CN106744920B - The preparation method of multi-layer graphene self-supporting pipe without clad skeleton - Google Patents
The preparation method of multi-layer graphene self-supporting pipe without clad skeleton Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention discloses a kind of preparation methods of the multi-layer graphene self-supporting pipe of no clad skeleton, including (1), and the immersion of wire dust technology to be taken to be placed in dehydrated alcohol ultrasonic, drying；(2) deposition graphene is grown in wire surface, obtains graphene/metal wire composite structure；(3) on the surface of graphene deposition cladding metallic catalyst template, then metallic catalyst template surface deposit graphene, repeatedly after formed have graphene/metallic catalyst repetitive structure composite material；(4) composite material is put into etching liquid to cleaning, drying after removing wire and metallic catalyst template, obtains the multi-layer graphene self-supporting pipe without clad skeleton.The multi-layer graphene self-supporting pipe of no clad skeleton provided by the invention has excellent mobility, mechanical strength, thermal conductivity and corrosion resistance, is suitable for the numerous areas such as microelectronics, transparent electrode, organic electro-optic device, energy-storage battery, multifunctional composite and biomedicine.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of multi-layer graphene self-supporting of no clad skeleton
The preparation method of pipe.
Background technique
A kind of two-dimentional allotrope of the graphene as carbon for obtaining various countries researcher extensive concern in recent years, has
Mobility is high, room temperature Hall effect is significant, diracelectron stable structure, translucency can compare favourably with ITO, mechanical strength is big and
The speciality such as thermal conductivity is excellent.For this purpose, graphene is in the numerous areas such as electrode of organic electro-optic device, various energy-storage batteries, compound
Material and biologic medical suffer from good application prospect.[specific visible document: H.Sun et
al.Adv.Mater.2013,25:2554.M.Mecklenburg et al.Adv.Mater.2012,24:3486.L.Tian
et al.Nat.Commun.2012,3:609.L.R.Meza et al.Science 2014,345:1322.]
Publication number CN102586869A discloses a kind of preparation method of three-dimensional grapheme tube, and the invention is in order to be had
The grapheme tube of enabling capabilities increases one layer of skeleton structure on graphene table side, and the grapheme tube framework material is poly- inclined
The organic materials such as vinyl fluoride, polyethylene glycol, polymethylacrylic acid.In addition, publication number CN102502604A discloses a kind of more function
Can grapheme tube preparation method, coating polymethyl methacrylate is also needed in the grapheme tube preparation process.These inventions
In, it is required to the self-supporting that coating organic material realizes grapheme tube as skeleton, above-mentioned material is enhancing grapheme tube
While mechanical strength, undoubtedly also it is greatly affected the electric conductivity of graphene.There has been no using wire as catalysis at present
Agent template deposits in wire surface and graphene/metal wire composite structure is made, and then coated catalysts mould on the surface of graphene
Plate deposits then at catalysts template surface and graphene/catalysts template/graphene/metal wire composite structure is made, repeatedly
The composite material for realizing multilayer " graphene/catalysts template " repetitive structure afterwards, eventually by removal catalysts template preparation one
The relevant report of multi-layer graphene self-supporting pipe of the kind without clad skeleton.
Summary of the invention
It is excellent it is an object of the invention to solve at least the above problems and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of multilayer stone of no clad skeleton is provided
The preparation method of black alkene self-supporting pipe, comprising the following steps:
Step 1: it is placed in ultrasound in dehydrated alcohol after taking wire dust technology to impregnate removal surface impurity and passivation layer,
Then it is dried for standby；
Step 2: being put into chemical vapor depsotition equipment and being grown on its surface using the wire of drying as growth substrate
Graphene is deposited, graphene/metal wire composite structure is obtained；
Step 3: depositing cladding metallic catalyst template in graphene/metal wire composite structure graphene surface, then
It places into chemical vapor depsotition equipment and deposits graphene, repeated deposition metallic catalyst mould in metallic catalyst template surface
Plate, graphene are repeatedly formed afterwards has graphene/metallic catalyst repetitive structure composite material；
Step 4: removing metal for being put into etching liquid with graphene/metallic catalyst repetitive structure composite material
It after silk and metallic catalyst template, dries, is obtained without clad bone after being cleaned with dehydrated alcohol and deionized water to products therefrom
The multi-layer graphene self-supporting pipe of frame.
