CN102586869B - Three-dimensional grapheme tube and preparation method thereof - Google Patents
Three-dimensional grapheme tube and preparation method thereof Download PDFInfo
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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
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of three-dimensional grapheme tube and preparation method thereof.
Background technology
Bidimensional (2D) the cycle honeycomb lattice structure that Graphene is made up of carbon six-ring, it is the soccerballene building 0D, the elementary cell of the carbon-based materials such as the carbon nanotube of 1D and the graphite of 3D.The crystalline structure of Graphene uniqueness makes it have excellent properties, as high heat conductance, high mechanical strength, peculiar electrical properties and optical property, therefore there is important theoretical investigation be worth, and the performance of the structure of its uniqueness and excellence likely makes it obtain great practical application in multiple field, for the economy in future, social development provide new strong growth point (K.S.Novoselov, et al.Science 2004,306,666.).From Graphene highly transparent optical angle, visible-near-infrared is absorbed as ~ 2.3% (R.Nair, et al.Science 2008,320,1308.); Graphene avoids conventional transparent conductive oxide near infrared photoabsorption, contributes to the near infrared sun power utilizing 900-1200nm, realizes making full use of sun power.Say 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, high mobility and the low carrier concentration of Graphene are conducive to electric charge fast transferring, improve solar cell and collect charge capability, improve photoelectric transformation efficiency, thus have broad application prospects in the field of renewable energy such as lithium ion battery, solar cell.Compared with the associated materials extensively adopted at present in above-mentioned application, Graphene has the low advantage of cost, can be prepared by raw material by graphite cheap and easy to get, and film forming realize by simple wet chemical method, thus possesses the price advantage that other materials is incomparable.
At present, researchist also prepares grapheme material by chemical stripping method, electric lonely electric discharge and chemical Vapor deposition process, and prepared graphene film and three-dimensional grapheme network structure by control growth conditions and follow-up process, 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 is open a kind of for a kind of composite conducting material, and described composite conducting material is composite conducting material Graphene and copper nano-wire being composited and being obtained by caking agent.In addition, have document openly to adopt Low Pressure Chemical Vapor Deposition, but graphene-structured defect prepared by described method is many.But, not yet have at present in atmospheric conditions direct using metal wire or wire as catalysts template at metal wire or the obtained three-dimensional graphene/metal line of wire deposition or metal wire composite structure and then the report being prepared Graphene tubular structure by removal metal wire or wire.
Summary of the invention
In the face of the problems referred to above that prior art exists, the present inventor recognizes that employing metal wire or wire are as catalytic templating, utilize chemical Vapor deposition process Direct precipitation Graphene, obtains graphene/metal line or metal wire composite structure.And after utilizing etching liquid to remove metal wire or wire, the three-dimensional grapheme tube of electroconductibility and rotproofness excellence can be prepared.
At this, the invention provides a kind of three-dimensional grapheme tube, the diameter of described grapheme tube is 10nm ~ 5mm, and length is 50nm ~ 5mm, and the number of plies of described Graphene is 1 ~ 100.
Preferably, the diameter of three-dimensional grapheme tube is 80nm ~ 100 μm.
Preferably, the number of plies of three-dimensional grapheme tube is 1 ~ 20.
Preferably, the length of three-dimensional grapheme tube is 100nm ~ 100 μm.
Preferably, three-dimensional grapheme tube of the present invention makes carbon source directly generate Graphene coating at described metal wire or outside surface wiry using metal wire or wire as catalysts template by chemical Vapor deposition process to form graphene/metal line or metal wire composite structure, remove metal wire or wire and obtained three-dimensional grapheme tube afterwards.
The present invention adopts chemical Vapor deposition process in atmospheric conditions to prepare three-dimensional grapheme tube, and its preparation method is simple, and without the need to vacuum apparatus, 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 grapheme tube, and the method comprises: make carbon source at described metal wire or wiry outside surface directly generate operation A that Graphene coating form graphene/metal line or metal wire composite structure as catalysts template by chemical Vapor deposition process using metal wire or wire; Remove metal wire or process B wiry by etching, thus obtain three-dimensional grapheme tube.
