CN106744920A - The preparation method of the multi-layer graphene self-supporting pipe without clad skeleton - Google Patents
The preparation method of the multi-layer graphene self-supporting pipe without clad skeleton Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
Take and ultrasound in absolute ethyl alcohol, drying are placed in after wire dust technology soaks the invention discloses a kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, including (1)；(2) deposited graphite alkene is grown in wire surface, obtains Graphene/metal wire composite structure；(3) in graphenic surface deposition cladding metallic catalyst template, then in metallic catalyst template surface deposited graphite alkene, the composite with Graphene/metallic catalyst repetitive structure is repeatedly formed afterwards；(4) composite is put into etching liquid and removes cleaning, drying after wire and metallic catalyst template, obtain the multi-layer graphene self-supporting pipe without clad skeleton.The multi-layer graphene self-supporting pipe without clad skeleton that the present invention is provided has excellent mobility, mechanical strength, thermal conductivity and corrosion resistance, it is adaptable to the numerous areas such as microelectronics, transparency 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 without clad skeleton
The preparation method of pipe.
Background technology
Graphene has as a kind of two-dimentional allotrope of the carbon for obtaining various countries' researcher's extensive concern in recent years
Mobility is high, room temperature Hall effect significantly, diracelectron Stability Analysis of Structures, translucency can be compared favourably with ITO, mechanical strength it is big and
The speciality such as thermal conductivity is excellent.Therefore, Graphene is in the numerous areas such as organic electro-optic device, electrode of 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 possessed
The grapheme tube of enabling capabilities, one layer of skeleton structure is increased on Graphene table side, and the grapheme tube framework material is poly- inclined
The organic materials such as PVF, polyethylene glycol, polymethylacrylic acid.Additionally, publication number CN102502604A discloses a kind of many work(
The preparation method of energy grapheme tube, also needs to coat polymethyl methacrylate in the grapheme tube preparation process.These inventions
In, it is required to coat the self-supporting that organic material realizes grapheme tube as skeleton, above-mentioned material is enhancing grapheme tube
While mechanical strength, undoubtedly it is greatly affected also the electric conductivity of Graphene.Not yet have at present using wire as catalysis
Agent template, Graphene/metal wire composite structure is obtained in wire surface deposition, and then in graphenic surface coated catalysts mould
Plate, then at catalysts template surface, deposition is obtained Graphene/catalysts template/Graphene/metal wire composite structure, repeatedly
The composite of multilayer " Graphene/catalysts template " repetitive structure is realized afterwards, and one is prepared eventually through removal catalysts template
Plant the relevant report of the multi-layer graphene self-supporting pipe without clad skeleton.
The content of the invention
It is an object of the invention to solve at least the above and/or defect, and provide at least will be described later excellent
Point.
In order to realize these purposes of the invention and further advantage, there is provided a kind of multilayer stone without clad skeleton
The preparation method of black alkene self-supporting pipe, comprises the following steps：
Step one, take wire dust technology immersion removal surface impurity and passivation layer after, be placed in absolute ethyl alcohol ultrasound,
Then dry for standby；
Step 2, the wire that will be dried are put into chemical vapor depsotition equipment in its superficial growth as growth substrate
Deposited graphite alkene, obtains Graphene/metal wire composite structure；
Step 3, the graphenic surface deposition cladding metallic catalyst template in Graphene/metal wire composite structure, then
Place into chemical vapor depsotition equipment in metallic catalyst template surface deposited graphite alkene, repeated deposition metallic catalyst mould
Plate, Graphene repeatedly form the composite with Graphene/metallic catalyst repetitive structure afterwards；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into etching liquid removes metal
After silk and metallic catalyst template, dried after being cleaned to products therefrom with absolute ethyl alcohol and deionized water, obtained without clad bone
The multi-layer graphene self-supporting pipe of frame.
Preferably, the wire is copper wire or nickel wire, a diameter of 10nm~1cm of the wire, and length is
10nm~1m.
Preferably, the dust technology concentration be 0.001~1mol/L, wire in dust technology soak time be 1s~
60min, a length of 1~60min during ultrasound in absolute ethyl alcohol；The drying is used in air dry oven, dried process temperature
It it is 40~200 DEG C, process time is 0.1~36h.
