CN106698403A - Method of preparing graphene roll in large area - Google Patents
Method of preparing graphene roll in large area Download PDFInfo
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- CN106698403A CN106698403A CN201710010773.1A CN201710010773A CN106698403A CN 106698403 A CN106698403 A CN 106698403A CN 201710010773 A CN201710010773 A CN 201710010773A CN 106698403 A CN106698403 A CN 106698403A
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- graphene
- graphene oxide
- large area
- roll
- solution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a method of preparing a graphene roll in a large area. The method comprises the following steps: by taking graphene oxide as a raw material, preparing a graphene oxide film in a monomolecular layer by using an LB membrane instrument; then soaking the film in a thiol solution for a certain time to prepare a graphene oxide film roll; and then reducing the roll with hydrazine hydrate to obtain the graphene roll. Compared with the prior art, the method provided by the invention is simple in process step, mild in reaction condition, easy to obtain raw materials and relatively low in cost.
Description
Technical field
The invention belongs to nano-functional material preparing technical field, and in particular to a kind of large area prepares the side of graphene roll
Method.
Background technology
Graphene roll is a kind of graphene film has the new of CNT and Graphene performance concurrently by what helix-coil was formed
Section bar material, simultaneously because the open architecture between its two ends and volume layer, it is easy to the curling parcel of nano particle, what is formed is compound
Material has huge application potential in lithium ion battery negative material.
How largely the research of graphene nano volume is still at an early stage at present, prepare Graphene in high conversion rate and receive
Rice volume is still a research puzzle of academia, after only largely can successfully preparing, could really realize that it is applied.Mesh
Before, prior art discloses the methods of various preparation graphene rolls, such as patent report of Application No. 201510006310.9
A kind of method for preparing graphene roll.Its step of, is as follows：1) graphene oxide raw material is dissolved in water, obtains mass fraction for 0-
1% graphene oxide solution；2) above-mentioned graphene oxide solution is restored to black with chemical reduction method and is uniformly dispersed；3)
Graphene solution liquid nitrogen or liquefied ammonia snap frozen after reduction are transferred in freeze drier and freeze to after solidifying；4) useization
Learn reducing process or high-temperature heat treatment method to reduce above-mentioned lyophilized sample depth, obtain graphene nano volume.
But nobody reported the method rolled up come synthesizing graphite alkene using mercaptan so far.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of method that large area prepares graphene roll,
It is relatively low that the preparation method of the graphene roll that the present invention is provided reacts gentle, simple to operate, cost.
The principle that technical scheme is based on is：By mercaptan and golden self-assembling reaction, mercaptan can be in gold surface
Spontaneous assembling forms one layer of closely orderly film, and it can drive graphene oxide edge to be tilted from substrate, once the side for tilting
Edge touches the other parts of Graphene, and the Π-Π of lap interact and will reduce the dilute total free energy of graphite oxide,
Its curly course will continue to go on, and form the dilute nanometer roll of graphite oxide.
With graphene oxide as raw material, the graphene oxide membrane of monolayer is obtained using LB films instrument, then be dipped in
Certain hour in thiol solution, i.e., obtained graphene oxide volume；Then reduced with hydrazine hydrate and obtained the graphene roll；
It is comprised the following steps that：
(1) graphene oxide solution of certain mass concentration is prepared by Hummers methods；
(2) graphene oxide solution obtained in step (1) and organic solvent are formed into certain proportioning；
(3) mixed solution obtained in step (2) is measured into certain volume and dropwise drips to water surface, stood and treated for a period of time
Langmuir-Blodgett experiments are carried out after the volatilization completely of machine solvent；
(4) water surface that the silicon chip of certain thickness gold is dipped vertically into step (3) will be coated with；
(5) silicon chip in step (4) is lifted with certain speed, treats that it dries naturally；
(6) silicon chip in step (5) is immersed in thiol solution and graphene oxide volume is formed by certain hour；
(7) the graphene oxide volume hydrazine hydrate reduction in step (6) can be formed into graphene roll.
Preferably, the mass concentration of the graphene oxide solution of the certain mass concentration described in step (1) is 0.01%-
5%.
Preferably, the organic solvent in step (2) is methyl alcohol, the one kind in toluene or chloroform.
Preferably, graphene oxide solution and organic solvent proportioning are 1 in step (2):1–1:20.
Preferably, graphene oxide solution and the volume of the mixed liquor of organic solvent are 0.01mL-5mL in step (3).
Preferably, mixed solution drips to water surface in step (3), stands a period of time for 1h -24h.
Preferably, the golden film of 5nm -60nm is coated with step (4) on silicon chip.
Preferably, lifted in the water surface with the speed of 1mm/min-10mm/min in step (5).
Preferably, the thiol solution is n-octyl mercaptan, n- dodecyl mereaptan, positive stearylmercaptan etc..
Preferably, the time that the silicon chip described in step (6) is immersed in thiol solution formation graphene oxide volume is 1h -48h.