Preferably, operation A also comprises and puts into chemical vapor deposition reaction chamber using as the metal wire of catalytic templating or wire, imports hydrogen and protection gas, is heated to temperature of reaction 400 ~ 1200 DEG C, the constant temperature operation A1 of 0 ~ 60 minute; Import the operation A2 that carbon source carries out reacting; Be cooled to room temperature, obtain the operation A3 of three-dimensional graphene/metal line or metal wire composite structure.
Preferably, in preparation method of the present invention, one deck framework material is formed at the described three-dimensional graphene/metal line obtained or metal wire composite structure surface before being also included in described process B, form the process B 1 of framework material/graphene/metal line or metal wire composite structure, and after described process B, remove the process B 2 of framework material.
Above-mentioned framework material can be formed at described three-dimensional graphene/metal line or metal wire composite structure surface drying by polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate or polydimethylsiloxane being dissolved in the solution made in water, ethanol, acetone, N, N bis--dimethyl formamide, N-Methyl pyrrolidone or methyl-phenoxide solvent.
After removing metal wire or wire by etching, ethanol, Virahol, acetone or their mixed solvent can be utilized to remove the framework material of graphenic surface.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 DEG C, and etching time is 20-800min.
In addition, the metal wire as catalysts template 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, Platinum Nanoparticles line, nanometer iridium line, Technique of Nano Pd line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nano V line or their alloy nano-wire.Metal wire can adopt hydrothermal method to prepare by metal-salt and reductive agent.In addition, metal wire can also utilize metal salt solution to be prepared by electrochemical deposition.Metal salt solution is such as made to be prepared by electrochemical deposition on porous anodic alumina template.Metal wire as catalytic templating contributes to carbon source molecular cleavage, produces carbon and form saturated solid solution wherein after making cracking.
Wire as catalysts template 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 B alloy wire.Wire as catalytic templating contributes to carbon source molecular cleavage, produces carbon and form saturated solid solution wherein after making cracking.
It is the carbon source generating Graphene importing as the present invention, 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, dimethyl formamide or their mixing liquid, or the solid-state carbon source of polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate, polydimethylsiloxane or their mixture.
The protection gas imported in the reaction system of metal wire or wire and carbon source can be nitrogen, argon gas, helium or their mixed gas.Importing shielding gas flow amount in the reaction process imported is 1 ~ 1000sccm, and hydrogen flowing quantity is 1 ~ 500sccm, and gaseous carbon source is 1 ~ 200sccm.The protection gas imported in 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, are preferably and protect gas and hydrogen gas throughput ratio to be 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 control at 1 minute ~ 20 hours.Be preferably 10 minutes ~ 120 minutes.When reaction completes, can control rate of temperature fall is 10 ~ 300 DEG C/min.Be preferably 100 ~ 300 DEG C/min.
Three-dimensional graphene/metal line provided by the invention or metal wire composite structure, grapheme tube, have excellent conductivity and erosion resistance.Technique 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.
Accompanying drawing explanation
Fig. 1 illustrates the stereoscan photograph of graphene/nickel filament composite structure of the present invention;
Fig. 2 illustrates the stereoscan photograph of three-dimensional grapheme tube of the present invention;
Fig. 3 illustrates the Raman spectrum of graphene/nickel filament composite structure of the present invention;
Fig. 4 illustrates the corrosion-resistant digital photograph of comparative example nickel wire and graphene/nickel filament composite structure of the present invention;
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 the present invention is further illustrated with the following embodiments.Should be understood that the drawings and the specific embodiments or embodiment are all only exemplary, but not for limiting the present invention.
The preparation method of three-dimensional graphene/metal line of the present invention or metal wire composite structure, grapheme tube specifically comprises the following steps: with metal wire or wire for catalytic templating, put into chemical vapor deposition reaction chamber, import hydrogen and protection gas, be heated to temperature of reaction 400-1200 DEG C, constant temperature 0-60min; Import the operation that carbon source carries out reacting, importing shielding gas flow amount in 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 reaction process, react complete, controlling rate of temperature fall is 10-300 DEG C/min, is cooled to room temperature, obtains three-dimensional graphene/metal line or metal wire composite structure.
