CN106477560A - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN106477560A CN106477560A CN201510570030.0A CN201510570030A CN106477560A CN 106477560 A CN106477560 A CN 106477560A CN 201510570030 A CN201510570030 A CN 201510570030A CN 106477560 A CN106477560 A CN 106477560A
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Abstract
The invention discloses a kind of preparation method of Graphene, comprise the following steps：By graphite dispersion in the solution containing LiOH, carry out pre- supersound process；Above-mentioned system is transferred in autoclave and carries out hydro-thermal reaction formation compound between graphite layers；Graphene is peeled off from compound between graphite layers.The present invention is greatly facilitated the formation of intercalation compound using the condition of high voltage of hydro-thermal method, improves the charge stripping efficiency of Graphene.The method prepares that Graphene process is simple, yield be considerable, low cost, pollution are few, possesses good application prospect.Prepared Graphene quality is high, can be widely applied to the industries such as integrated circuit, Heat Conduction Material, photo-sensitive cell, energy storage material, catalyst and field.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene, more particularly, to a kind of hydro-thermal method auxiliary system
Standby compound between graphite layers simultaneously peel off the method obtaining Graphene.
Background technology
Peace moral strong K sea nurse since Univ Manchester UK in 2004 et al. success is from graphite
On isolate self-existent single or multiple lift Graphene using the method for micromechanics stripping, this
Material is just because its unique property has caused people widely to pay close attention to, and has been expected extremely
Wide application prospect.Mono-layer graphite is Graphene, due to its special Colloidal particles
There is excellent power, heat, light, electric property, its Young's modulus, up to 11,000GPa, is broken
Resistance to spalling reaches 125GPa；Thermal conductivity is up to 5,000W/ (m K)；Opacity is 2.3%, and
Unrelated with optical wavelength；Carrier transport rate is up to 200,000cm2/V·s；Theoretical specific surface area
Up to 2,630m2/g.This makes Graphene brilliant in single-molecule detection device, integrated circuit, field effect
The aspects such as body pipe, Heat Conduction Material, photo-sensitive cell, energy storage material, catalyst carrier have or not desirable
The using value in generation.
Graphene preparation method relatively conventional at present can be divided into physics, chemical two kinds of approach.Thing
Logos includes micromechanics stripping method, solvent stripping method, and arc discharge method etc., wherein micromechanics are shelled
The extremely limited graphene film of quantity can only be produced from method, substantially only use for scientific research；Molten
Agent stripping method low yield, size is uncontrollable；Arc discharge method is relatively costly.And commonly use at present
Chemistry route includes oxidation-reduction method, chemical vapour deposition technique, solvent-thermal method, electrolysis etc..
Oxidation-reduction method inevitably relate to the use of strong oxidizer, during toxic waste more,
And a large amount of defects can be introduced, the presence specific surface area due to reuniting effect is greatly reduced；Chemistry
Vapour deposition process high cost, complex process, the acquisition of single-layer graphene needs the tight of various parameters
Lattice control, and yield is relatively fewer；The Graphene quality that solvent-thermal method produces is unstable；And it is electric
Solution rule can introduce the impurity being difficult to remove.Therefore need badly a kind of technique relatively easy, inexpensive,
The method that green, high yield produce high-quality graphene.
For the material with layer structure, such as graphite, molybdenum bisuphide, tungsten disulfide, dioxy
Change manganese etc., the graft process between Physical and chemical method be a kind of preferably peel off monolayer or
The method of multi-layer nano piece.In liquid phase environment, intercalator, such as multiple inorganic matters, Organic substance
Or its complex, may be inserted into material under certain conditions between layers, increase layer
The distance between with layer, thus reducing the interaction of interlayer, thus make it easier to ultrasonic
Deng under the conditions of separate monolayer material.Valeria Nicolosi et al. is in Liquid Exfoliation
The systematic discussion to liquid phase stripped laminar material in of Layered Materials mono- literary composition.