Beneficial effect：Using technical scheme compared with prior art, the present invention will be coated with the silicon chip of gold
Single-layer graphene oxide reacted with certain density thiol solution, obtain graphene oxide volume, its provide Graphene
The preparation method reaction condition of volume is gentle, cost is relatively low, simple to operate.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of graphene roll prepared in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope diagram of graphene roll prepared in the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope diagram of graphene roll prepared in the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope diagram of graphene roll prepared in the embodiment of the present invention 3.
Specific embodiment
The present invention is specifically described by specific embodiment below in conjunction with the accompanying drawings, the present embodiment is served only for the present invention
It is described further, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is of the invention
Content makes some nonessential changes and adjustment, belongs to protection scope of the present invention.
The step of preparation method of graphene nano volume, is as follows：(1) graphene oxide prepared by Hummers methods is dissolved in water
And stir, obtain graphene oxide solution of the weight/mass percentage composition 0.1% to 5%；Wherein, graphene oxide chip size is
0.01μm2Any of the above size.
(2) graphene oxide solution and organic solvent methyl alcohol, toluene or three chloromethanes that volume is 0.01mL-5mL are measured
One kind in alkane is with 1:1–1:The mixed solution that ratio in 50 is mixed for carrying out Langmuir-Blodgett experiments,
It is dropwise instilled liquid level, 1h-48h is stood.
(3) thickness will be coated with for the silicon chip of 5nm-60nm gold is dipped vertically into below the water surface, with 1mm/min-10mm/min
Speed is lifted once, treats that it dries naturally；
(4) silicon chip is immersed in n-octyl mercaptan, 1h -48h are in the thiol solution such as n- dodecyl mereaptan or positive stearylmercaptan
Graphene oxide volume can be formed；
(5) above-mentioned graphene oxide is rolled up with existing chemical reduction method and is reduced, obtain reduced graphene volume；Wherein, also
Former agent can be the solution with reproducibility such as hydrazine hydrate solution, hydroiodic acid solution, sodium ascorbate solution.Recovery time, also
Depending on the reducing degree of the visual graphene oxide of concentration of former temperature and reducing agent.
Embodiment 1：
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and with methanol solution with 1:5 ratio mixing, forms stabilization
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops dropwise to instill the water surface and stand 6 hours；
3) thickness will be coated with for the silicon chip of 5nm-60nm gold is dipped vertically into below the water surface, is lifted with 1mm/min speed, treated
It dries naturally；
4) silicon chip is immersed in the thiol solutions such as 3% positive stearylmercaptan and graphene oxide volume is formed by 24h；
5) reduced with hydrazine hydrate solution and obtained graphene nano volume.
Obtained graphene nano volume rolls up the coil structure with different directions as shown in figure 1, Graphene is received, and length is several
Ten microns to hundreds of microns.
Embodiment 2：
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and with methanol solution with 1:5 ratio mixing, forms stabilization
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops dropwise to instill the water surface and stand 6 hours；
3) thickness will be coated with for the silicon chip of 5nm-60nm gold is dipped vertically into below the water surface, is lifted with 1mm/min speed, treated
It dries naturally；
4) silicon chip is immersed in the thiol solutions such as 3% n- dodecyl mereaptan and graphene oxide volume is formed by 12h；
5) reduced with hydrazine hydrate solution and obtained graphene nano volume.
Obtained graphene nano volume rolls up the coil structure with different directions as shown in Fig. 2 Graphene is received, and length is several
Ten microns to hundreds of microns.
Embodiment 3：
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and with methanol solution with 1:5 ratio mixing, forms stabilization
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops dropwise to instill the water surface and stand 6 hours；
3) thickness will be coated with for the silicon chip of 5nm-60nm gold is dipped vertically into the water surface, is lifted with 1mm/min speed, treat it
Naturally dry；
4) silicon chip is immersed in the thiol solutions such as 1% n-octyl mercaptan and graphene oxide volume is formed by 3h；
5) reduced with hydrazine hydrate solution and obtained graphene nano volume.
Obtained graphene nano volume rolls up the coil structure with different directions as shown in figure 3, Graphene is received, and length is several
Ten microns to hundreds of microns.
Embodiment 4：
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and with methanol solution with 1:5 ratio mixing, forms stabilization
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops dropwise to instill the water surface and stand 6 hours；
3) thickness will be coated with for the silicon chip of 5nm-60nm gold is dipped vertically into the water surface, is lifted with 1mm/min speed, treat it
Naturally dry；
4) silicon chip is immersed in the thiol solutions such as 0.3% n-octyl mercaptan and graphene oxide volume is formed by 1h；
5) reduced with hydrazine hydrate solution and obtained graphene nano volume.
Obtained graphene nano volume rolls up the coil structure with different directions as shown in figure 4, Graphene is received, and length is several
Ten microns to hundreds of microns.