Preferably, in the step 3, in the graphenic surface deposition cladding metal of Graphene/metal wire composite structure
The deposition process of catalysts template is in magnetron sputtering, hot evaporation, pulsed laser deposition, chemical plating or electrochemical deposition method
Any one；The sedimentation rate for depositing nano noble metal particles clad is 0.1nm/s~10 μm/s, the metallic catalyst mould
Plate is any one or more alloy material being combined into copper, nickel, silver, gold, platinum, palladium, titanium, ruthenium, niobium.
Preferably, a diameter of 10nm~1cm of the multi-layer graphene self-supporting pipe without clad skeleton, length is
10nm~1m.
Preferably, in the step 2 and three, in chemical vapor depsotition equipment, wire surface growth Graphene mistake
The reaction atmosphere of journey is the gaseous mixture of hydrogen and inert gas, on the premise of programming rate is 5~30 DEG C/min, is heated to anti-
800~1500 DEG C of temperature is answered, 0~120min of constant temperature after importing carbon source is reacted, is cooled to room temperature, obtains Graphene/metal
Filament composite structure；The carbon source is the mixed of one or more in methanol steam, alcohol vapour, acetone steam, xylene steam
Close；The flow of the carbon source is 10~30sccm.
Preferably, in the step 4, etching liquid is molten nitric acid, hydrochloric acid, perchloric acid, liquor potassic permanganate, iron chloride
The combination of one or more in liquid.
Preferably, the process of the step 3 is replaced with：The Graphene that step 2 is obtained/metal wire composite structure is made
It is the Rotation of receiver device of electrostatic spinning, is blended with the polymer spin dope electrostatic spinning of Graphene to the graphite of rotation
On alkene/metal wire composite structure, polymer covering layer is formed, be then placed again into chemical vapor depsotition equipment in polymer bag
Clad surface deposited graphite alkene, repeats electrostatic spinning polymer covering layer, Graphene and is repeatedly formed afterwards with Graphene/polymer
The composite of clad repetitive structure；The process of the step 4 is replaced with, and will be repeated with Graphene/polymer covering layer
The composite of structure is put into after removing wire in etching liquid, is added into DMF, N, N- dimethyl second
24h is soaked in acid amides or toluene, is dried after then being cleaned to products therefrom with absolute ethyl alcohol and deionized water, obtained without clad
The multi-layer graphene self-supporting pipe of skeleton.
Preferably, the polymer spin dope is PLA solution, PMA solution, polyvinylpyrrolidine
One kind in ketone solution, butyl polyacrylate solution, polystyrene solution, polyimide solution；The polymer spin dope
Concentration be 5~15wt%；The Graphene is 1 with the mass ratio of polymer spin dope：100~150；The Graphene with
The mixed process of polymer spin dope is：Graphene is mixed with polymer spin dope, be subsequently adding dispersant 1- ethyls-
3- methylimidazolium chlorides, low whipping speed keeps it to react under the conditions of 1000r/min, mixed solution to be heated into 80 DEG C
24h, is cooled to room temperature, obtains being mixed with the polymer spin dope of Graphene；The dispersant 1- ethyls -3- methyl chloride miaows
Azoles is 1 with the weight ratio of Graphene:10~20；
The electrospinning process is：It is blended with the polymer spin dope spray of the injection with stainless steel shower nozzle of Graphene
Penetrate in container, then applied the voltage on stainless steel shower nozzle with high voltage power supply, and using the propulsion pump being connected with spray containers
Polymer spin dope in spray containers is connect by Graphene/metal wire composite structure that stainless steel shower nozzle is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning is：Environment temperature is 50~80 DEG C, the output voltage of high voltage power supply for 15~
The rotary speed that distance is 10~15cm between 25kv, wire and stainless steel shower nozzle, flow velocity is 10~15mL/h, reception device
It is 60~120r/min；
Preferably, Graphene/gold of the polymer spin dope electrostatic spinning for being blended with Graphene to rotation
While on category filament composite structure, by graphene dispersing solution ultrasonic atomizatio on the Graphene/metal wire composite structure of rotation；Institute
State raw material of the graphene dispersing solution including following weight portion：10~15 parts of Graphene, 1- ethyl-3-methylimidazoles lactic acid 1~3
Part, 30~50 parts of cyclohexanone, 30~50 parts of N- cyclohexyl pyrrolidones, 30~50 parts of propandiol butyl ether acetate；The graphite
The power of alkene dispersion liquid ultrasonic atomizatio is 80W, and frequency is 2.5MHz, and condensation rate is 2~10mL/min, the ejiction opening of ultrasonic atomizatio
It is 5~15cm with the distance of reception device..