Further, the three-dimensional graphene/metal line of preparation or metal wire composite structure can also be put into framework material solution at its surface deposition one deck framework material, drying is solidified; Framework material/graphene/metal line or metal wire composite structure are put into etching liquid, removes metal wire or wire, obtain framework material/Graphene; Repeatedly wash framework material/Graphene with deionized water, then organic solvent will be placed in go to move graphenic surface framework material, finally obtain three-dimensional grapheme tube.
Three-dimensional graphene/metal line of the present invention or metal wire composite structure, three-dimensional grapheme tube preparation method have the advantage that grapheme tube conductivity is excellent, preparation cost is low that technique is simple, process is easy to control, make, and are therefore suitable for solar device, energy-storage battery, conducing composite material and the 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, Platinum Nanoparticles line, nanometer iridium line, Technique of Nano Pd line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nano V 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 B alloy wire.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, dimethyl formamide or their mixing liquid, or the solid-state carbon source of polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate, polydimethylsiloxane or their mixture.
Protection gas in the present invention is nitrogen, argon gas, helium or their mixed gas.The protection gas imported in 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 polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate or polydimethylsiloxane is dissolved in the solution made in water, ethanol, acetone, N, N bis--dimethyl formamide, N-Methyl pyrrolidone or 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 DEG C, and etching time can be 20-800min.
Above-mentioned organic solvent can be ethanol, Virahol, acetone or their mixed solvent.
Metal nanometer line in the present invention can adopt hydrothermal method and template electric-sedimentation legal system standby.
Exemplarily, the hydro-thermal preparation preparing metal nanometer line is as follows: take metal (iron, copper, cobalt, nickel, ruthenium, molybdenum, niobium, platinum, iridium, palladium, titanium, pick, thallium, tungsten or vanadium) nitrate, halide salt and vitriol put into container, add a certain amount of deionized water, borane reducing agent sodium hydride is added under strong stirring condition, glucose, hydrazine hydrate, aliphatic alkylamine (tetradecy lamine, cetylamine and stearylamine), the mol ratio controlling metal ion and reductive agent is 1: 20-1000: 1, strong stirring 1-10h, then, loaded in reactor, 120-300 DEG C is warming up to after sealing, constant temperature 1-60h, naturally cool to room temperature, adopt deionized water, ethanol and normal hexane carry out centrifuge washing, namely clean metal nano wire is obtained after vacuum-drying.
The galvanic deposit preparation of metal nanometer line is as follows: the nitrate, halide salt and the vitriol that take metal (iron, copper, cobalt, nickel, ruthenium, molybdenum, niobium, platinum, iridium, palladium, titanium, pick, thallium, tungsten or vanadium) put into container, add a certain amount of deionized water, load a certain amount of boric acid simultaneously, form uniform solution.Metal salt concentrations is 0.1-10M, and boric acid concentration is 0.02-10M, utilizes and prepares metal nanometer line in porous anodic alumina template galvanic deposit, 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 by above method or diameter wiry is 10nm ~ 5mm, the number of plies of Graphene is three-dimensional graphene/metal line or the metal wire composite structure of 1 ~ 100.
In addition, can also be prepared by above method that diameter is 10nm ~ 5mm, length is 50nm ~ 5mm, the number of plies of Graphene is the three-dimensional grapheme tube of 1 ~ 100.
Three-dimensional graphene/metal line of the present invention or metal wire composite structure, three-dimensional grapheme tube conductivity and rotproofness are excellent, are suitable for solar device, energy-storage battery, conducing composite material and the field such as corrosion-resistant.
Illustrate the preparation method of three-dimensional grapheme tube below further.
Embodiment 1
(1) adopt nickel wire as catalytic templating, the mean diameter of nickel wire is 25 μm.After ethanol, acetone and Virahol ultrasonic cleaning, nickel wire is loaded in chemical vapour deposition reactor furnace, pass into 100sccm hydrogen and 100sccm argon gas, start after 60min to be heated to 1000 DEG C, after constant temperature 30min, pass into 5sccm methane, reaction times 30min, reaction terminates rear stopping and passing into methane, closes electric furnace, is cooled fast to room temperature, obtain graphene/nickel filament composite structure, stereoscan photograph as shown in Figure 1.
