CN106698403B - A kind of method of large area preparation graphene roll - Google Patents
A kind of method of large area preparation graphene roll Download PDFInfo
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- CN106698403B CN106698403B CN201710010773.1A CN201710010773A CN106698403B CN 106698403 B CN106698403 B CN 106698403B CN 201710010773 A CN201710010773 A CN 201710010773A CN 106698403 B CN106698403 B CN 106698403B
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Abstract
The present invention relates to a kind of methods of large area preparation graphene roll, this method is using graphene oxide as raw material, the graphene oxide membrane of monolayer is made using LB film instrument, certain time is dipped in thiol solution again, graphene oxide volume is obtained, is then restored with hydrazine hydrate and obtains the graphene roll.Compared with prior art, present invention process step is simple, and reaction condition is mild, and raw material is easy to get, and cost is relatively low.
Description
Technical field
The invention belongs to nano-functional material preparation technical fields, and in particular to a kind of side of large area preparation graphene roll
Method.
Background technique
Graphene roll, which is a kind of graphene film, has both the new of carbon nanotube and graphene performance by what helix-coil was formed
Profile material, simultaneously because the open architecture between its both ends and volume layer, is easy to the curling package of nano particle, is formed by 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 its application.Mesh
Before, prior art discloses the methods of a variety of preparation graphene rolls, such as the patent report application No. is 201510006310.9
A method of preparing graphene roll.Its steps is as follows: 1) graphene oxide raw material being dissolved in water, obtaining mass fraction is 0-
1% graphene oxide solution；2) above-mentioned graphene oxide solution is restored to black with chemical reduction method and be uniformly dispersed；3)
Graphene solution after reduction is rapidly frozen with liquid nitrogen or liquefied ammonia to solidification, is transferred in freeze drier and is lyophilized；4) useization
It learns reduction method or high-temperature heat treatment method restores above-mentioned freeze-drying sample depth, obtain graphene nano volume.
But nobody reported the method rolled up using mercaptan come synthesizing graphite alkene so far.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of method of large area preparation graphene roll,
The preparation method reaction of graphene roll provided by the invention is mild, easy to operate, cost is relatively low.
Technical solution of the present invention based on principle be: by mercaptan and gold self-assembling reaction, mercaptan can be in gold surface
Spontaneous assembling forms one layer of close orderly film, and graphene oxide edge can be driven to tilt from substrate, once the side tilted
Edge touches the other parts of graphene, and the Π-Π interaction of lap 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.
Using graphene oxide as raw material, the graphene oxide membrane of monolayer is made using LB film instrument, then is dipped in
Certain time in thiol solution, the graphene oxide volume obtained；It is then restored to obtain the graphene roll with hydrazine hydrate；
The specific steps of which are as follows:
(1) graphene oxide solution of certain mass concentration is prepared by Hummers method；
(2) graphene oxide solution made from step (1) and organic solvent are formed into certain proportion；
(3) the measurement certain volume of mixed solution made from step (2) is dripped into water surface dropwise, stands a period of time wait have
Langmuir-Blodgett experiment is carried out after solvent volatilization completely；
(4) water surface being dipped vertically into the silicon wafer for being coated with certain thickness gold in step (3)；
(5) silicon wafer in step (4) is lifted with certain speed, to its naturally dry；
(6) by the silicon wafer in step (5) be immersed in certain time in thiol solution can be formed graphene oxide volume；
(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 certain mass concentration described in step (1) is 0.01%-
5%.
Preferably, the organic solvent in step (2) is methanol, one of toluene or chloroform.
Preferably, graphene oxide solution and organic solvent proportion are 1:1-1:20 in step (2).
Preferably, the volume of the mixed liquor of graphene oxide solution and organic solvent is 0.01mL-5mL in step (3).
Preferably, mixed solution drips to water surface in step (3), stand a period of time be 1h-for 24 hours.
Preferably, the golden film of 5nm -60nm is coated in step (4) on silicon wafer.
Preferably, it is lifted with the speed of 1mm/min-10mm/min in the water surface in step (5).
Preferably, the thiol solution is n-octyl mercaptan, n- dodecyl mereaptan, positive stearylmercaptan etc..
Preferably, silicon wafer described in step (6) is immersed in thiol solution and forms the time that graphene oxide is rolled up as 1h -48h.