The present invention at least includes following beneficial effect：Preparation method of the invention is repeatable with operation is simple
By force, environmentally safe the characteristics of.The multi-layer graphene self-supporting pipe without clad skeleton that the present invention is provided has excellent
Mobility, mechanical strength, thermal conductivity and corrosion resistance, it is adaptable to microelectronics, transparency electrode, organic electro-optic device, energy-storage battery,
The numerous areas such as multifunctional composite and biomedicine.
Further advantage of the invention, target and feature embody part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Brief description of the drawings：
Fig. 1 is：Grown without multilayer " Graphene/metallic catalyst " repetitive structure in preparation process obtained in (a) comparative example 1
The grapheme tube stereoscan photograph that operation is obtained；After spin coating polymethyl methacrylate prepared by (b) comparative example 2, then use benzene
The grapheme tube stereoscan photograph obtained after methyl ether removal polymethyl methacrylate；Nothing prepared by (c) embodiment of the present invention 1
The stereoscan photograph that the multi-layer graphene self-supporting pipe test of clad skeleton is obtained；
Fig. 2 is the multi-layer graphene self-supporting pipe without clad skeleton after removal growth substrate in the embodiment of the present invention 1
Optical microscope photograph.
Specific embodiment：
The present invention is described in further detail below in conjunction with the accompanying drawings, to make those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that it is used herein such as " have ", "comprising" and " including " term do not allot one or many
The presence or addition of individual other elements or its combination.
Embodiment 1：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 0.1mol/ liter dust technology immersion 2min removal surface impurities for taking 15 μm of diameter, length 5cm
And after passivation layer, ultrasound 20min in absolute ethyl alcohol is placed in, it is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 30 DEG C/min, is heated to 1000 DEG C, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in Graphene/copper wire composite junction
The graphenic surface deposition coated copper catalysts template of structure, forms Nanometer Copper catalysts template/Graphene/copper wire composite construction,
The preparation process of Graphene is obtained graphene/nano then at Nanometer Copper catalysts template surface deposited graphite alkene in repeat step two
Rice copper catalyst/Graphene/copper wire composite construction, repeated deposition copper catalyst template, Graphene are repeatedly formed afterwards has graphite
The composite of alkene/nanometer copper catalyst repetitive structure；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into iron chloride etching liquid
After except copper wire and Nanometer Copper catalysts template, with absolute ethyl alcohol, the solution such as deionized water is positioned over drum after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in wind drying box, 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 ESEM shine
Piece.
Embodiment 2：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the nickel wire 0.1mol/ liter dust technology immersion 2min removal surface impurities for taking 15 μm of diameter, length 5cm
And after passivation layer, ultrasound 20min in absolute ethyl alcohol is placed in, it is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the nickel wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 30 DEG C/min, is heated to 1000 DEG C, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains graphene/nickel silk compound
Structure；
Step 3, by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in graphene/nickel silk composite junction
The graphenic surface deposition coated copper catalysts template of structure, forms Nanometer Copper catalysts template/graphene/nickel filament composite structure,
The preparation process of Graphene is obtained graphene/nano then at Nanometer Copper catalysts template surface deposited graphite alkene in repeat step two
Rice copper catalyst/graphene/nickel filament composite structure, repeated deposition copper catalyst template, Graphene are repeatedly formed afterwards has graphite
The composite of alkene/nanometer copper catalyst repetitive structure；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into iron chloride etching liquid
After except nickel wire and Nanometer Copper catalysts template, with absolute ethyl alcohol, the solution such as deionized water is positioned over drum after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in wind drying box.