(2) step (1) being prepared product is placed in the acetone soln of 4wt% polymethylmethacrylate, take out 100 DEG C and dry 3h, make its surface deposition one deck polymethylmethacrylate, put into the 5M salpeter solution 4h of 100ml, remove nickel wire, then put into acetone soln and remove polymethylmethacrylate, obtain three-dimensional grapheme tube, as shown in Figures 2 and 3, the Graphene number of plies is 1-10 for stereoscan photograph and Raman spectrum, and graphene-structured is perfect to be fallen into.
Embodiment 2
Preparation method is substantially with embodiment 1, and difference is: in step (1), and employing diameter is the nickel wire of 100 μm is catalytic templating, and the number of plies obtaining three-dimensional grapheme tube is 10-20, and graphene-structured is perfect to be fallen into.
Embodiment 3
Preparation method is substantially with embodiment 1, and difference is: in step (1), and chemical vapour deposition temperature is 900 DEG C, reaction times 10min, and the number of plies obtaining three-dimensional grapheme tube is 1-3, and graphene-structured is perfect to be fallen into.
Embodiment 4
(1) 1mmol copper sulfate is taken and 2mmol stearylamine puts into 100ml deionized water, after strong stirring 2h, transferred in reactor, carry out hydro-thermal reaction after sealing, temperature of reaction is 170 DEG C, reaction times is 36h, reaction terminates 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 monocrystal copper nanowires of 100 μm.Copper nano-wire is loaded in chemical vapour deposition reactor furnace, pass into 50sccm hydrogen and 100sccm nitrogen, start after 60min to be heated to 650 DEG C, pass into 10sccm acetylene after constant temperature 10min, reaction times 10min, reaction terminates rear stopping and passing through acetylene, close electric furnace, naturally cool to room temperature, obtain Graphene/copper nano-wire composite structure, transmission electron microscope photo as shown in Figure 5.
(2) Graphene/copper nano-wire composite structure prepared by step (1) is placed in the polyvinyl alcohol water solution of 5%, takes out and 130 DEG C of oven dry 1h, put into the 5M FeCl of 100ml
3stir 4h in solution, remove Nano line of metal copper, then put into acetone soln and remove polymethylmethacrylate, obtain three-dimensional grapheme tube, as shown in Figure 6, the Graphene number of plies is 3-5 to Raman spectrum, and graphene-structured is perfect to be fallen into.
Embodiment 5
Preparation method is substantially with embodiment 4, and difference is: in step (1), reaction times 30min, and the number of plies obtaining three-dimensional grapheme tube is 5-10, and graphene-structured is perfect to be fallen into.
Embodiment 6
Preparation method is substantially with embodiment 4, and difference is: in step (1), and adopt ethene as carbon source, the number of plies obtaining three-dimensional grapheme tube is 1-3, and graphene-structured is perfect to be fallen into.
Embodiment 7
(1) with the electroplate liquid that the mixing solutions of the boric acid of the rose vitriol of 0.2mol/L and 45g/L is cobalt, its pH value is transferred to 2-3.Be anode with graphite flake, the voltage applying 2V between anodic oxidation aluminium formwork and graphite flake carries out direct current electroless plating, and growth cobalt nanowire, growth temperature is 30 DEG C, and growth time is 5min.Then, be immersed in the mixing solutions of the 0.2mol/L chromic acid of 60 DEG C and 0.4mol/L phosphoric acid, removed alumina formwork, obtained cobalt nanowire.Preparing mean diameter is 60nm, and length is the monocrystalline cobalt nanowire of 20 μm.Cobalt nanowire is loaded in chemical vapour deposition reactor furnace, pass into 300sccm hydrogen and 600sccm helium, start after 60min to be heated to 850 DEG C, 5sccm propane is passed into after constant temperature 10min, reaction times 15min, reaction terminates rear stopping by propane, closes electric furnace, naturally cool to room temperature, obtain Graphene/cobalt nanowire composite structure.
(2) Graphene/cobalt nanowire composite structure prepared by step (1) is placed in the N-Methyl pyrrolidone solution of the polyvinylidene difluoride (PVDF) of 2%, take out and 180 DEG C 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 polyvinylidene difluoride (PVDF), obtain three-dimensional grapheme tube, the Graphene number of plies is 3-5, and graphene-structured is perfect to be fallen into.
