dimensional Graphene pipe is 80nm~100 μ m.
Preferably, the number of plies of three-dimensional Graphene pipe is 1~20.
Preferably, the length of three-dimensional Graphene pipe is 100nm~100 μ m.
Preferably, three-dimensional Graphene pipe of the present invention is to make carbon source at said metal wire or wiry outside surface directly generate Graphene coating as catalysts through chemical Vapor deposition process with metal wire or wire to form Graphene/metal wire or metal wire combined structure, remove the three-dimensional Graphene pipe that metal wire or wire make afterwards.
The present invention is employed in that chemical Vapor deposition process prepares three-dimensional Graphene pipe under the condition of normal pressure, and its preparation method is simple, needing no vacuum equipment, and preparation cost is cheap, and the graphene-structured of growth is perfect to be fallen into.
Again; The present invention also provides a kind of preparation method of three-dimensional Graphene pipe, and this method comprises: make carbon source at said metal wire or wiry outside surface directly generate operation A that Graphene coating form Graphene/metal wire or metal wire combined structure as catalysts through chemical Vapor deposition process with metal wire or wire; Remove metal wire or process B wiry through etching, thereby obtain three-dimensional Graphene pipe.
Preferably, operation A also comprises metal wire or wire as catalytic templating is put into chemical vapor deposition reaction chamber, imports hydrogen and protection gas, is heated to 400~1200 ℃ of temperature of reaction, 0~60 minute operation A1 of constant temperature; Import the operation A2 that carbon source is reacted; Be cooled to room temperature, obtain the operation A3 of three-dimensional Graphene/metal wire or metal wire combined structure.
Preferably; Among the preparation method of the present invention; Form one deck framework material at said three-dimensional Graphene/metal wire that obtains or metal wire combined body structure surface before also being included in said process B; Form the process B 1 of framework material/Graphene/metal wire or metal wire combined structure, and the process B 2 of after said process B, removing framework material.
Can be through pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate or YSR 3286 be dissolved in water, ethanol, acetone, N, the solution of processing in N two-N, N-Methyl pyrrolidone or the methyl-phenoxide solvent is dry and form above-mentioned framework material at said three-dimensional Graphene/metal wire or metal wire combined body structure surface.
After removing metal wire or wire, can utilize ethanol, Virahol, acetone or their mixed solvent to remove the framework material on Graphene surface through etching.In addition, the etching liquid that etching process adopts can be hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, iron trichloride or their mixing solutions, and etching temperature is 30-80 ℃, and etching time is 20-800min.
In addition, the metal wire as catalysts of the present invention can adopt nanometer iron wire, NANO CRYSTAL COPPER WIRE, nanometer cobalt line, nanometer nickel wire, nanometer ruthenium line, nanometer molybdenum wire, nanometer niobium line, nanometer platinum line, nanometer iridium line, nanometer palladium line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nanometer vanadium line or their alloy nano-wire.Metal wire can adopt Hydrothermal Preparation by metal-salt and reductive agent.In addition, metal wire can also utilize metal salt solution to pass through the electrochemical deposition preparation.Metal salt solution is prepared through electrochemical deposition on porous anodic alumina template.Metal wire as catalytic templating helps the cracking of carbon source molecule, can make to produce carbon after the cracking and form saturated solid solution therein.
Wire as catalysts of the present invention can be commercial iron wire, copper wire, cobalt silk, nickel wire, ruthenium silk, molybdenum filament, niobium silk, platinum filament, iridium wire, palladium silk, titanium silk, pick silk, thallium silk, tungsten filament, vanadium silk or their alloy silk.Wire as catalytic templating helps the cracking of carbon source molecule, can make to produce carbon after the cracking and form saturated solid solution therein.
As the carbon source of the present invention for the importing of generation Graphene; It can be the gaseous carbon source of methane, ethene, acetylene, ethane, propane, propylene or their mixed gas; The liquid carbon source of methyl alcohol, ethanol, propyl alcohol, butanols, acetone, toluene, N-Methyl pyrrolidone, N or their mixing liquid, or the solid-state carbon source of pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate, YSR 3286 or their mixture.