Embodiment 3：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 0.1mol/ liter dust technology immersion 2min removal surface impurities for taking 15 μm of diameter, length 5cm
And after passivation layer, ultrasound 20min in absolute ethyl alcohol is placed in, it is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 20 DEG C/min, is heated to 1050 DEG C, and constant temperature 30min is passed through alcohol vapour
20sccm is reacted, and reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, by magnetron sputtering method, under conditions of deposition velocity is 20nm/s, in Graphene/copper wire composite junction
The graphenic surface deposition coated copper catalysts template of structure, forms Nanometer Copper catalysts template/Graphene/copper wire composite construction,
The preparation process of Graphene is obtained graphene/nano then at Nanometer Copper catalysts template surface deposited graphite alkene in repeat step two
Rice copper catalyst/Graphene/copper wire composite construction, repeated deposition copper catalyst template, Graphene are repeatedly formed afterwards has graphite
The composite of alkene/nanometer copper catalyst repetitive structure；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into iron chloride etching liquid
After except copper wire and Nanometer Copper catalysts template, with absolute ethyl alcohol, the solution such as deionized water is positioned over drum after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in wind drying box.
Embodiment 4：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 0.1mol/ liter dust technology immersion 2min removal surface impurities for taking 15 μm of diameter, length 5cm
And after passivation layer, ultrasound 20min in absolute ethyl alcohol is placed in, it is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 30 DEG C/min, is heated to 1000 DEG C, and constant temperature 60min is passed through alcohol vapour
10sccm is reacted, and reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, by chemical plating method, in the graphenic surface deposition cladding copper catalysis of Graphene/copper wire composite construction
Agent template, forms Nanometer Copper catalysts template/Graphene/copper wire composite construction, the preparation process of Graphene in repeat step two
Then at Nanometer Copper catalysts template surface deposited graphite alkene, graphene/nanometer copper catalyst/Graphene/copper wire composite junction is obtained
Structure, repeated deposition copper catalyst template, Graphene repeatedly form compound with graphene/nanometer copper catalyst repetitive structure afterwards
Material；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into iron chloride etching liquid
After except copper wire and Nanometer Copper catalysts template, with absolute ethyl alcohol, the solution such as deionized water is positioned over drum after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in wind drying box.
In order to illustrate effect of the invention, there is provided comparative example is as follows：
Comparative example 1：
(1) copper wire for taking 15 μm of diameter, length 5cm rises dust technology and soaks 2min and removes surface impurity and blunt with 0.1mol/
After changing layer, ultrasound 20min in absolute ethyl alcohol is placed in, is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
(2) will dry copper wire as catalysts template, be put into chemical vapor depsotition equipment, reaction atmosphere be hydrogen and
The gaseous mixture of nitrogen, under the programming rate of 30 DEG C/min, is heated to 1000 DEG C, and constant temperature 60min is passed through alcohol vapour 10sccm
Reacted, reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire composite construction；
(3) use ferric chloride solution as etching liquid, removal Nanometer Copper is urged during above-mentioned composite construction is immersed in into etching liquid
After agent and copper wire, with absolute ethyl alcohol, the solution such as deionized water is positioned over 60 DEG C in air dry oven after being cleaned to products therefrom
Drying 2h, obtains the grapheme tube prepared without multilayer " Graphene/metallic catalyst " repetitive structure growth operation, and Fig. 1 a show
The stereoscan photograph of the grapheme tube.
Comparative example 2：
(1) copper wire for taking 15 μm of diameter, length 5cm rises dust technology and soaks 2min and removes surface impurity and blunt with 0.1mol/
After changing layer, ultrasound 20min in absolute ethyl alcohol is placed in, is then placed into 60 DEG C of drying 2h dry for standby in air dry oven；
(2) will dry copper wire as catalysts template, be put into chemical vapor depsotition equipment, reaction atmosphere be hydrogen and
The gaseous mixture of nitrogen, under the programming rate of 30 DEG C/min, is heated to 1000 DEG C, and constant temperature 60min is passed through alcohol vapour 10sccm
Reacted, reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains 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 on drying table 60 DEG C and dries 3min；
(4) use ferric chloride solution as etching liquid, removal Nanometer Copper is urged during above-mentioned composite construction is immersed in into etching liquid
After agent and copper wire, with absolute ethyl alcohol, the solution such as deionized water is positioned over 60 DEG C in air dry oven after being cleaned to products therefrom
Drying 2h, obtains the outside grapheme tube by polymethyl methacrylate cladding support；
(5) drip methyl phenyl ethers anisole makes polymethyl methacrylate quilt in the grapheme tube surface of polymethyl methacrylate cladding
Dissolving, at edge, filter paper siphons away organic solution, and Fig. 1 b show the stereoscan photograph of the grapheme tube.