Embodiment 8
Preparation method is substantially with embodiment 7, and difference is: in step (1), chemical vapour deposition 15min, and the number of plies obtaining three-dimensional grapheme tube is 5-10, and graphene-structured is perfect to be fallen into.
Embodiment 9
Preparation method is substantially with embodiment 7, and difference is: in step (1), be quickly cooled to room temperature, and the number of plies obtaining three-dimensional grapheme tube is 1-3, and graphene-structured is perfect to be fallen into.
Embodiment 10
Preparation method is substantially with embodiment 7, and difference is: in step (1), 15sccm propane reaction times 30min, and the number of plies obtaining three-dimensional grapheme tube is 10-20, and graphene-structured is perfect to be fallen into.
Embodiment 11
(1) adopt three-electrode system, take anodic oxidation aluminium formwork as working electrode, ruthenium titanium net is supporting electrode, and saturated calomel electrode is as reference electrode.Nickel plating solution sulfur acid nickel 160g/L, boric acid 30g/L, solution ph is 3.0-3.5, and sedimentation potential is-0.9V; Copper plating solution sulfur acid copper 75g/L, sodium sulfate 1-5g/L, solution ph is 2.5-3.0, and sedimentation potential is-0.08V.Adopt each 3min of alternating deposit copper and mickel, employing 1mol/L sodium hydroxide solution in the porous anodic alumina template of double flute method controlling potential to remove porous anodic alumina template, the copper/nickel bielement nano line mean diameter of acquisition is 80nm, and length is 25 μm.By traditional thread binding for copper/nickel bielement nano enter in chemical vapour deposition reactor furnace, pass into 50sccm hydrogen and 300sccm argon gas and helium mix gas (argon gas: helium=1: 1), start after 120min to be heated to 600 DEG C, after constant temperature 10min, 20sccm bubbling argon ethanol as carbon source, reaction times 15min, reaction terminates rear stopping and passing into carbon source, close electric furnace, cool fast, obtain Graphene/copper/nickel nanowire composite structures.
(2) Graphene/copper/nickel nanowire composite structures prepared by step (1) is placed in the methyl-phenoxide solution of the polymethylmethacrylate of 3%, takes out and 150 DEG C of oven dry 10min, put into the 1M hydrochloric acid/2M FeCl of 100ml
31h in mixing solutions, removes metallic copper/nickel nano wire, then puts into acetone soln and remove polymethylmethacrylate, and obtain three-dimensional grapheme tube, the Graphene number of plies is 1-2, and graphene-structured is perfect to be fallen into.
Embodiment 12
Preparation method is substantially with embodiment 11, and difference is: in step (1), and adopt 50sccm bubbling argon ethanol as carbon source, the number of plies obtaining three-dimensional grapheme tube is 3-5, and graphene-structured is perfect to be fallen into.
Embodiment 13
Preparation method is substantially with embodiment 11, and difference is: in step (1), and adopt 50sccm bubbling argon ethanol as carbon source, reaction times 30min, obtains the number of plies 3-10 of three-dimensional grapheme tube, and graphene-structured is perfect to be fallen into.
Embodiment 14
(1) adopt diameter 150 μm of Mo-Ni alloy silks as catalytic templating, at its surface deposition one deck polymethylmethacrylate, load in chemical vapour deposition reactor furnace, pass into 50sccm hydrogen and 300sccm argon gas and helium mix gas (argon gas: helium=1: 1), after 60min, 5min quickly heats up to 1100 DEG C, after constant temperature 10min, close electric furnace, be quickly cooled to room temperature, obtain Graphene/molybdenum/nickel nanowire composite structures.
(2) Graphene/molybdenum/nickel nanowire composite structures prepared by step (1) is placed in the acetone soln of the polydimethylsiloxane of 5%, take out and 120 DEG C 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 polydimethylsiloxane, obtain three-dimensional grapheme tube, the number of plies of Graphene is 1-3, and graphene-structured is perfect to be fallen into.