The protection gas that in the reaction system of metal wire or wire and carbon source, imports can be nitrogen, argon gas, helium or their mixed gas.Importing the protection airshed in the reaction process that imports is 1~1000sccm, and hydrogen flowing quantity is 1~500sccm, and gaseous carbon source is 1~200sccm.Protection gas that imports in the reaction process and hydrogen gas throughput ratio are 0.1~100, and protection gas and gaseous state carbon-source gas throughput ratio are 1~1000, and being preferably protection gas and hydrogen gas throughput ratio is 1~10, and protection gas and gaseous state carbon-source gas throughput ratio are 1~30.
Carbon source and metal wire or reaction times wiry can be controlled at 1 minute~20 hours.Be preferably 10 minutes~120 minutes.Accomplish when reaction, can control rate of temperature fall is 10~300 ℃/min.Be preferably 100~300 ℃/min.
Three-dimensional Graphene/metal wire provided by the invention or metal wire combined structure, Graphene pipe have excellent conductivity and erosion resistance.Technology provided by the invention is simple, and process is easy to control, and conductivity is excellent, and preparation cost is low, is suitable for solar device, energy-storage battery, conducing composite material and corrosion-resistant field.
Description of drawings
Fig. 1 illustrates the stereoscan photograph of Graphene of the present invention/nickel wire composite structure;
Fig. 2 illustrates the stereoscan photograph of the three-dimensional Graphene pipe of the present invention;
Fig. 3 illustrates the Raman spectrum of Graphene of the present invention/nickel wire composite structure;
Fig. 4 illustrates the corrosion-resistant digital photograph of Comparative Examples nickel wire and Graphene of the present invention/nickel wire composite structure;
Fig. 5 illustrates the transmission electron microscope photo of Graphene of the present invention/copper nano-wire composite structure;
Fig. 6 illustrates the Raman spectrum of Graphene of the present invention/copper nano-wire composite structure.
Embodiment
Below, with reference to accompanying drawing, and combine following embodiment to further specify the present invention.Should be understood that accompanying drawing and embodiment or embodiment only are exemplary, but not be used to limit the present invention.
The preparation method of three-dimensional Graphene/metal wire of the present invention or metal wire combined structure, Graphene pipe specifically may further comprise the steps: with metal wire or wire is catalytic templating; Put into chemical vapor deposition reaction chamber; Import hydrogen and protection gas; Be heated to temperature of reaction 400-1200 ℃, constant temperature 0-60min; Import the operation that carbon source is reacted, importing the protection airshed in the reaction process is 1~1000sccm, and hydrogen flowing quantity is 1~500sccm, and gaseous carbon source is 1~200sccm.1 minute to 20 hours reaction times; Keep gas flow in the reaction process, reaction finishes, and the control rate of temperature fall is 10-300 ℃/min, is cooled to room temperature, obtains three-dimensional Graphene/metal wire or metal wire combined structure.
Further, can also the three-dimensional Graphene/metal wire or the metal wire combined structure of preparation be put into framework material solution at its surface deposition one deck framework material, through baking and curing; Framework material/Graphene/metal wire or metal wire combined structure are put into etching liquid, remove metal wire or wire, obtain framework material/Graphene; Repeatedly wash framework material/Graphene with deionized water, will place organic solvent to remove to move Graphene surface framework material again, finally obtain three-dimensional Graphene pipe.
Therefore the advantage that Graphene pipe conductivity is excellent, preparation cost is low that three-dimensional Graphene/metal wire of the present invention or metal wire combined structure, three-dimensional Graphene tube preparation method have that technology is simple, process is easy to control, make is suitable for solar device, energy-storage battery, conducing composite material and field such as corrosion-resistant.