Preferably, the wire is copper wire or nickel wire, and the diameter of the wire is 10nm~1cm, and length is
10nm~1m.
Preferably, the dust technology concentration be 0.001~1mol/L, wire in dust technology soaking time be 1s~
60min, a length of 1~60min when ultrasonic in dehydrated alcohol；The drying is dried temperature using in air dry oven
It is 40~200 DEG C, the processing time is 0.1~36h.
Preferably, in the step 3, cladding metal is deposited in graphene/metal wire composite structure graphene surface
The deposition method of catalysts template is in magnetron sputtering, hot evaporation, pulse laser deposition, chemical plating or electrochemical deposition method
Any one；The deposition rate for depositing nano noble metal particles clad is 0.1nm/s~10 μm/s, the metallic catalyst mould
Plate is copper, nickel, silver, gold, platinum, palladium, titanium, ruthenium, any one or more alloy material being combined into niobium.
Preferably, the diameter of the multi-layer graphene self-supporting pipe of the no clad skeleton is 10nm~1cm, and length is
10nm~1m.
Preferably, in the step 2 and three, in chemical vapor depsotition equipment, wire surface grows graphene mistake
The reaction atmosphere of journey is the gaseous mixture of hydrogen and inert gas, under the premise of heating rate is 5~30 DEG C/min, is heated to anti-
800~1500 DEG C of temperature, 0~120min of constant temperature are answered, after importing carbon source is reacted, is cooled to room temperature, obtains graphene/metal
Filament composite structure；The carbon source is one of methanol steam, alcohol vapour, acetone steam, xylene steam or a variety of mixed
It closes；The flow of the carbon source is 10~30sccm.
Preferably, in the step 4, etching liquid is that nitric acid, hydrochloric acid, perchloric acid, liquor potassic permanganate, iron chloride are molten
The combination of one or more of liquid.
Preferably, the process replacement of the step 3 are as follows: the graphene for obtaining step 2/metal wire composite structure is made
For the Rotation of receiver device of electrostatic spinning, the polymer spin dope electrostatic spinning of graphene is blended with to the graphite of rotation
On alkene/metal wire composite structure, polymer covering layer is formed, is then placed again into chemical vapor depsotition equipment in polymer packet
Clad surface deposits graphene, repeats electrostatic spinning polymer covering layer, graphene and is repeatedly formed afterwards with graphene/polymer
The composite material of clad repetitive structure；The process of the step 4 replaces with, and will have graphene/polymer covering layer to repeat
The composite material of structure is put into etching liquid after removal wire, is added into n,N-Dimethylformamide, N, N- dimethyl second
It impregnates in amide or toluene for 24 hours, is dried after then being cleaned with dehydrated alcohol and deionized water to products therefrom, obtained without clad
The multi-layer graphene self-supporting pipe of skeleton.