Comparative example 1
Adopt nickel wire as catalytic templating, the mean diameter of nickel wire is 25 μm.After ethanol, acetone and Virahol ultrasonic cleaning, nickel wire is loaded in chemical vapour deposition reactor furnace, pass into 100sccm hydrogen and 100sccm argon gas, start after 60min to be heated to 1000 DEG C, after constant temperature 40min, close electric furnace, be cooled fast to room temperature, obtain the nickel wire not having graphene growth.
For the ease of contrast graphene/nickel filament composite structure and nickel wire, test their conductivity and erosion resistance respectively.Compared with nickel wire, the electric conductivity of graphene/nickel filament composite structure can improve 20%.In addition, graphene/nickel silk and nickel wire are put in dilute hydrochloric acid and find after 10min, there is no the nickel wire complete reaction formation light green solution of growing graphene, and graphene/nickel filament composite structure can keep stable in dilute hydrochloric acid, as shown in Figure 4.The erosion resistance indicating graphene/nickel filament composite structure is obviously better than nickel wire.
Industrial applicability: three-dimensional grapheme of the present invention and prepare the method for this three-dimensional grapheme, there is 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 (18)
1. a three-dimensional grapheme tube, is characterized in that, the diameter of described grapheme tube is 25 μm ~ 5mm, and length is 50nm ~ 5mm, and the number of plies of described Graphene is 1 ~ 100, and described graphene-structured is perfect to be fallen into.
2. three-dimensional grapheme tube according to claim 1, is characterized in that, the diameter of described grapheme tube is 25 μm ~ 100 μm.
3. three-dimensional grapheme tube according to claim 1, is characterized in that, the number of plies of described grapheme tube is 1 ~ 20.
4. the three-dimensional grapheme tube according to any one of claim 1-3, is characterized in that, the length of described grapheme tube is 100nm ~ 100 μm.
5. the preparation method of arbitrary described three-dimensional grapheme tube in a Claims 1-4, it is characterized in that, comprise: make carbon source at described metal wire or wiry outside surface directly generate operation A that Graphene coating form graphene/metal line or metal wire composite structure as catalysts template by chemical Vapor deposition process using metal wire or wire, wherein, described operation A comprises and puts into chemical vapor deposition reaction chamber using as the metal wire of catalytic templating or wire, import hydrogen and protection gas, be heated to temperature of reaction 400 ~ 1200 DEG C, the constant temperature operation A1 of 0 ~ 60 minute, import the operation A2 that carbon source carries out reacting, be cooled to room temperature, obtain the operation A3 of three-dimensional graphene/metal line or metal wire composite structure, the protection gas imported in reaction process and hydrogen gas throughput ratio are 0.1 ~ 6, remove metal wire or process B wiry by etching, thus obtain three-dimensional grapheme tube.
6. preparation method according to claim 5, it is characterized in that, one deck framework material is formed at the described three-dimensional graphene/metal line obtained or metal wire composite structure surface before being also included in described process B, form the process B 1 of framework material/graphene/metal line or metal wire composite structure, and after described process B, remove the process B 2 of framework material.
7. the preparation method according to claim 5 or 6, it is characterized in that, described 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, Platinum Nanoparticles line, nanometer iridium line, Technique of Nano Pd line, nanometer titanium wire, nanometer pick line, nanometer thallium line, nanometer tungsten line, nano V line or their alloy nano-wire, described 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 B alloy wire.
8. the preparation method according to claim 5 or 6, is characterized in that, described metal wire adopts hydrothermal method to prepare by metal-salt and reductive agent.
9. the preparation method according to claim 5 or 6, is characterized in that, described metal wire utilizes metal salt solution to be prepared by electrochemical deposition.
10. the preparation method according to claim 5 or 6, it is characterized in that, described 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, dimethyl formamide or their mixing liquid, or the solid-state carbon source of polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate, polydimethylsiloxane or their mixture.
11. preparation methods according to claim 6, it is characterized in that, described framework material polyvinylidene difluoride (PVDF), polyvinylpyrrolidone, polyoxyethylene glycol, polyvinyl alcohol, polymethylmethacrylate or polydimethylsiloxane is dissolved in the solution made in water, ethanol, acetone, N, N bis--dimethyl formamide, N-Methyl pyrrolidone or methyl-phenoxide solvent to be formed at described three-dimensional graphene/metal line or metal wire composite structure surface drying.