With reference to shown in Fig. 1 c, we are this it appears that comparative example 1 and grapheme tube obtained in contrast 2 have very serious
Situation is collapsed, and the self-supporting of the multi-layer graphene pipe without clad skeleton prepared by the present invention is substantially better than above-mentioned two
Grapheme tube obtained in comparative example.
Embodiment 5：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the nickel wire 0.5mol/ liter dust technology immersion 2min removal surface impurities for taking 30 μm of diameter, length 10cm
And after passivation layer, ultrasound 30min in absolute ethyl alcohol is placed in, it is then placed into 100 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the nickel wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 20 DEG C/min, is heated to 1200 DEG C, and constant temperature 80min is passed through xylene steam
20sccm is reacted, and reaction stops being passed through xylene steam after terminating, and is quickly cooled to room temperature, obtains graphene/nickel silk multiple
Close structure；
Step 3, by thermal evaporation deposition, in the graphenic surface deposition cladding silver catalyst of graphene/nickel filament composite structure
Template, forms nano-silver catalyst template/graphene/nickel filament composite structure, and the preparation process of Graphene is again in repeat step two
In nano-silver catalyst template surface deposited graphite alkene, graphene/nano silver catalyst/graphene/nickel filament composite structure is obtained,
Repeated deposition silver catalyst template, Graphene repeatedly form the composite wood with graphene/nano silver catalyst repetitive structure afterwards
Material；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into Nitric acid etching liquid and removes
After nickel wire and nano-silver catalyst template, with absolute ethyl alcohol, the solution such as deionized water is positioned over air blast after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in drying box.
Embodiment 6：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 0.5mol/ liter dust technology immersion 2min removal surface impurities for taking 50 μm of diameter, length 5cm
And after passivation layer, ultrasound 30min in absolute ethyl alcohol is placed in, it is then placed into 100 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 25 DEG C/min, is heated to 1500 DEG C, and constant temperature 80min is passed through methanol steam
20sccm is reacted, and reaction stops being passed through methanol steam after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, by pulsed laser deposition, deposit Coated with Palladium in the graphenic surface of Graphene/copper wire composite construction
Catalysts template, forms nano Pd catalyst template/Graphene/copper wire composite construction, the preparation of Graphene in repeat step two
Process is obtained graphene/nanometer palladium catalyst/Graphene/copper wire multiple then at nano Pd catalyst template surface deposited graphite alkene
Structure is closed, repeated deposition palladium catalyst template, Graphene are repeatedly formed with graphene/nanometer palladium catalyst repetitive structure afterwards
Composite；
Step 4, the composite with graphene/nanometer palladium catalyst repetitive structure is put into Nitric acid etching liquid
After except copper wire and nano Pd catalyst template, with absolute ethyl alcohol, the solution such as deionized water is positioned over drum after being cleaned to products therefrom
60 DEG C of drying 2h, obtain the multi-layer graphene self-supporting pipe without clad skeleton in wind drying box.
Embodiment 7：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 0.5mol/ liter dust technology immersion 2min removal surface impurities for taking 50 μm of diameter, length 5cm
And after passivation layer, ultrasound 30min in absolute ethyl alcohol is placed in, it is then placed into 100 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 25 DEG C/min, is heated to 1500 DEG C, and constant temperature 80min is passed through methanol steam
20sccm is reacted, and reaction stops being passed through methanol steam after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, the Graphene for obtaining step 2/copper wire composite construction, will used as the Rotation of receiver device of electrostatic spinning
The polymer spin dope electrostatic spinning of Graphene is mixed with to the Graphene/metal wire composite structure of rotation, polymerization is formed
Thing clad, is then placed again into chemical vapor depsotition equipment, in polymer overmold layer surface deposited graphite alkene, repeating electrostatic
Spinning polymer clad, Graphene repeatedly form the composite with Graphene/polymer covering layer repetitive structure afterwards；
Step 4, the composite with Graphene/polymer covering layer repetitive structure is put into gold is removed in etching liquid
After category silk, it is added into soaking 24h in DMF, DMA or toluene, then uses anhydrous second
Alcohol and deionized water are dried after being cleaned to products therefrom, obtain 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 Graphene is 1 with the mass ratio of polymer spin dope：100；The mixing of the Graphene and polymer spin dope
Cheng Wei：Graphene is mixed with polymer spin dope, dispersant 1- ethyl -3- methylimidazolium chlorides are subsequently adding, in stirring
Speed keeps its reaction 24h under the conditions of 1000r/min, mixed solution to be heated into 80 DEG C, is cooled to room temperature, is mixed
There is the polymer spin dope of Graphene；The dispersant 1- ethyl -3- methylimidazolium chlorides are 1 with the weight ratio of Graphene:
10；
The electrospinning process is：It is blended with the polymer spin dope spray of the injection with stainless steel shower nozzle of Graphene
Penetrate in container, then applied the voltage on stainless steel shower nozzle with high voltage power supply, and using the propulsion pump being connected with spray containers
Polymer spin dope in spray containers is connect by Graphene/metal wire composite structure that stainless steel shower nozzle is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning is：Environment temperature is 50 DEG C, the output voltage of high voltage power supply is 15kv, gold
Category silk and stainless steel shower nozzle between distance be 10cm, flow velocity be 10mL/h, reception device rotary speed be 60r/min.