Above-mentioned metal wire can adopt nanometer iron wire, NANO CRYSTAL COPPER WIRE, nanometer cobalt line, nanometer nickel wire, nanometer ruthenium line, nanometer molybdenum wire, nanometer niobium line, nanometer platinum line, nanometer iridium line, nanometer palladium line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nanometer vanadium line or their alloy nano-wire, and wire can adopt commercial iron wire, copper wire, cobalt silk, nickel wire, ruthenium silk, molybdenum filament, niobium silk, platinum filament, iridium wire, palladium silk, titanium silk, pick silk, thallium silk, tungsten filament, vanadium silk or their alloy silk.Above-mentioned metal nano linear diameter can be 10-1000nm, and length can be 200nm-500mm; Wire diameter can be 1-1000mm, and length can be 0.5-1000mm.
Above-mentioned carbon source can be the gaseous carbon source of methane, ethene, acetylene, ethane, propane, propylene or their mixed gas; The liquid carbon source of methyl alcohol, ethanol, propyl alcohol, butanols, acetone, toluene, N-Methyl pyrrolidone, N or their mixing liquid, the perhaps solid-state carbon source of pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate, YSR 3286 or their mixture.
Protection gas among the present invention is nitrogen, argon gas, helium or their mixed gas.Protection gas that imports in the reaction process and hydrogen gas throughput ratio are 0.1~100, and protection gas and gaseous state carbon-source gas throughput ratio are 1~1000.
Above-mentioned framework material solution is that pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate or YSR 3286 are dissolved in water, ethanol, acetone, N, the solution of processing in N two-N, N-Methyl pyrrolidone or the methyl-phenoxide solvent.
The etching liquid that above-mentioned etching process adopts is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, iron trichloride or their mixing solutions, and etching temperature can be 30-80 ℃, and etching time can be 20-800min.
Above-mentioned organic solvent can be ethanol, Virahol, acetone or their mixed solvent.
Metal nanometer line among the present invention can adopt hydrothermal method and the preparation of template electric-sedimentation method.
As an example, the hydrothermal preparation of preparation metal nanometer line is through following steps: the nitrate salt, halide salt and the vitriol that take by weighing metal (iron, copper, cobalt, nickel, ruthenium, molybdenum, niobium, platinum, iridium, palladium, titanium, pick, thallium, tungsten or vanadium) are put into container, add a certain amount of deionized water; Under powerful agitation condition, add borane reducing agent sodium hydride, glucose, Hydrazine Hydrate 80, aliphatic alkylamine (tetradecy lamine, cetylamine and stearylamine); The mol ratio of control metals ion and reductive agent is 1: 20-1000: 1, and the powerful 1-10h that stirs, then; In its reaction kettle of packing into; Be warming up to 120-300 ℃ after the sealing, constant temperature 1-60h naturally cools to room temperature; Adopt deionized water, ethanol and normal hexane to carry out centrifuge washing, promptly obtain the clean metal nano wire after the vacuum-drying.
The prepared by electrodeposition of metal nanometer line is through following steps: the nitrate salt, halide salt and the vitriol that take by weighing metal (iron, copper, cobalt, nickel, ruthenium, molybdenum, niobium, platinum, iridium, palladium, titanium, pick, thallium, tungsten or vanadium) are put into container; Add a certain amount of deionized water; A certain amount of boric acid of packing into simultaneously forms uniform solution.Metal salt concentrations is 0.1-10M, and boric acid concentration is 0.02-10M, is utilized in porous anodic alumina template prepared by electrodeposition metal nanometer line, and galvanic deposit voltage is 0.1-10V, and current density is 0.01-10A/cm 2, depositing time is 1-200min.
Can prepare metal wire or diameter wiry is 10nm~5mm through above method, the number of plies of Graphene is 1~100 three-dimensional Graphene/metal wire or metal wire combined structure.
In addition, can also prepare diameter through above method is that 10nm~5mm, length are that the number of plies of 50nm~5mm, Graphene is 1~100 three-dimensional Graphene pipe.