The utility model has the advantages that compared with prior art using technical solution of the present invention, the present invention will be on the silicon wafer for being coated with gold
Single-layer graphene oxide react with certain density thiol solution, obtain graphene oxide volume, provide graphene
The preparation method reaction condition of volume is mild, cost is relatively low, easy to operate.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram for the graphene roll being prepared in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope diagram for the graphene roll being prepared in the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope diagram for the graphene roll being prepared in the embodiment of the present invention 3.
Fig. 4 is the scanning electron microscope diagram for the graphene roll being prepared in the embodiment of the present invention 3.
Specific embodiment
The present invention is specifically described by specific embodiment with reference to the accompanying drawing, the present embodiment is served only for the present invention
It is described further, should not be understood as limiting the scope of the invention, those skilled in the art is according to the present invention
Content makes some nonessential changes and adjustment, all belongs to the scope of protection of the present invention.
The step of preparation method of graphene nano volume, is as follows: (1) graphene oxide prepared by Hummers method being dissolved in water
And stir, obtain graphene oxide solution of the mass percentage 0.1% to 5%；Wherein, graphene oxide sheet having a size of
0.01μm2Any of the above size.
(2) graphene oxide solution and organic solvent methanol, toluene or three chloromethanes that volume is 0.01mL-5mL are measured
The mixed solution that one of alkane is mixed with the ratio in 1:1-1:50 is used to carry out Langmuir-Blodgett experiment,
It is instilled to liquid level dropwise, stands 1h-48h.
(3) silicon wafer for being coated with a thickness of 5nm-60nm gold is dipped vertically into the water surface hereinafter, with 1mm/min-10mm/min
Speed lifting is primary, to its naturally dry；
(4) silicon wafer is immersed in n-octyl mercaptan, 1h -48h is in the thiol solutions 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 restored, obtain reduced graphene volume；Wherein, also
Former agent can have the solution of reproducibility for hydrazine hydrate solution, hydroiodic acid solution, sodium ascorbate solution etc..Recovery time goes back
Former temperature and the concentration of reducing agent can be depending on the reducing degrees of graphene oxide.
Embodiment 1:
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and mixed with methanol solution with the ratio of 1:5, formed and stablized
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops and instills the water surface and standing 6 hours dropwise；
3) silicon wafer for being coated with a thickness of 5nm-60nm gold is dipped vertically into the water surface hereinafter, with the lifting of 1mm/min speed, to
Its naturally dry；
4) graphene oxide volume can be formed for 24 hours by silicon wafer being immersed in the thiol solutions such as 3% positive stearylmercaptan；
5) it is restored to obtain graphene nano volume with hydrazine hydrate solution.
Graphene nano volume obtained rolls up the coil structure with different directions as shown in Figure 1, graphene is received, and length is several
Ten microns are differed to several hundred microns.
Embodiment 2:
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and mixed with methanol solution with the ratio of 1:5, formed and stablized
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops and instills the water surface and standing 6 hours dropwise；
3) silicon wafer for being coated with a thickness of 5nm-60nm gold is dipped vertically into the water surface hereinafter, with the lifting of 1mm/min speed, to
Its naturally dry；
4) graphene oxide volume can be formed by silicon wafer being immersed in 12h in the thiol solutions such as 3% n- dodecyl mereaptan；
5) it is restored to obtain graphene nano volume with hydrazine hydrate solution.
Graphene nano volume obtained rolls up the coil structure with different directions as shown in Fig. 2, graphene is received, and length is several
Ten microns are differed to several hundred microns.
Embodiment 3:
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and mixed with methanol solution with the ratio of 1:5, formed and stablized
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops and instills the water surface and standing 6 hours dropwise；
3) silicon wafer for being coated with a thickness of 5nm-60nm gold is dipped vertically into the water surface, with the lifting of 1mm/min speed, to it
Naturally dry；
4) graphene oxide volume can be formed by silicon wafer being immersed in 3h in the thiol solutions such as 1% n-octyl mercaptan；
5) it is restored to obtain graphene nano volume with hydrazine hydrate solution.
Graphene nano volume obtained rolls up the coil structure with different directions as shown in figure 3, graphene is received, and length is several
Ten microns are differed to several hundred microns.
