CN103771402A - Graphene preparation method - Google Patents
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- CN103771402A CN103771402A CN201310747304.XA CN201310747304A CN103771402A CN 103771402 A CN103771402 A CN 103771402A CN 201310747304 A CN201310747304 A CN 201310747304A CN 103771402 A CN103771402 A CN 103771402A
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Abstract
The invention belongs to the technical field of carbon material preparation, and discloses a graphene preparation method based on a liquid phase stripping method and a hydrothermal method. The graphene preparation method comprises the following steps: adding powdered graphite and water into a reaction kettle; sealing, then stirring, heating to a reaction temperature, keeping constant temperature, continuously stirring and reacting; after ending reaction, cooling, taking out a mixed solution in the reaction kettle so as to carry out centrifugal separation, wherein solids at a lower layer are unreacted powered graphite, and supernatant liquid is graphene dispersion liquid; and carrying out centrifugal separation on the graphene dispersion liquid so as to obtain solids, namely graphene. According to the graphene preparation method, water is used as a solvent so as to overcome the shortcomings that an organic solvent is high in boiling point and difficult to remove and has toxicity, or as Hansen solubility parameters of the organic solvent cannot meet the solubility parameters of graphene, the concentration of the dispersion liquid is relatively low. The yield of the prepared graphene is high; the prepared graphene has very few defects and is very low in oxygen content; and the intrinsic electrical property of the graphene is maintained.
Description
Technical field
The invention belongs to carbon material preparing technical field, be specifically related to a kind of method of preparing Graphene.
Background technology
Graphene has excellent physics, chemistry and mechanical property, prepares high-quality Graphene most important to the application of Graphene.The method of preparing at present Graphene is a lot, mainly comprises mechanically peel method, chemical Vapor deposition process, oxidation reduction process, silicon carbide epitaxial growth method.Mechanically peel legal system is best in quality for Graphene, but randomness is very large, to comparatively difficulty of number of plies control; Graphene quality prepared by chemical Vapor deposition process is higher, but the electronic property of the Graphene making is subject to substrate effect very large, and performance is not so good as the Graphene that mechanically peel method makes; Oxidation reduction process can obtain a large amount of single-layer graphenes, but oxidized graphite is difficult to reduce completely, causes the deficiency of some character of Graphene; The Graphene that silicon carbide epitaxial growth method makes is difficult to separate from silicon carbide substrates, can not become the method for a large amount of manufacture Graphenes.
Since the method that adopts liquid phase to peel off graphite from Coleman seminar in 2008 is prepared Graphene, liquid phase stripping method has obtained larger development, not only for the preparation of Graphene but also for the preparation of other two-dimensional nano material (as molybdenumdisulphide, boron nitride etc.).Compared with oxidation reduction process, liquid phase stripping method is directly peeled off graphite and has been obtained the non-oxide monoatomic layer Graphene of high quality, has avoided oxidation reduction process thoroughly not reduce and has caused a large amount of textural defect of Graphene.This method can be used to produce matrix material and the film based on Graphene, and other many application, for example thin film transistor, transparency conductive electrode etc.But there is high, the toxic and difficult removal of organic solvent boiling point or do not mate and cannot realize the shortcoming of peeling off with the hansen solubility parameter of Graphene in existing liquid phase stripping method.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, the object of the present invention is to provide a kind of method of preparing high-quality Graphene based on liquid phase stripping method and hydrothermal method.
Object of the present invention is achieved through the following technical solutions:
A method of preparing Graphene, comprises the steps:
(1) powdered graphite and water are added in reactor;
(2) after closed reactor, stir and heat, being heated to constant temperature after temperature of reaction and continuing stirring reaction;
(3) reaction finishes rear coolingly, after cooling mixing solutions in reactor is taken out and carries out centrifugation, and centrifugal rear lower floor solid is the complete powdered graphite of unreacted, and supernatant liquid is graphene dispersing solution;
(4) get the described graphene dispersing solution of step (3) and carry out high speed centrifugation separation, separating obtained solids is Graphene.