Three-dimensional Graphene/metal wire of the present invention or metal wire combined structure, three-dimensional Graphene pipe conductivity and rotproofness are excellent, are suitable for solar device, energy-storage battery, conducing composite material and field such as corrosion-resistant.
Further illustrate the preparation method of three-dimensional Graphene pipe below.
Embodiment 1
(1) adopt nickel wire as catalytic templating, the mean diameter of nickel wire is 25 μ m.After ethanol, acetone and Virahol ultrasonic cleaning, nickel wire is packed in the chemical vapour deposition reactor furnace, feed 100sccm hydrogen and 100sccm argon gas; Begin to be heated to 1000 ℃ behind the 60min, feed 5sccm methane, reaction times 30min behind the constant temperature 30min; Reaction stops to feed methane after finishing, and closes electric furnace, is cooled fast to room temperature; Obtain Graphene/nickel wire composite structure, stereoscan photograph is as shown in Figure 1.
(2) step (1) preparation product is placed in the acetone soln of 4wt% polymethylmethacrylate, takes out 100 ℃ of oven dry 3h, make its surface deposition one deck polymethylmethacrylate; Put into the 5M salpeter solution 4h of 100ml, remove nickel wire, put into acetone soln again and remove polymethylmethacrylate; Obtain three-dimensional Graphene pipe; Stereoscan photograph and Raman spectrum as shown in Figures 2 and 3, the Graphene number of plies is 1-10, graphene-structured is perfect to be fallen into.
Embodiment 2
The preparation method is basically with embodiment 1, and difference is: in the step (1), the employing diameter is that the nickel wire of 100 μ m is a catalytic templating, and the number of plies that obtains three-dimensional Graphene pipe is 10-20, and graphene-structured is perfect to be fallen into.
Embodiment 3
The preparation method is basically with embodiment 1, and difference is: in the step (1), the chemical vapour deposition temperature is 900 ℃, reaction times 10min, and the number of plies that obtains three-dimensional Graphene pipe is 1-3, graphene-structured is perfect to be fallen into.
Embodiment 4
(1) take by weighing 1mmol copper sulfate and the 2mmol stearylamine is put into the 100ml deionized water, powerful stir 2h after, it is transferred in the reaction kettle; Carry out hydro-thermal reaction after the sealing, temperature of reaction is 170 ℃, and the reaction times is 36h; Reaction finishes to take out, and with deionized water, ethanol and normal hexane centrifuging, obtains copper nano-wire; Preparing mean diameter is 100nm, and length is the single crystal Cu nano wire of 100 μ m.Copper nano-wire is packed in the chemical vapour deposition reactor furnace, feed 50sccm hydrogen and 100sccm nitrogen, begin to be heated to 650 ℃ behind the 60min; Feed 10sccm acetylene behind the constant temperature 10min, reaction times 10min, reaction stops through acetylene after finishing; Close electric furnace; Naturally cool to room temperature, obtain Graphene/copper nano-wire composite structure, transmission electron microscope photo is as shown in Figure 5.
(2) Graphene/copper nano-wire composite structure with step (1) preparation places 5% polyvinyl alcohol water solution, takes out and 130 ℃ of oven dry 1h, puts into the 5M FeCl of 100ml 3Stir 4h in the solution, remove Nano line of metal copper, put into acetone soln again and remove polymethylmethacrylate, obtain three-dimensional Graphene pipe, Raman spectrum is as shown in Figure 6, and the Graphene number of plies is 3-5, and graphene-structured is perfect to be fallen into.
Embodiment 5
The preparation method is basically with embodiment 4, and difference is: in the step (1), and reaction times 30min, the number of plies that obtains three-dimensional Graphene pipe is 5-10, graphene-structured is perfect to be fallen into.
Embodiment 6
The preparation method is basically with embodiment 4, and difference is: in the step (1), adopt ethene as carbon source, the number of plies that obtains three-dimensional Graphene pipe is 1-3, and graphene-structured is perfect to be fallen into.