Graphite is typical stratotype material, is firm hexagonal netted planar carbon layer in aspect, layer
Between then combined with faint Van der Waals force, spacing is larger, can be inserted into multiple intercalating agent, such as alkali gold
Belong to, halogen, metal halide, strong oxidizing property oxyacid etc..Compound between graphite layers are sent out earliest
Now in 1841, native graphite is immersed in dense HNO by German Schaufautl3With dense
H2SO4Mixed liquor in, find there occurs expansion along cleavage direction graphite volume.Graphite layers
Compound not only remains the original property of graphite, and imparts original graphite and intercalated material
The new property all not possessed, enjoys material scholar, physicss as a kind of new function material
Family and the favor of chemist.
Content of the invention
For above problems of the prior art, the present invention proposes one kind and utilizes hydro-thermal method
Auxiliary is prepared compound between graphite layers and is peeled off the method obtaining Graphene, methods described Graphene
Yield relatively significant, size is controlled, and maintains its original performance.
Technical solution of the present invention is as follows：
A kind of preparation method of Graphene is it is characterised in that described preparation method includes following step
Suddenly：
1) by graphite dispersion in the solution containing intercalator, carry out pre- supersound process.Described stone
Ink is one of electrographite, natural scale stone, expansible graphite, high temperature pyrolysis graphite etc.,
Intercalator used is LiOH, and described solution solvent takes water.Solution is LiOH in room temperature
Under unsaturated solution；
2) above-mentioned system is transferred in autoclave and carries out hydro-thermal reaction, will by hydro-thermal reaction
LiOH is adequately inserted between graphite flake layer, forms the compound between graphite layers of LiOH intercalation；
3), after system cooling, peel off Graphene from compound between graphite layers.
Wherein, in step 1) in, the mass ratio of graphite and solution 1: 20～100, preferably
1: 40～50；LiOH molar concentration is in 0.1～5mol/L, preferably 0.5～1mol/L.
In step 1) in, can choose whether to add surfactant, such as poly- second in aqueous solution
Alkene pyrrolidone, polyvinyl alcohol, dodecylbenzene sodium sulfonate, cetyl trimethylammonium bromide,
One or a combination set of sodium lauryl sulphate etc., the quality of surfactant and the volume ratio of water exist
0.1～10g: 100mL, preferably 0.2～2g: 100mL.
In step 1) in, in 500～2000W, the time is in 30min～2h for pre- ultrasonic power.
In step 2) in, the volume ratio of container used by sealing and water between 0.6: 1～0.9: 1,
, at 150～220 DEG C, the response time is in 6～48h for reaction temperature.
In step 3) in, described cooling means is natural cooling or program cooling；From graphite linings
Between to peel off the method for Graphene in compound be ultrasonic vibration, ultrasonic power exists
1000～2000W, the time is in 1～24h.The Graphene separating takes centrifugation or vacuum filtration
Mode carry out separating, pass through drying after deionized water wash, such as baking the affected part after applying some drugs do, lyophilization,
Deng acquisition powder product.
Advantages of the present invention：
Present invention process is relatively easy, during do not have using the material having larger pollution to environment,
Cost is relatively low, and yield is considerable.During in Graphene, do not introduce new impurity, gained graphite
The better performances of alkene, are a kind of preparation methoies with commercial exploitation.Prepared graphite
Alkene can be widely applied to integrated circuit, Heat Conduction Material, photo-sensitive cell, energy storage material, catalyst
Etc. industry and field.
Brief description
Fig. 1 is that the optical microscope of the Graphene being obtained using the graphene preparation method of the present invention is shone
Piece.
Fig. 2 is the scanning electron microscopy of the Graphene being obtained using the graphene preparation method of the present invention
Mirror photo.
Fig. 3 is the atomic force microscope of the Graphene being obtained using the graphene preparation method of the present invention
Photo.
Specific embodiment
Below in conjunction with the accompanying drawings, by embodiment, the present invention will be further described.