Preferably, the polymer spin dope is PLA solution, polymethyl acrylate solution, polyvinylpyrrolidine
One of ketone solution, butyl polyacrylate solution, polystyrene solution, polyimide solution；The polymer spin dope
Concentration be 5~15wt%；The mass ratio of the graphene and polymer spin dope is 1:100~150；The graphene with
The mixed process of polymer spin dope are as follows: graphene is mixed with polymer spin dope, dispersing agent 1- ethyl-is then added
Mixed solution is heated to 80 DEG C, keeps its reaction by 3- methylimidazolium chloride under the conditions of low whipping speed is 1000r/min
For 24 hours, it is cooled to room temperature, obtains the polymer spin dope for being mixed with graphene；The dispersing agent 1- ethyl -3- methyl chloride miaow
The weight ratio of azoles and graphene is 1:10~20；
The electrospinning process are as follows: be blended with spray of the polymer spin dope injection with stainless steel spray head of graphene
It penetrates in container, is then applied the voltage on stainless steel spray head with high voltage power supply, and pumped using the propulsion being connect with spray containers
Polymer spin dope in spray containers is connect by graphene/metal wire composite structure that stainless steel spray head is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning are as follows: environment temperature is 50~80 DEG C, the output voltage of high voltage power supply be 15~
Distance is 10~15cm between 25kv, wire and stainless steel spray head, flow velocity is 10~15mL/h, the rotation speed of reception device
For 60~120r/min；
Preferably, graphene/gold of the polymer spin dope electrostatic spinning for being blended with graphene to rotation
While category on filament composite structure, by graphene dispersing solution ultrasonic atomizatio on graphene/metal wire composite structure of rotation；Institute
State the raw material that graphene dispersing solution includes following parts by weight: 10~15 parts of graphene, 1- ethyl-3-methylimidazole lactic acid 1~3
Part, 30~50 parts of cyclohexanone, 30~50 parts of N- cyclohexyl pyrrolidone, 30~50 parts of propylene glycol butyl ether acetate；The graphite
The power of alkene dispersion liquid ultrasonic atomizatio is 80W, and frequency 2.5MHz, condensation rate is 2~10mL/min, the ejiction opening of ultrasonic atomizatio
With at a distance from reception device be 5~15cm.
The present invention is include at least the following beneficial effects: preparation method of the invention have operation is simple, repeatability
By force, the characteristics of no pollution to the environment.The multi-layer graphene self-supporting pipe of no clad skeleton provided by the invention has excellent
Mobility, mechanical strength, thermal conductivity and corrosion resistance, be suitable for microelectronics, transparent electrode, organic electro-optic device, energy-storage battery,
The numerous areas such as multifunctional composite and biomedicine.
Further advantage, target and feature of the invention will be partially reflected by the following instructions, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Detailed description of the invention:
Fig. 1 are as follows: grown in preparation process made from (a) comparative example 1 without multilayer " graphene/metallic catalyst " repetitive structure
The grapheme tube stereoscan photograph that process obtains；(b) after spin coating polymethyl methacrylate prepared by comparative example 2, then benzene is used
The grapheme tube stereoscan photograph obtained after methyl ether removal polymethyl methacrylate；(c) nothing prepared by the embodiment of the present invention 1
The stereoscan photograph that the multi-layer graphene self-supporting pipe of clad skeleton is tested；
Fig. 2 is that the multi-layer graphene self-supporting pipe without clad skeleton after growth substrate is removed in the embodiment of the present invention 1
Optical microscope photograph.
Specific embodiment:
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art referring to specification text
Word can be implemented accordingly.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 15 μm of diameter, the copper wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1000 DEG C under the heating rate of 30 DEG C/min, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/copper wire composite junction
The graphene surface of structure deposits coated copper catalysts template, forms Nanometer Copper catalysts template/graphene/copper wire composite construction,
The preparation process for repeating graphene in step 2 deposits graphene then at Nanometer Copper catalysts template surface, and graphene/nano is made
Rice copper catalyst/graphene/copper wire composite construction, repeated deposition copper catalyst template, graphene are repeatedly formed afterwards has graphite
Alkene/nanometer copper catalyst repetitive structure composite material；
Step 4: by being put into iron chloride etching liquid with graphene/metallic catalyst repetitive structure composite material
After copper wire and Nanometer Copper catalysts template, with dehydrated alcohol, the solution such as deionized water are placed in drum after cleaning to products therefrom
60 DEG C of drying 2h in wind drying box, obtain the multi-layer graphene self-supporting pipe without clad skeleton, Fig. 2 and Fig. 1 c show catalysis
Agent template be etched after the multi-layer graphene self-supporting pipe without clad skeleton optical microscope photograph and scanning electron microscope shine
Piece.