Embodiment 7
(1) mixing solutions with the boric acid of the rose vitriol of 0.2mol/L and 45g/L is the electroplate liquid of cobalt, and its pH value is transferred to 2-3.With the graphite flake is anode, and the voltage that between anodic oxidation aluminium formwork and graphite flake, applies 2V carries out the direct current electroless plating, the growth cobalt nanowire, and growth temperature is 30 ℃, growth time is 5min.Then, it is immersed in 60 ℃ the mixing solutions of 0.2mol/L chromic acid and 0.4mol/L phosphoric acid, removes alumina formwork, obtain cobalt nanowire.Preparing mean diameter is 60nm, and length is the monocrystalline cobalt nanowire of 20 μ m.Cobalt nanowire is packed in the chemical vapour deposition reactor furnace, feed 300sccm hydrogen and 600sccm helium, begin to be heated to 850 ℃ behind the 60min; Feed 5sccm propane behind the constant temperature 10min; Reaction times 15min, reaction stops to close electric furnace through propane after finishing; Naturally cool to room temperature, obtain Graphene/cobalt nanowire composite structure.
(2) Graphene/cobalt nanowire composite structure of step (1) preparation is placed the N-Methyl pyrrolidone solution of 2% pvdf; Take out and 180 ℃ of oven dry 3min, put into the 1M hydrochloric acid soln 1h of 100ml, remove metal cobalt nanowire; Put into acetone soln again and remove pvdf; Obtain three-dimensional Graphene pipe, the Graphene number of plies is 3-5, and graphene-structured is perfect to be fallen into.
Embodiment 8
The preparation method is basically with embodiment 7, and difference is: in the step (1), and chemical vapour deposition 15min, the number of plies that obtains three-dimensional Graphene pipe is 5-10, graphene-structured is perfect to be fallen into.
Embodiment 9
The preparation method is basically with embodiment 7, and difference is: in the step (1), be quickly cooled to room temperature, the number of plies that obtains three-dimensional Graphene pipe is 1-3, and graphene-structured is perfect to be fallen into.
Embodiment 10
The preparation method is basically with embodiment 7, and difference is: in the step (1), and 15sccm propane reaction times 30min, the number of plies that obtains three-dimensional Graphene pipe is 10-20, graphene-structured is perfect to be fallen into.
Embodiment 11
(1) adopting three-electrode system, is working electrode with the anodic oxidation aluminium formwork, and ruthenium titanium net is a supporting electrode, and SCE is as reference electrode.Nickel plating solution sulfur acid nickel 160g/L, boric acid 30g/L, the pH value of solution value is 3.0-3.5, sedimentation potential is-0.9V; Copper plating solution sulfur acid copper 75g/L, sodium sulfate 1-5g/L, the pH value of solution value is 2.5-3.0, sedimentation potential is-0.08V.Adopt interior each 3min of alternating deposit copper and mickel of porous anodic alumina template of double flute method CONTROLLED POTENTIAL, adopt the 1mol/L sodium hydroxide solution to remove porous anodic alumina template, the copper of acquisition/nickel bielement nano line mean diameter is 80nm, and length is 25 μ m.Go in the chemical vapour deposition reactor furnace copper/nickel bielement nano is traditional thread binding, feed 50sccm hydrogen and 300sccm argon gas and helium mix gas (argon gas: helium=1: 1), begin to be heated to 600 ℃ behind the 120min; Behind the constant temperature 10min, 20sccm argon gas bubbling ethanol is as carbon source, reaction times 15min; Reaction stops to feed carbon source after finishing; Close electric furnace, cooling fast obtains Graphene/copper/nickel nano wire composite structure.
(2) Graphene/copper/nickel nano wire composite structure of step (1) preparation is placed the methyl-phenoxide solution of 3% polymethylmethacrylate, take out and 150 ℃ of oven dry 10min, put into 1M hydrochloric acid/2M FeCl of 100ml 31h in the mixing solutions removes metallic copper/nickel nano wire, puts into acetone soln again and removes polymethylmethacrylate, obtains three-dimensional Graphene pipe, and the Graphene number of plies is 1-2, and graphene-structured is perfect to be fallen into.