Embodiment 8：
A kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, comprises the following steps：
Step one, the copper wire 1mol/ liter dust technology immersion 2min removal surface impurities for taking 100 μm of diameter, length 10cm
And after passivation layer, ultrasound 30min in absolute ethyl alcohol is placed in, it is then placed into 100 DEG C of drying 2h dry for standby in air dry oven；
Step 2, the copper wire that will be dried are put into chemical vapor depsotition equipment as catalysts template, and reaction atmosphere is hydrogen
The gaseous mixture of gas and nitrogen, under the programming rate of 15 DEG C/min, is heated to 1300 DEG C, and constant temperature 80min is passed through alcohol vapour
20sccm is reacted, and reaction stops being passed through alcohol vapour after terminating, and is quickly cooled to room temperature, obtains Graphene/copper wire and is combined
Structure；
Step 3, the Graphene for obtaining step 2/copper wire composite construction, will used as the Rotation of receiver device of electrostatic spinning
The polymer spin dope electrostatic spinning of Graphene is mixed with to the Graphene/copper wire composite construction of rotation, polymer is formed
Clad, is then placed again into chemical vapor depsotition equipment, in polymer overmold layer surface deposited graphite alkene, repeating Static Spinning
Silk polymer covering layer, Graphene repeatedly form the composite with Graphene/polymer covering layer repetitive structure afterwards；
Step 4, the composite with Graphene/polymer covering layer repetitive structure is put into gold is removed in etching liquid
After category silk, it is added into soaking 24h in DMF, it is then clear to products therefrom with absolute ethyl alcohol and deionized water
Dried after washing, obtain 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 Graphene is 1 with the mass ratio of polymer spin dope：120；The Graphene and polymer spin dope
Mixed process is：Graphene is mixed with polymer spin dope, dispersant 1- ethyl -3- methylimidazolium chlorides are subsequently adding,
Low whipping speed keeps its reaction 24h under the conditions of 1000r/min, mixed solution to be heated into 80 DEG C, is cooled to room temperature, obtains
To the polymer spin dope for being mixed with Graphene；The weight of the dispersant 1- ethyl -3- methylimidazolium chlorides and Graphene
Than being 1:15；
The electrospinning process is：It is blended with the polymer spin dope spray of the injection with stainless steel shower nozzle of Graphene
Penetrate in container, then applied the voltage on stainless steel shower nozzle with high voltage power supply, and using the propulsion pump being connected with spray containers
Polymer spin dope in spray containers is connect by Graphene/metal wire composite structure that stainless steel shower nozzle is sprayed to rotation
On receiving apparatus, the injection conditions of the electrostatic spinning is：Environment temperature is 80 DEG C, the output voltage of high voltage power supply is 20kv, gold
Category silk and stainless steel shower nozzle between distance be 12cm, flow velocity be 15mL/h, reception device rotary speed be 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；Obtain without cladding
The multi-layer graphene self-supporting pipe of layer skeleton.