Embodiment 2:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 15 μm of diameter, the nickel wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the nickel wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1000 DEG C under the heating rate of 30 DEG C/min, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/nickel silk
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/nickel silk composite junction
The graphene surface of structure deposits coated copper catalysts template, forms Nanometer Copper catalysts template/graphene/nickel filament composite structure,
The preparation process for repeating graphene in step 2 deposits graphene then at Nanometer Copper catalysts template surface, and graphene/nano is made
Rice copper catalyst/graphene/nickel filament composite structure, repeated deposition copper catalyst template, graphene are repeatedly formed afterwards has graphite
Alkene/nanometer copper catalyst repetitive structure composite material；
Step 4: by being put into iron chloride etching liquid with graphene/metallic catalyst repetitive structure composite material
After nickel wire and Nanometer Copper catalysts template, with dehydrated alcohol, the solution such as deionized water are placed in drum after cleaning to products therefrom
60 DEG C of drying 2h in wind drying box obtain the multi-layer graphene self-supporting pipe without clad skeleton.
Embodiment 3:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 15 μm of diameter, the copper wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1050 DEG C under the heating rate of 20 DEG C/min, and constant temperature 30min is passed through alcohol vapour
20sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/copper wire composite junction
The graphene surface of structure deposits coated copper catalysts template, forms Nanometer Copper catalysts template/graphene/copper wire composite construction,
The preparation process for repeating graphene in step 2 deposits graphene then at Nanometer Copper catalysts template surface, and graphene/nano is made
Rice copper catalyst/graphene/copper wire composite construction, repeated deposition copper catalyst template, graphene are repeatedly formed afterwards has graphite
Alkene/nanometer copper catalyst repetitive structure composite material；
Step 4: by being put into iron chloride etching liquid with graphene/metallic catalyst repetitive structure composite material
After copper wire and Nanometer Copper catalysts template, with dehydrated alcohol, the solution such as deionized water are placed in drum after cleaning to products therefrom
60 DEG C of drying 2h in wind drying box obtain the multi-layer graphene self-supporting pipe without clad skeleton.
Embodiment 4:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 15 μm of diameter, the copper wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1000 DEG C under the heating rate of 30 DEG C/min, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: by chemical plating method, in the deposition coated copper catalysis of graphene/copper wire composite construction graphene surface
Agent template forms Nanometer Copper catalysts template/graphene/copper wire composite construction, repeats the preparation process of graphene in step 2
Graphene is deposited then at Nanometer Copper catalysts template surface, graphene/nanometer copper catalyst/graphene/copper wire composite junction is made
Structure, repeated deposition copper catalyst template, graphene are repeatedly formed afterwards has the compound of graphene/nanometer copper catalyst repetitive structure
Material；
Step 4: by being put into iron chloride etching liquid with graphene/metallic catalyst repetitive structure composite material
After copper wire and Nanometer Copper catalysts template, with dehydrated alcohol, the solution such as deionized water are placed in drum after cleaning to products therefrom
60 DEG C of drying 2h in wind drying box obtain the multi-layer graphene self-supporting pipe without clad skeleton.
In order to illustrate effect of the invention, it is as follows to provide comparative example:
Comparative example 1:
(1) 15 μm of diameter is taken, the copper wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity and blunt
After changing layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
(2) using the copper wire of drying as catalysts template, be put into chemical vapor depsotition equipment, reaction atmosphere be hydrogen and
The gaseous mixture of nitrogen is heated to 1000 DEG C under the heating rate of 30 DEG C/min, and constant temperature 60min is passed through alcohol vapour 10sccm
It is reacted, stops being passed through alcohol vapour after reaction, be rapidly cooled to room temperature, obtain graphene/copper wire composite construction；
(3) it uses ferric chloride solution as etching liquid, above-mentioned composite construction is immersed in removal Nanometer Copper in etching liquid and is urged
After agent and copper wire, with dehydrated alcohol, the solution such as deionized water are placed in air dry oven 60 DEG C after cleaning to products therefrom
2h is dried, the grapheme tube without the growth process preparation of multilayer " graphene/metallic catalyst " repetitive structure is obtained, Fig. 1 a is shown
The stereoscan photograph of the grapheme tube.