Below schematically creation of the invention and embodiments thereof are described, protection scope of the present invention includes
But it is not limited to the description above.Shown in accompanying drawing is also one of implementation method of the invention, and actual structure is not
It is confined to this.So, if one of ordinary skill in the art is subject to, and this practicality is new to enlighten, do not departing from creation of the invention
In the case of objective, frame mode and the embodiment similar to technical scheme is designed without creative, all should
Belong to the protection domain of this patent.
Claims (10)
1. a kind of method that large area prepares graphene roll, it is characterised in that：With graphene oxide as raw material, using LB film instrument systems
The graphene oxide membrane of monolayer is obtained, then is dipped in certain hour in thiol solution, obtained graphene oxide volume；With
Reduced with hydrazine hydrate afterwards and obtained graphene roll；It is comprised the following steps that：
(1) graphene oxide solution of certain mass concentration is prepared by Hummers methods；
(2) graphene oxide solution obtained in step (1) and organic solvent are formed into certain proportioning；
(3) mixed solution obtained in step (2) is measured into certain volume and dropwise drips to water surface, stood and treat organic molten for a period of time
Langmuir-Blodgett experiments are carried out after agent volatilization completely；
(4) silicon chip that will be coated with certain thickness gold is dipped vertically into below the water surface in step (3)；
(5) silicon chip for being coated with gold in step (4) is lifted with certain speed, treats that it dries naturally；
(6) silicon chip in step (5) is immersed in certain hour in thiol solution, forms graphene oxide volume；
(7) by the graphene oxide volume hydrazine hydrate reduction in step (6), graphene roll is formed.
2. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(1) mass concentration of the graphene oxide solution of certain mass concentration is 0.01%-5% in.
3. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(2) organic solvent in is methyl alcohol, the one kind in toluene or chloroform.
4. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(2) graphene oxide solution and organic solvent proportioning are 1 in:1–1:20.
5. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(3) volume of mixed liquor is 0.01mL-5mL in.
6. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(3) mixed solution drips to water surface in, and time of repose is 1h -24h.
7. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(4) gold of 5nm -60nm thickness is coated with silicon chip.
8. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(5) silicon chip is lifted with the speed of 1mm/min-10mm/min in.
9. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(6) thiol solution is n-octyl mercaptan, n- dodecyl mereaptan, positive stearylmercaptan or other alkyl hydrosulfides in.
10. the method that a kind of large area according to claim 1 prepares graphene roll, it is characterised in that described step
(6) time that silicon chip is immersed in thiol solution formation graphene oxide volume in is 1h -48h.
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| CN201710010773.1A CN106698403B (en) | 2017-01-06 | 2017-01-06 | A kind of method of large area preparation graphene roll |
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| CN106698403B CN106698403B (en) | 2019-01-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976316A (en) * | 2012-12-19 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene roll |
| CN103387228A (en) * | 2013-07-19 | 2013-11-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene scrolls |
| CN104140096A (en) * | 2014-07-25 | 2014-11-12 | 同济大学 | Method for manufacturing graphene roll |
| CN104576083A (en) * | 2015-01-07 | 2015-04-29 | 浙江碳谷上希材料科技有限公司 | Preparation method for supercapacitor made of graphene nanoscrolls |
-
2017
- 2017-01-06 CN CN201710010773.1A patent/CN106698403B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976316A (en) * | 2012-12-19 | 2013-03-20 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene roll |
| CN103387228A (en) * | 2013-07-19 | 2013-11-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene scrolls |
| CN104140096A (en) * | 2014-07-25 | 2014-11-12 | 同济大学 | Method for manufacturing graphene roll |
| CN104576083A (en) * | 2015-01-07 | 2015-04-29 | 浙江碳谷上希材料科技有限公司 | Preparation method for supercapacitor made of graphene nanoscrolls |
Non-Patent Citations (6)
| Title |
|---|
| BINGNA ZHENG ET AL: "Massive Production of Graphene Nanoscrolls and Their Assist for High Rate Performance Supercapacitors", 《NANOSCALE》 * |
| HAI LI ET AL: "Graphene Oxide Scrolls on Hydrophobic Substrates Fabricated by Molecular Combing and Their Application in Gas Sensing", 《SMALL》 * |
| JUMIATI WU ET AL: "Graphene Oxide Architectures Preparaed by Molecular Combing on Hydrophilic-Hydrophobic Micropatterns", 《SMALL》 * |
| MANABU OHTOMO ET AL: "Etchant-free graphene transfer using facile intercalation of alkanthiol self-assembled molecules at graphene/metal interfaces", 《NANOSCALE》 * |
| QIANGBIN ZHENG ET AL: "Structure control of ultra-large grapheme oxide sheets by the Langmuir-blodgett mothod", 《RSC ADVANCES》 * |
| YAN GAO ET AL: "Highly-efficient fabrication of nanoscrolls from functionalized graphene oxide by Langmuir-Blodgett method", 《CARBON》 * |
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