Embodiment one
The preparation method of the Graphene of the present embodiment, comprises the following steps：
1) at room temperature 1g LiOH is added in 40ml deionized water, and be sufficiently stirred for, shape
Become the required solution containing intercalator；
2) 1g expanded graphite is added in above-mentioned solution, after stirring, 1000W surpasses
After sound 1h, it is transferred in the 50ml Teflon inner bag of autoclave；
3), after sealing autoclave, reacting by heating 24h at 220 DEG C, thus form graphite linings
Between compound；
4) after product is cooled to room temperature, ultrasonic 12h under the power of 1000W；
5) with the centrifugation 30min of 1000 turns/min after said process, supernatant is taken to be stone
Black alkene dispersion liquid, repeat the above steps twice, remove the graphite layers not being completely exfoliated
Compound；
6) by the graphene dispersing solution being obtained lyophilization, deionized water rinsing several times after
It is vacuum dried at 60 DEG C, obtains a size of 5～15um, thickness is less than the powder of 10nm
The highly purified Graphene of last shape, as shown in Figure 1, Fig. 1 is scanning electron microscope SEM
Figure.
Embodiment two
The preparation method of the Graphene of the present embodiment, comprises the following steps：
1) at room temperature 1g LiOH is added in 40ml deionized water, add 0.5g ten afterwards
Dialkyl benzene sulfonic acids sodium is simultaneously sufficiently stirred for, solution needed for formation；
2) 1g graphite powder is added in above-mentioned solution, after stirring, 1000W is ultrasonic
It is transferred to after 30min in the 50ml Teflon inner bag of autoclave；
3), after sealing autoclave, reacting by heating 24h at 200 DEG C, thus form graphite linings
Between compound；
4) after product is cooled to room temperature, ultrasonic 6h under the power of 1000W；
5) with the centrifugation 30min of 2000 turns/min after said process, supernatant is taken to be stone
Black alkene dispersion liquid, repeat the above steps twice, remove the graphite layers not being completely exfoliated
Compound；
6) by the graphene dispersing solution being obtained lyophilization, deionized water rinsing several times after
It is vacuum dried at 60 DEG C, obtains a size of 5～15um, thickness is less than the powder of 10nm
The highly purified Graphene of last shape, as shown in Figure 2.
Embodiment three
The preparation method of the Graphene of the present embodiment, comprises the following steps：
1) at room temperature 2g LiOH is added in 40ml deionized water, after stirring,
Solution needed for formation；
2) 0.5g graphite powder is added in above-mentioned solution, after stirring, 1000W surpasses
It is transferred to after sound 30min in the 50ml Teflon inner bag of autoclave；
3) after sealing autoclave, steady temperature heats sealing container, heats at 180 DEG C
24 hours, thus forming compound between graphite layers；
4) after product is cooled to room temperature, ultrasonic 8h under the power of 1500W；
5) with the centrifugation 30min of 3000 turns/min after said process, take supernatant, weight
Multiple above-mentioned steps once, remove the compound between graphite layers impurity not being completely exfoliated；
6) graphene dispersing solution is carried out vacuum filtration, filter cake deionization using sand core funnel
After water rinses, vacuum drying at 60 DEG C obtains graphene powder, the Graphene being obtained
A size of 5～15um, thickness is less than 5nm, as shown in Figure 3.
It is finally noted that, the purpose publicizing and implementing mode is that help further understands this
Invention, but it will be appreciated by those skilled in the art that：Without departing from the present invention and appended power
In the spirit and scope that profit requires, various substitutions and modifications are all possible.Therefore, the present invention
Should not be limited to embodiment disclosure of that, the scope of protection of present invention is with claim
The scope that book defines is defined.
Claims (8)
1. a kind of preparation method of Graphene it is characterised in that described preparation method include with
Lower step：
1) by graphite dispersion in the solution containing intercalator, carry out pre- supersound process；
2) above-mentioned system is transferred in autoclave and carries out hydro-thermal reaction, form graphite linings
Between compound；
3) treat that system cools down, peel off Graphene from compound between graphite layers.
2. preparation method as claimed in claim 1 is it is characterised in that in step 1) in,
Described graphite be electrographite, natural scale stone, expansible graphite, high temperature pyrolysis graphite etc. it
One.The mass ratio of graphite and solution is 1: 20～100, preferably 1: 40～50.