Comparative example 2:
(1) 15 μm of diameter is taken, the copper wire of length 5cm rises dust technology with 0.1mol/ and impregnates 2min removal surface impurity and blunt
After changing layer, it is placed in ultrasound 20min in dehydrated alcohol, 60 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
(2) using the copper wire of drying as catalysts template, be put into chemical vapor depsotition equipment, reaction atmosphere be hydrogen and
The gaseous mixture of nitrogen is heated to 1000 DEG C under the heating rate of 30 DEG C/min, and constant temperature 60min is passed through alcohol vapour 10sccm
It is reacted, stops being passed through alcohol vapour after reaction, be rapidly cooled to room temperature, obtain graphene/copper wire composite construction；
(3) in composite structure surface spin coating polymethyl methacrylate protective coating obtained above, design parameter:
600rpm coats 60s, is placed in 60 DEG C of dry 3min on drying table；
(4) it uses ferric chloride solution as etching liquid, above-mentioned composite construction is immersed in removal Nanometer Copper in etching liquid and is urged
After agent and copper wire, with dehydrated alcohol, the solution such as deionized water are placed in air dry oven 60 DEG C after cleaning to products therefrom
2h is dried, the external grapheme tube by polymethyl methacrylate cladding support is obtained；
(5) dripping methyl phenyl ethers anisole makes polymethyl methacrylate quilt in the grapheme tube surface that polymethyl methacrylate coats
Dissolution, is siphoned away organic solution with filter paper at edge, Fig. 1 b show the stereoscan photograph of the grapheme tube.
In conjunction with shown in Fig. 1 c, we this it appears that comparative example 1 and comparison 2 made from grapheme tube have it is very serious
Collapse situation, and the self-supporting of the multi-layer graphene pipe prepared by the present invention without clad skeleton be substantially better than it is above-mentioned two
Grapheme tube made from comparative example.
Embodiment 5:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 30 μm of diameter, the nickel wire of length 10cm rises dust technology with 0.5mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, 100 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the nickel wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1200 DEG C under the heating rate of 20 DEG C/min, and constant temperature 80min is passed through xylene steam
20sccm is reacted, and is stopped being passed through xylene steam after reaction, is rapidly cooled to room temperature, it is multiple to obtain graphene/nickel silk
Close structure；
Step 3: by thermal evaporation deposition, in the graphene surface deposition cladding silver catalyst of graphene/nickel filament composite structure
Template forms nano-silver catalyst template/graphene/nickel filament composite structure, repeats the preparation process of graphene in step 2 again
Graphene is deposited in nano-silver catalyst template surface, graphene/nano silver catalyst/graphene/nickel filament composite structure is made,
Repeated deposition silver catalyst template, graphene repeatedly form the composite wood with graphene/nano silver catalyst repetitive structure afterwards
Material；
Step 4: being removed being put into Nitric acid etching liquid with graphene/metallic catalyst repetitive structure composite material
After nickel wire and nano-silver catalyst template, with dehydrated alcohol, the solution such as deionized water are placed in air blast after cleaning to products therefrom
60 DEG C of drying 2h in drying box obtain the multi-layer graphene self-supporting pipe without clad skeleton.
Embodiment 6:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 50 μm of diameter, the copper wire of length 5cm rises dust technology with 0.5mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, 100 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1500 DEG C under the heating rate of 25 DEG C/min, and constant temperature 80min is passed through methanol steam
20sccm is reacted, and is stopped being passed through methanol steam after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: depositing Coated with Palladium in graphene/copper wire composite construction graphene surface by pulsed laser deposition
Catalysts template forms nano Pd catalyst template/graphene/copper wire composite construction, repeats the preparation of graphene in step 2
Process deposits graphene then at nano Pd catalyst template surface, and it is multiple that graphene/nanometer palladium catalyst/graphene/copper wire is made
Structure is closed, repeated deposition palladium catalyst template, graphene are repeatedly formed afterwards has graphene/nanometer palladium catalyst repetitive structure
Composite material；
Step 4: the composite material with graphene/nanometer palladium catalyst repetitive structure is put into Nitric acid etching liquid
After copper wire and nano Pd catalyst template, with dehydrated alcohol, the solution such as deionized water are placed in drum after cleaning to products therefrom