Embodiment 12
The preparation method is basically with embodiment 11, and difference is: in the step (1), adopt 50sccm argon gas bubbling ethanol as carbon source, the number of plies that obtains three-dimensional Graphene pipe is 3-5, and graphene-structured is perfect to be fallen into.
Embodiment 13
The preparation method is basically with embodiment 11, and difference is: in the step (1), adopt 50sccm argon gas bubbling ethanol as carbon source, reaction times 30min obtains the number of plies 3-10 of three-dimensional Graphene pipe, and graphene-structured is perfect to be fallen into.
Embodiment 14
(1) adopt diameter 150 μ m Mo-Ni alloy silks as catalytic templating, at its surface deposition one deck polymethylmethacrylate, in the chemical vapour deposition reactor furnace of packing into; (argon gas: helium=1: 1), behind the 60min, 5min quickly heats up to 1100 ℃ to feed 50sccm hydrogen and 300sccm argon gas and helium mix gas; Behind the constant temperature 10min; Close electric furnace, be quickly cooled to room temperature, obtain Graphene/molybdenum/nickel nano wire composite structure.
(2) Graphene/molybdenum/nickel nano wire composite structure of step (1) preparation is placed the acetone soln of 5% YSR 3286; Take out and 120 ℃ of oven dry 60min, put into the 2M sulphuric acid soln 1h of 100ml, remove metal molybdenum/nickel nano wire; Put into acetone soln again and remove YSR 3286; Obtain three-dimensional Graphene pipe, the number of plies of Graphene is 1-3, and graphene-structured is perfect to be fallen into.
Comparative Examples 1
Adopt nickel wire as catalytic templating, the mean diameter of nickel wire is 25 μ m.After ethanol, acetone and Virahol ultrasonic cleaning, nickel wire is packed in the chemical vapour deposition reactor furnace, feed 100sccm hydrogen and 100sccm argon gas; Begin to be heated to 1000 ℃ behind the 60min, behind the constant temperature 40min, close electric furnace; Be cooled fast to room temperature, obtain not have the nickel wire of Graphene growth.
For the ease of contrast Graphene/nickel wire composite structure and nickel wire, the conductivity and the erosion resistance of having tested them respectively.Compare with nickel wire, the electric conductivity of Graphene/nickel wire composite structure can improve 20%.In addition, Graphene/nickel wire and nickel wire be put in the Hydrogen chloride find behind the 10min that the nickel wire of the Graphene of not growing complete reaction forms light green solution, and Graphene/nickel wire composite structure can keep stable in Hydrogen chloride, as shown in Figure 4.The erosion resistance that has shown Graphene/nickel wire composite structure obviously is superior to nickel wire.
Industrial applicability: three-dimensional Graphene of the present invention and the method for preparing this three-dimensional Graphene; Have electroconductibility and excellent corrosion resistance, process is easy to control, preparation cost is low advantage, have broad application prospects in solar device, energy-storage battery and conducing composite material field.

Claims (19)

1. a three-dimensional Graphene pipe is characterized in that, the diameter of said Graphene pipe is 10nm~5mm, and length is 50nm~5mm, and the number of plies of said Graphene is 1~100.
2. three-dimensional Graphene pipe according to claim 1 is characterized in that, the diameter of said Graphene pipe is 80nm~100 μ m.
3. three-dimensional Graphene pipe according to claim 1 is characterized in that the number of plies of said Graphene pipe is 1~20.
4. according to each described three-dimensional Graphene pipe among the claim 1-3, it is characterized in that the length of said Graphene pipe is 100nm~100 μ m.
5. the preparation method of arbitrary described three-dimensional Graphene pipe in the claim 1 to 4; It is characterized in that, comprising: make carbon source directly generate the operation A that the Graphene coating forms Graphene/metal wire or metal wire combined structure as catalysts through chemical Vapor deposition process at said metal wire or outside surface wiry with metal wire or wire; Remove metal wire or process B wiry through etching, thereby obtain three-dimensional Graphene pipe.