12. preparation methods according to claim 6, is characterized in that, after removing metal wire or wire, utilize ethanol, Virahol, acetone or their mixed solvent to remove the framework material of graphenic surface, obtain three-dimensional grapheme tube by etching.
13. preparation methods according to claim 5 or 6, it is characterized in that, the etching liquid that described etching process adopts is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, iron trichloride or their mixing solutions, and etching temperature is 30-80 DEG C, and etching time is 20-800min.
14. preparation methods according to claim 5 or 6, it is characterized in that, described protection gas is nitrogen, argon gas, helium or their mixed gas.
15. preparation methods according to claim 5 or 6, it is characterized in that, importing shielding gas flow amount in reaction process is 1 ~ 1000sccm, and hydrogen flowing quantity is 1 ~ 500sccm, and gaseous carbon source is 1 ~ 200sccm.
16. preparation methods according to claim 15, is characterized in that, protect gas and gaseous state carbon-source gas throughput ratio to be 1 ~ 1000 in reaction process.
17. preparation methods according to claim 5 or 6, is characterized in that, the reaction times controlling reaction process is 1 minute ~ 20 hours.
18. preparation methods according to claim 5 or 6, is characterized in that, it is 10 ~ 300 DEG C/min that process of cooling controls rate of temperature fall.
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| CN110176332A (en) * | 2019-05-24 | 2019-08-27 | 徐新敏 | A kind of Graphene electrodes material and preparation method thereof |
| CN110436446A (en) * | 2019-09-20 | 2019-11-12 | 张小云 | A kind of graphene and preparation method thereof |
| CN115215328B (en) * | 2022-07-26 | 2023-09-08 | 中国科学院上海硅酸盐研究所 | Bamboo-shaped graphene tube array and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04331008A (en) * | 1991-05-07 | 1992-11-18 | Agency Of Ind Science & Technol | Manufacture of diamond-coated tool |
| US5275850A (en) * | 1988-04-20 | 1994-01-04 | Hitachi, Ltd. | Process for producing a magnetic disk having a metal containing hard carbon coating by plasma chemical vapor deposition under a negative self bias |
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| CN102070141A (en) * | 2011-03-10 | 2011-05-25 | 武汉大学 | Method for preparing graphene |
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
| CN102176338A (en) * | 2011-03-10 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Graphene/copper nanowire composite electric-conducting material and preparation method thereof |
| CN102190294A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院大连化学物理研究所 | Preparation method for carbon nanotube or graphene nano-carbon material |
-
2012
- 2012-01-20 CN CN201210019901.6A patent/CN102586869B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275850A (en) * | 1988-04-20 | 1994-01-04 | Hitachi, Ltd. | Process for producing a magnetic disk having a metal containing hard carbon coating by plasma chemical vapor deposition under a negative self bias |
| JPH04331008A (en) * | 1991-05-07 | 1992-11-18 | Agency Of Ind Science & Technol | Manufacture of diamond-coated tool |
| CN102190294A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院大连化学物理研究所 | Preparation method for carbon nanotube or graphene nano-carbon material |
| CN101831622A (en) * | 2010-05-20 | 2010-09-15 | 中国科学院化学研究所 | Grapheme foam and preparation method thereof |
| CN101913598A (en) * | 2010-08-06 | 2010-12-15 | 浙江大学 | Method for preparing graphene membrane |
| CN102070141A (en) * | 2011-03-10 | 2011-05-25 | 武汉大学 | Method for preparing graphene |
| CN102176338A (en) * | 2011-03-10 | 2011-09-07 | 中国科学院上海硅酸盐研究所 | Graphene/copper nanowire composite electric-conducting material and preparation method thereof |
| CN102134067A (en) * | 2011-04-18 | 2011-07-27 | 北京大学 | Method for preparing single-layer graphene |
Non-Patent Citations (2)
| Title |
|---|
| Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition;Zongping Chen等;《nature materials》;20110410;第10卷;424-428 * |
| 石墨烯的化学气相沉积法制备;任文才等;《新型炭材料》;20110228;71-80 * |
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