60 DEG C of drying 2h in wind drying box obtain the multi-layer graphene self-supporting pipe without clad skeleton.
Embodiment 7:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 50 μm of diameter, the copper wire of length 5cm rises dust technology with 0.5mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, 100 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1500 DEG C under the heating rate of 25 DEG C/min, and constant temperature 80min is passed through methanol steam
20sccm is reacted, and is stopped being passed through methanol steam after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: the graphene that step 2 is obtained/copper wire composite construction is incited somebody to action as the Rotation of receiver device of electrostatic spinning
It is mixed on the polymer spin dope electrostatic spinning to graphene/metal wire composite structure of rotation of graphene, forms polymerization
Then object clad is placed again into chemical vapor depsotition equipment and deposits graphene in polymer overmold layer surface, repeat electrostatic
Spinning polymer clad, graphene are repeatedly formed afterwards has graphene/polymer covering layer repetitive structure composite material；
Step 4: removing gold for being put into etching liquid with graphene/polymer covering layer repetitive structure composite material
After belonging to silk, it is added into n,N-Dimethylformamide, n,N-dimethylacetamide or toluene and impregnates for 24 hours, then with anhydrous second
Pure and mild deionized water is dried after cleaning to products therefrom, obtains the multi-layer graphene self-supporting pipe without clad skeleton；
Wherein, the polymer spin dope is PLA solution；The concentration of the polymer spin dope is 5wt%；
The mass ratio of the graphene and polymer spin dope is 1:100；The mixing of the graphene and polymer spin dope
Journey are as follows: graphene is mixed with polymer spin dope, dispersing agent 1- ethyl -3- methylimidazolium chloride is then added, is stirring
Under the conditions of speed is 1000r/min, mixed solution is heated to 80 DEG C, its reaction is kept for 24 hours, is cooled to room temperature, is mixed
There is the polymer spin dope of graphene；The weight ratio of the dispersing agent 1- ethyl -3- methylimidazolium chloride and graphene is 1:
10；
The electrospinning process are as follows: be blended with spray of the polymer spin dope injection with stainless steel spray head of graphene
It penetrates in container, is then applied the voltage on stainless steel spray head with high voltage power supply, and pumped using the propulsion being connect with spray containers
Polymer spin dope in spray containers is connect by graphene/metal wire composite structure that stainless steel spray head is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning are as follows: environment temperature is 50 DEG C, the output voltage of high voltage power supply is 15kv, gold
Distance is 10cm between category silk and stainless steel spray head, the rotation speed of flow velocity 10mL/h, reception device is 60r/min.
Embodiment 8:
A kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, comprising the following steps:
Step 1: taking 100 μm of diameter, the copper wire of length 10cm rises dust technology with 1mol/ and impregnates 2min removal surface impurity
And after passivation layer, it is placed in ultrasound 30min in dehydrated alcohol, 100 DEG C of drying 2h in air dry oven is then placed into and is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the copper wire of drying as catalysts template, reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen is heated to 1300 DEG C under the heating rate of 15 DEG C/min, and constant temperature 80min is passed through alcohol vapour
20sccm is reacted, and is stopped being passed through alcohol vapour after reaction, is rapidly cooled to room temperature, it is compound to obtain graphene/copper wire
Structure；
Step 3: the graphene that step 2 is obtained/copper wire composite construction is incited somebody to action as the Rotation of receiver device of electrostatic spinning
It is mixed on the polymer spin dope electrostatic spinning of graphene to the graphene of rotation/copper wire composite construction, forms polymer
Then clad is placed again into chemical vapor depsotition equipment and deposits graphene in polymer overmold layer surface, repeat Static Spinning
Silk polymer covering layer, graphene are repeatedly formed afterwards with graphene/polymer covering layer repetitive structure composite material；
Step 4: removing gold for being put into etching liquid with graphene/polymer covering layer repetitive structure composite material
After belonging to silk, it is added into n,N-Dimethylformamide and impregnates for 24 hours, it is then clear to products therefrom with dehydrated alcohol and deionized water