3. preparation method as claimed in claim 1 is it is characterised in that in step 1) in,
Intercalator used is LiOH.Described solution solvent takes water.Solution is for LiOH at normal temperatures
Unsaturated solution, molar concentration is in 0.1～5mol/L, preferably 0.5～1mol/L.
4. preparation method as claimed in claim 1 is it is characterised in that in step 1) in,
Can choose whether in solution to add surfactant, such as Polyvinylpyrrolidone, polyvinyl alcohol,
Dodecylbenzene sodium sulfonate, one of cetyl trimethylammonium bromide, sodium lauryl sulphate etc.
Or a combination thereof, the quality of surfactant and the volume ratio of water are 0.1～10g: 100mL, excellent
Elect 0.2～2g as: 100mL.
5. preparation method as claimed in claim 1 is it is characterised in that in step 1) in,
, in 500～2000W, the time is in 30min～2h for pre- ultrasonic power.
6. the method for claim 1 is it is characterised in that in step 2) in, institute
With the volume ratio of hydro-thermal reaction sealing container and water between 0.6: 1～0.9: 1, temperature exists
150～220 DEG C, the response time is in 6～48h.
7. the method for claim 1 is it is characterised in that in step 3) in, institute
Stating cooling means is natural cooling or program cooling；Graphene is peeled off from compound between graphite layers
Method be ultrasonic vibration, in 1000～2000W, the time is in 1～24h for ultrasonic power.
8. the method for claim 1 is it is characterised in that in step 3) in, stripping
The Graphene separating out takes centrifugation or the mode of vacuum filtration to carry out separating, after deionized water wash
By drying, such as dry, lyophilization of baking the affected part after applying some drugs etc. obtains powder product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516541A (en) * | 2018-04-02 | 2018-09-11 | 西安工程大学 | A kind of novel C VD graphenes dry method transfer method |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN110451565A (en) * | 2019-09-10 | 2019-11-15 | 深圳中科智车联合发展有限公司 | A method of preparing two-dimensional layer nano material |
| CN111217367A (en) * | 2020-01-14 | 2020-06-02 | 中国石油大学(华东) | Multi-element composite intercalated low-temperature expandable graphite system for profile control and water shutoff of deep reservoir and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583351A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of fewer-layer graphene |
| CN103183331A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Preparation method for graphene |
| CN103771402A (en) * | 2013-12-30 | 2014-05-07 | 华南农业大学 | Graphene preparation method |
| CN103910354A (en) * | 2014-03-25 | 2014-07-09 | 复旦大学 | Method for preparing graphene through large-scale aqueous phase |
-
2015
- 2015-09-01 CN CN201510570030.0A patent/CN106477560A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183331A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Preparation method for graphene |
| CN102583351A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of fewer-layer graphene |
| CN103771402A (en) * | 2013-12-30 | 2014-05-07 | 华南农业大学 | Graphene preparation method |
| CN103910354A (en) * | 2014-03-25 | 2014-07-09 | 复旦大学 | Method for preparing graphene through large-scale aqueous phase |
Non-Patent Citations (1)
| Title |
|---|
| 刘玉荣 著: "《碳材料在超级电容器中的应用》", 31 January 2013, 国防工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516541A (en) * | 2018-04-02 | 2018-09-11 | 西安工程大学 | A kind of novel C VD graphenes dry method transfer method |
| CN108516541B (en) * | 2018-04-02 | 2021-06-04 | 西安工程大学 | CVD graphene dry transfer method |
| CN109368623A (en) * | 2018-09-20 | 2019-02-22 | 苏州博努奇纺织有限公司 | A kind of nano metal intercalated graphite alkene preparation method |
| CN110451565A (en) * | 2019-09-10 | 2019-11-15 | 深圳中科智车联合发展有限公司 | A method of preparing two-dimensional layer nano material |
| CN111217367A (en) * | 2020-01-14 | 2020-06-02 | 中国石油大学(华东) | Multi-element composite intercalated low-temperature expandable graphite system for profile control and water shutoff of deep reservoir and preparation method and application thereof |
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Application publication date: 20170308 |