Embodiment 4:
1) graphene oxide raw material is dissolved in water and dilutes 10 times, and mixed with methanol solution with the ratio of 1:5, formed and stablized
Mixed solution；
2) above-mentioned mixed solution is measured into 10 drops and instills the water surface and standing 6 hours dropwise；
3) silicon wafer for being coated with a thickness of 5nm-60nm gold is dipped vertically into the water surface, with the lifting of 1mm/min speed, to it
Naturally dry；
4) graphene oxide volume can be formed by silicon wafer being immersed in 1h in the thiol solutions such as 0.3% n-octyl mercaptan；
5) it is restored to obtain graphene nano volume with hydrazine hydrate solution.
Graphene nano volume obtained rolls up the coil structure with different directions as shown in figure 4, graphene is received, and length is several
Ten microns are differed to several hundred microns.
Schematically creation of the invention and embodiments thereof are described above, protection scope of the present invention includes
But it is not limited to the description above.Shown in the drawings is also one of the embodiment of the invention, and actual structure is not
It is confined to this.So if those skilled in the art are not being departed from creation of the invention by this practical new enlightenment
In the case where objective, frame mode similar with technical solution of the present invention and embodiment are not inventively designed, it should all
Belong to the protection scope of this patent.
Claims (10)
1. a kind of method of large area preparation graphene roll, it is characterised in that: using graphene oxide as raw material, using LB film instrument system
The graphene oxide membrane of monolayer is obtained, then is dipped in certain time in thiol solution, graphene oxide volume obtained；With
It is restored to obtain graphene roll with hydrazine hydrate afterwards；The specific steps of which are as follows:
(1) graphene oxide solution of certain mass concentration is prepared by Hummers method；
(2) graphene oxide solution made from step (1) and organic solvent are formed into certain proportion；
(3) the measurement certain volume of mixed solution made from step (2) is dripped into water surface dropwise, stands a period of time to organic molten
Langmuir-Blodgett experiment is carried out after agent volatilization completely；
(4) silicon wafer for being coated with certain thickness gold is dipped vertically into the water surface in step (3) or less；
(5) silicon wafer for being coated with gold in step (4) is lifted with certain speed, to its naturally dry；
(6) silicon wafer in step (5) is immersed in certain time in thiol solution, forms graphene oxide volume；
(7) by the graphene oxide volume hydrazine hydrate reduction in step (6), graphene roll is formed.
2. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(1) mass concentration of the graphene oxide solution of certain mass concentration is 0.01%-5% in.
3. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(2) organic solvent in is methanol, one of toluene or chloroform.
4. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(2) graphene oxide solution and organic solvent proportion are 1:1-1:20 in.
5. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(3) volume of mixed liquor is 0.01mL-5mL in.
6. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(3) mixed solution drips to water surface in, time of repose be 1h-for 24 hours.
7. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(4) gold of 5nm -60nm thickness is coated on silicon wafer.
8. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(5) silicon wafer is lifted in the speed of 1mm/min-10mm/min.
9. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(6) thiol solution is n-octyl mercaptan, n- dodecyl mereaptan, positive stearylmercaptan or other alkyl hydrosulfides in.
10. a kind of method of large area preparation graphene roll according to claim 1, which is characterized in that the step
(6) silicon wafer is immersed in thiol solution and forms the time that graphene oxide is rolled up as 1h -48h in.
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| 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 |
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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 |
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| Etchant-free graphene transfer using facile intercalation of alkanthiol self-assembled molecules at graphene/metal interfaces;Manabu Ohtomo et al;《Nanoscale》;20160506;全文 |
| Graphene Oxide Architectures Preparaed by Molecular Combing on Hydrophilic-Hydrophobic Micropatterns;Jumiati Wu et al;《Small》;20140318;第10卷(第11期);试验部分、第2241页右栏第1段、图1、图3 |
| Graphene Oxide Scrolls on Hydrophobic Substrates Fabricated by Molecular Combing and Their Application in Gas Sensing;Hai Li et al;《Small》;20121015;第9卷(第3期);全文 |
| Highly-efficient fabrication of nanoscrolls from functionalized graphene oxide by Langmuir-Blodgett method;Yan Gao et al;《Carbon》;20100811;第48卷;全文 |
| Massive Production of Graphene Nanoscrolls and Their Assist for High Rate Performance Supercapacitors;Bingna Zheng et al;《Nanoscale》;20151126;全文 |
| Structure control of ultra-large grapheme oxide sheets by the Langmuir-blodgett mothod;Qiangbin Zheng et al;《RSC Advances》;20130116;第3卷;试验部分 |
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