It is dried after washing, obtains the multi-layer graphene self-supporting pipe without clad skeleton；
Wherein, the polymer spin dope is polystyrene solution；The concentration of the polymer spin dope is
10wt%；The mass ratio of the graphene and polymer spin dope is 1:120；The graphene and polymer spin dope
Mixed process are as follows: graphene is mixed with polymer spin dope, dispersing agent 1- ethyl -3- methylimidazolium chloride is then added,
Under the conditions of low whipping speed is 1000r/min, mixed solution is heated to 80 DEG C, its reaction is kept for 24 hours, is cooled to room temperature, obtains
To the polymer spin dope for being mixed with graphene；The weight of dispersing agent the 1- ethyl -3- methylimidazolium chloride and graphene
Than for 1:15；
The electrospinning process are as follows: be blended with spray of the polymer spin dope injection with stainless steel spray head of graphene
It penetrates in container, is then applied the voltage on stainless steel spray head with high voltage power supply, and pumped using the propulsion being connect with spray containers
Polymer spin dope in spray containers is connect by graphene/metal wire composite structure that stainless steel spray head is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning are as follows: environment temperature is 80 DEG C, the output voltage of high voltage power supply is 20kv, gold
Distance is 12cm between category silk and stainless steel spray head, the rotation speed of flow velocity 15mL/h, reception device is 100r/min.
Embodiment 9:
In step 3 of the present invention, while electrostatic spinning, by graphene dispersing solution ultrasonic atomizatio in the graphite of rotation
On alkene/metal wire composite structure；Remaining parameter with it is identical in example 7, technical process is also identical；It obtains without cladding
The multi-layer graphene self-supporting pipe of layer skeleton.
The graphene dispersing solution includes the raw material of following parts by weight: 10 parts of graphene, 1- ethyl-3-methylimidazole lactic acid
1 part, 30 parts of cyclohexanone, 30 parts of N- cyclohexyl pyrrolidone, 30 parts of propylene glycol butyl ether acetate；The graphene dispersing solution ultrasound
The power of atomization is 80W, and frequency 2.5MHz, condensation rate 5mL/min, the ejiction opening of ultrasonic atomizatio is at a distance from reception device
For 10cm.
Embodiment 10:
In step 3 of the present invention, while electrostatic spinning, by graphene dispersing solution ultrasonic atomizatio in the graphite of rotation
On alkene/metal wire composite structure；Remaining parameter with it is identical in example 8, technical process is also identical；It obtains without cladding
The multi-layer graphene self-supporting pipe of layer skeleton.
The graphene dispersing solution includes the raw material of following parts by weight: 12 parts of graphene, 1- ethyl-3-methylimidazole lactic acid
2 parts, 50 parts of cyclohexanone, 40 parts of N- cyclohexyl pyrrolidone, 50 parts of propylene glycol butyl ether acetate；The graphene dispersing solution ultrasound
The power of atomization is 80W, and frequency 2.5MHz, condensation rate 8mL/min, the ejiction opening of ultrasonic atomizatio is at a distance from reception device
For 15cm.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (8)
1. a kind of preparation method of the multi-layer graphene self-supporting pipe of no clad skeleton, which comprises the following steps:
Step 1: being placed in ultrasound in dehydrated alcohol, then after taking wire dust technology to impregnate removal surface impurity and passivation layer
It is dried for standby；
Step 2: being put into chemical vapor depsotition equipment using the wire of drying as growth substrate and growing deposition on its surface
Graphene obtains graphene/metal wire composite structure；
Step 3: graphene/metal wire composite structure that step 2 is obtained will be mixed as the Rotation of receiver device of electrostatic spinning
Conjunction has on the polymer spin dope electrostatic spinning of graphene to graphene/metal wire composite structure of rotation, forms polymer
Then clad is placed again into chemical vapor depsotition equipment and deposits graphene in polymer overmold layer surface, repeat Static Spinning
Silk polymer covering layer, graphene are repeatedly formed afterwards with graphene/polymer covering layer repetitive structure composite material；
Step 4: removing wire for being put into etching liquid with graphene/polymer covering layer repetitive structure composite material
Afterwards, be added into n,N-Dimethylformamide, n,N-dimethylacetamide or toluene and impregnate for 24 hours, then with dehydrated alcohol and
Deionized water is dried after cleaning to products therefrom, obtains the multi-layer graphene self-supporting pipe without clad skeleton.
2. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
The wire is copper wire or nickel wire, and the diameter of the wire is 10nm~1cm, and length is 10nm~1m.
3. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
The dust technology concentration is 0.001~1mol/L, and wire soaking time in dust technology is 1s~60min, in dehydrated alcohol
A length of 1~60min when middle ultrasound；The drying is 40~200 DEG C using temperature in air dry oven, is dried, processing
Time is 0.1~36h.
4. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
The diameter of the multi-layer graphene self-supporting pipe of the no clad skeleton is 10nm~1cm, and length is 10nm~1m.
5. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
In the step 2, in chemical vapor depsotition equipment, wire surface grow graphene process reaction atmosphere be hydrogen and
The gaseous mixture of inert gas is heated to 800~1500 DEG C of reaction temperature, perseverance under the premise of heating rate is 5~30 DEG C/min
0~120min of temperature is cooled to room temperature after importing carbon source is reacted, and obtains graphene/metal wire composite structure；The carbon source
For one of methanol steam, alcohol vapour, acetone steam, xylene steam or a variety of mixing；The flow of the carbon source is
10~30sccm.
6. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
In the step 4, etching liquid is one or more of nitric acid, hydrochloric acid, perchloric acid, liquor potassic permanganate, ferric chloride solution
Combination.
7. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
The polymer spin dope is PLA solution, polymethyl acrylate solution, polyvinylpyrrolidonesolution solution, polyacrylic acid fourth
One of ester solution, polystyrene solution, polyimide solution；The concentration of the polymer spin dope is 5~15wt%；
The mass ratio of the graphene and polymer spin dope is 1:100~150；The graphene and polymer spin dope it is mixed
Conjunction process are as follows: graphene is mixed with polymer spin dope, dispersing agent 1- ethyl -3- methylimidazolium chloride is then added,
Under the conditions of mixing speed is 1000r/min, mixed solution is heated to 80 DEG C, its reaction is kept for 24 hours, is cooled to room temperature, obtains
It is mixed with the polymer spin dope of graphene；The weight ratio of dispersing agent the 1- ethyl -3- methylimidazolium chloride and graphene
For 1:10~20；
The electrospinning process are as follows: the polymer spin dope for being blended with graphene, which injects the injection with stainless steel spray head, to be held
It in device, is then applied the voltage on stainless steel spray head with high voltage power supply, and will spray using the propulsion pump being connect with spray containers
The polymer spin dope penetrated in container, which is sprayed by stainless steel spray head to the graphene of rotation/metal wire composite structure, receives dress
Set, the injection conditions of the electrostatic spinning are as follows: environment temperature is 50~80 DEG C, the output voltage of high voltage power supply be 15~
Distance is 10~15cm between 25kv, wire and stainless steel spray head, flow velocity is 10~15mL/h, the rotation speed of reception device
For 60~120r/min.
8. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as described in claim 1, which is characterized in that
It is same on the polymer spin dope electrostatic spinning for being blended with graphene to graphene/metal wire composite structure of rotation
When, by graphene dispersing solution ultrasonic atomizatio on graphene/metal wire composite structure of rotation；The graphene dispersing solution includes
The raw material of following parts by weight: 10~15 parts of graphene, 1~3 part of 1- ethyl-3-methylimidazole lactic acid, 30~50 parts of cyclohexanone, N-
30~50 parts of cyclohexyl pyrrolidone, 30~50 parts of propylene glycol butyl ether acetate；The function of the graphene dispersing solution ultrasonic atomizatio
Rate is 80W, and frequency 2.5MHz, condensation rate is 2~10mL/min, and the ejiction opening of ultrasonic atomizatio is 5 at a distance from reception device
~15cm.
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