6. preparation method according to claim 5; It is characterized in that said operation A comprises metal wire or wire as catalytic templating are put into chemical vapor deposition reaction chamber, imports hydrogen and protection gas; Be heated to 400~1200 ℃ of temperature of reaction, 0~60 minute operation A1 of constant temperature; Import the operation A2 that carbon source is reacted; Be cooled to room temperature, obtain the operation A3 of three-dimensional Graphene/metal wire or metal wire combined structure.
7. preparation method according to claim 5; It is characterized in that; Form one deck framework material at said three-dimensional Graphene/metal wire that obtains or metal wire combined body structure surface before also being included in said process B; Form the process B 1 of framework material/Graphene/metal wire or metal wire combined structure, and the process B 2 of after said process B, removing framework material.
8. according to each described preparation method among the claim 5-7; It is characterized in that; Said metal wire adopts nanometer iron wire, NANO CRYSTAL COPPER WIRE, nanometer cobalt line, nanometer nickel wire, nanometer ruthenium line, nanometer molybdenum wire, nanometer niobium line, nanometer platinum line, nanometer iridium line, nanometer palladium line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nanometer vanadium line or their alloy nano-wire, and said wire is commercial iron wire, copper wire, cobalt silk, nickel wire, ruthenium silk, molybdenum filament, niobium silk, platinum filament, iridium wire, palladium silk, titanium silk, pick silk, thallium silk, tungsten filament, vanadium silk or their alloy silk.
9. according to each described preparation method among the claim 5-7, it is characterized in that said metal wire adopts Hydrothermal Preparation by metal-salt and reductive agent.
10. according to each described preparation method among the claim 5-7, it is characterized in that said metal wire utilizes metal salt solution to pass through the electrochemical deposition preparation.
11. according to each described preparation method among the claim 5-7; It is characterized in that; Said carbon source is the gaseous carbon source of methane, ethene, acetylene, ethane, propane, propylene or their mixed gas; The liquid carbon source of methyl alcohol, ethanol, propyl alcohol, butanols, acetone, toluene, N-Methyl pyrrolidone, N or their mixing liquid, or the solid-state carbon source of pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate, YSR 3286 or their mixture.
12. preparation method according to claim 7; It is characterized in that; Said framework material is that pvdf, Vinylpyrrolidone polymer, polyoxyethylene glycol, Z 150PH, polymethylmethacrylate or YSR 3286 are dissolved in water, ethanol, acetone, N, and the solution of processing in N two-N, N-Methyl pyrrolidone or the methyl-phenoxide solvent is dry and form at said three-dimensional Graphene/metal wire or metal wire combined body structure surface.
13. preparation method according to claim 7 is characterized in that, after etching removal metal wire or wire, utilizes ethanol, Virahol, acetone or their mixed solvent to remove the framework material on Graphene surface, obtains three-dimensional Graphene pipe.
14. according to each described preparation method among the claim 5-7; It is characterized in that; The etching liquid that said etching process adopts is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, iron trichloride or their mixing solutions, and etching temperature is 30-80 ℃, and etching time is 20-800min.
15., it is characterized in that said protection gas is nitrogen, argon gas, helium or their mixed gas according to each described preparation method among the claim 5-7.
16., it is characterized in that importing the protection airshed in the reaction process is 1~1000sccm according to each described preparation method among the claim 5-7, hydrogen flowing quantity is 1~500sccm, gaseous carbon source is 1~200sccm.
17. preparation method according to claim 16 is characterized in that, protection gas that imports in the reaction process and hydrogen gas throughput ratio are 0.1~100, and protection gas and gaseous state carbon-source gas throughput ratio are 1~1000.
18., it is characterized in that the reaction times of control reaction process is 1 minute~20 hours according to each described preparation method among the claim 5-7.
19., it is characterized in that process of cooling control rate of temperature fall is 10~300 ℃/min according to each described preparation method among the claim 5-7.
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