The graphene dispersing solution includes the raw material of following weight portion：10 parts of Graphene, 1- ethyl-3-methylimidazole lactic acid
1 part, 30 parts of cyclohexanone, 30 parts of N- cyclohexyl pyrrolidones, 30 parts of propandiol butyl ether acetate；The graphene dispersing solution ultrasound
The power of atomization is 80W, and frequency is 2.5MHz, and condensation rate is 5mL/min, the ejiction opening of ultrasonic atomizatio and the distance of reception device
It is 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；Obtain without cladding
The multi-layer graphene self-supporting pipe of layer skeleton.
The graphene dispersing solution includes the raw material of following weight portion：12 parts of Graphene, 1- ethyl-3-methylimidazole lactic acid
2 parts, 50 parts of cyclohexanone, 40 parts of N- cyclohexyl pyrrolidones, 50 parts of propandiol butyl ether acetate；The graphene dispersing solution ultrasound
The power of atomization is 80W, and frequency is 2.5MHz, and condensation rate is 8mL/min, the ejiction opening of ultrasonic atomizatio and the distance of reception device
It is 15cm.
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in specification and implementation method
With, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the legend with description.
Claims (10)
1. a kind of preparation method of the multi-layer graphene self-supporting pipe without clad skeleton, it is characterised in that comprise the following steps：
Step one, take wire dust technology immersion removal surface impurity and passivation layer after, be placed in absolute ethyl alcohol ultrasound, then
Dry for standby；
Step 2, the wire that will be dried are put into chemical vapor depsotition equipment in its superficial growth deposition as growth substrate
Graphene, obtains Graphene/metal wire composite structure；
Step 3, the graphenic surface deposition cladding metallic catalyst template in Graphene/metal wire composite structure, then put again
Enter in chemical vapor depsotition equipment in metallic catalyst template surface deposited graphite alkene, repeated deposition metallic catalyst template, stone
Black alkene repeatedly forms the composite with Graphene/metallic catalyst repetitive structure afterwards；
Step 4, the composite with Graphene/metallic catalyst repetitive structure is put into etching liquid remove wire and
After metallic catalyst template, dried after being cleaned to products therefrom with absolute ethyl alcohol and deionized water, obtained without clad skeleton
Multi-layer graphene self-supporting pipe.
2. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
The wire is copper wire or nickel wire, and a diameter of 10nm~1cm of the wire, length is 10nm~1m.
3. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
The dust technology concentration is 0.001~1mol/L, and wire soak time in dust technology is 1s~60min, in absolute ethyl alcohol
A length of 1~60min when middle ultrasonic；Using in air dry oven, dried process temperature is 40~200 DEG C, treatment for the drying
Time is 0.1~36h.
4. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
In the step 3, in the deposition of the graphenic surface deposition cladding metallic catalyst template of Graphene/metal wire composite structure
Method is any one in magnetron sputtering, hot evaporation, pulsed laser deposition, chemical plating or electrochemical deposition method；Deposition is received
Rice noble metal clad sedimentation rate be 0.1nm/s~10 μm/s, the metallic catalyst template be copper, nickel, silver,
Any one or more alloy material being combined into gold, platinum, palladium, titanium, ruthenium, niobium.
5. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
A diameter of 10nm~1cm of the multi-layer graphene self-supporting pipe without clad skeleton, length is 10nm~1m.
6. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
In the step 2 and three, in chemical vapor depsotition equipment, the reaction atmosphere of wire surface growth Graphene process is hydrogen
The gaseous mixture of gas and inert gas, on the premise of programming rate is 5~30 DEG C/min, is heated to reaction temperature 800~1500
DEG C, 0~120min of constant temperature after importing carbon source is reacted, is cooled to room temperature, obtains Graphene/metal wire composite structure；It is described
Carbon source is the mixing of one or more in methanol steam, alcohol vapour, acetone steam, xylene steam；The stream of the carbon source
It is 10~30sccm to measure.
7. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
In the step 4, etching liquid is one or more in nitric acid, hydrochloric acid, perchloric acid, liquor potassic permanganate, ferric chloride solution
Combination.
8. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 1, it is characterised in that
The process of the step 3 is replaced with：Rotation of the Graphene/metal wire composite structure that step 2 is obtained as electrostatic spinning
Reception device, is blended with the polymer spin dope electrostatic spinning of Graphene to the Graphene/metal wire composite structure of rotation
On, polymer covering layer is formed, then it is placed again into chemical vapor depsotition equipment in polymer overmold layer surface deposited graphite
Alkene, repeats electrostatic spinning polymer covering layer, Graphene and is repeatedly formed afterwards with Graphene/polymer covering layer repetitive structure
Composite；The process of the step 4 is replaced with, and the composite with Graphene/polymer covering layer repetitive structure is put
Enter after removing wire in etching liquid, be added into being soaked in DMF, DMA or toluene
24h, dries after then being cleaned to products therefrom with absolute ethyl alcohol and deionized water, obtains the multi-layer graphene without clad skeleton
Self-supporting pipe.
9. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 8, it is characterised in that
The polymer spin dope is PLA solution, PMA solution, polyvinylpyrrolidonesolution solution, polyacrylic acid fourth
One kind in ester solution, polystyrene solution, polyimide solution；The concentration of the polymer spin dope is 5~15wt%；
The Graphene is 1 with the mass ratio of polymer spin dope：100~150；The Graphene is mixed with polymer spin dope
Conjunction process is：Graphene is mixed with polymer spin dope, dispersant 1- ethyl -3- methylimidazolium chlorides are subsequently adding,
Mixing speed keeps its reaction 24h under the conditions of 1000r/min, mixed solution to be heated into 80 DEG C, is cooled to room temperature, obtains
It is mixed with the polymer spin dope of Graphene；The weight ratio of the dispersant 1- ethyl -3- methylimidazolium chlorides and Graphene
It is 1:10~20；
The electrospinning process is：The polymer spin dope for being blended with Graphene injects the injection appearance with stainless steel shower nozzle
In device, then applied the voltage on stainless steel shower nozzle with high voltage power supply, and will be sprayed using the propulsion pump being connected with spray containers
The polymer spin dope penetrated in container is sprayed to the Graphene of rotation/metal wire composite structure by stainless steel shower nozzle and receives dress
Put, the injection conditions of the electrostatic spinning is：Environment temperature is 50~80 DEG C, the output voltage of high voltage power supply for 15~
The rotary speed that distance is 10~15cm between 25kv, wire and stainless steel shower nozzle, flow velocity is 10~15mL/h, reception device
It is 60~120r/min.
10. the preparation method of the multi-layer graphene self-supporting pipe without clad skeleton as claimed in claim 8, its feature exists
In the polymer spin dope electrostatic spinning of Graphene that is blended with is to the Graphene/metal wire composite structure of rotation
While, by graphene dispersing solution ultrasonic atomizatio on the Graphene/metal wire composite structure of rotation；The graphene dispersing solution
Raw material including following weight portion：10~15 parts of Graphene, 1~3 part of 1- ethyl-3-methylimidazoles lactic acid, cyclohexanone 30~50
Part, 30~50 parts of N- cyclohexyl pyrrolidones, 30~50 parts of propandiol butyl ether acetate；The graphene dispersing solution ultrasonic atomizatio
Power be 80W, frequency is 2.5MHz, and condensation rate is 2~10mL/min, the ejiction opening of ultrasonic atomizatio and the distance of reception device
It is 5~15cm.
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| CN108821264A (en) * | 2018-07-10 | 2018-11-16 | 杭州高烯科技有限公司 | A kind of nanoscale sonic generator |
| CN110330013A (en) * | 2019-08-21 | 2019-10-15 | 电子科技大学 | A kind of deflocculated graphite alkene transfer method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20120128573A1 (en) * | 2010-11-19 | 2012-05-24 | Research & Business Foundation Sungkyunkwan University | Method for fabricating three dimensional graphene structures using catalyst templates |
| CN102502604A (en) * | 2011-11-03 | 2012-06-20 | 东南大学 | Preparation method of multifunctional graphene tube |
| CN102586869A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Three-dimensional grapheme tube and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120128573A1 (en) * | 2010-11-19 | 2012-05-24 | Research & Business Foundation Sungkyunkwan University | Method for fabricating three dimensional graphene structures using catalyst templates |
| CN102502604A (en) * | 2011-11-03 | 2012-06-20 | 东南大学 | Preparation method of multifunctional graphene tube |
| CN102586869A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Three-dimensional grapheme tube and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108821264A (en) * | 2018-07-10 | 2018-11-16 | 杭州高烯科技有限公司 | A kind of nanoscale sonic generator |
| CN110330013A (en) * | 2019-08-21 | 2019-10-15 | 电子科技大学 | A kind of deflocculated graphite alkene transfer method |
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