Preferably, the described powdered graphite of step (1) is any one powdered graphite made in natural flake graphite, highly oriented pyrolytic graphite or expanded graphite, and described powdered graphite is of a size of 10～500 microns.
Preferably, the stir speed (S.S.) of the described stirring reaction of step (2) is 500～1500rpm, and temperature of reaction is 180～300 ℃, and the reaction times is 180～360 minutes.
Preferably, the rotating speed of the described centrifugation of step (3) is 500～10000rpm, and centrifugation time is 30～90 minutes.
Preferably, the rotating speed that the described high speed centrifugation of step (4) separates is 500～10000rpm, and centrifugation time is 5～90 minutes.
Preferably, step (1) is described adds tensio-active agent and/or intercalator when powdered graphite and water are added in reactor.
Preferably, the mass ratio of described powdered graphite and described tensio-active agent is 1:(0～2); The mass ratio of described powdered graphite and described intercalator is 1:(0～2).
Preferably, described tensio-active agent is more than one in sodium laurylsulfonate, hexadecyl benzene sulfonic acid sodium salt, Triton X-100, polystyrene, sodium polystyrene sulfonate, polyaniline, polyamine base benzene sulfonic acid sodium salt, polypyrrole, Polythiophene, poly-ethylenedioxy thiophene, butyrolactone, n-propyl alcohol or Virahol; Described intercalator is more than one in basic metal, alkaline-earth metal, transition metal, halogen simple substance, interhalogen compounds or transition metal chloride.
Preferably, described intercalator is K, Rb, Cs, Ba, Ca, Mn, Fe, Co, Ni, Br
2, ICl, IBr, MnCl
2, CoCl
2, FeCl
2, FeCl
3, CuCl
2or NiCl
2in more than one.
Preferably, described step (4) also comprises before the complete powdered graphite of the described unreacted of step (3) is repeated to the step of step (1) to step (3).
Principle of the present invention:
Liquid phase is peeled off preparing graphite alkene, Graphene peeling off and disperseing concentration the highest in this kind of solvent mainly considered in the selection of solvent, according to dissolving principle, solvent molecule must overcome and disintegrate the mutual reactive force of solute molecule, infiltrate between solute molecule and around, the contact between the molecule of solvent own simultaneously, also wants solute molecule infiltration and disintegrate, therefore the reactive force between solvent molecule, between solute molecule and between solvent and solute must be roughly equal, and now solubleness is the highest.By enthalpy of mixing theory:
Wherein, Δ H
mixit is the enthalpy of mixing of dispersion system; V
mixit is the volume of dispersion system; E
s,Sthe surface that is the solvent of dispersion can; E
s,Gthe surface that is Graphene can; Φ is Graphene volume fraction; T
flakethe thickness of graphene film; Now peel off the required energy minimum of Graphene, enthalpy of mixing minimum, peels off Graphene easier.
For the solvent disperseing, its surface can be along with the environmental change such as temperature, pressure.Along with temperature raises, the thermal motion aggravation of fluid molecule, kinetic energy increases, and intermolecular attraction weakens, and fluid molecule is reduced to the required energy in surface by inside.The surface tension of same material raises and weakens with temperature, and the volume of most of materials can expand, and intermolecular distance is increased, and intermolecular attracting each other weakened.In sizable temperature range, surface tension and the temperature of material are linear, and while reaching critical temperature, liquid-gas interface disappears, and surface tension is zero.In addition, pressure is also larger on the impact of material surface tension force, and under high pressure, gas density is large, and the molecule discontinuity equalization degree in liquid meter surface layer is reduced, and surface tension of liquid diminishes; Under high pressure, the solubleness of gas in liquid strengthens, and changes liquid composition.Generally, pressure increase surface tension of liquid mostly increases and declines with pressure.According to interfacial chemistry and thermodynamic argument, can estimate the surface tension of material below critical temperature.The gibbs equation of surface tension of liquid and temperature relation as follows:
G
s=γ=H
s-TS
s
For water, H
s=117.3mJ m
-2,
=-0.152mJ m
-2k
-1.
Can parameter E according to the surface of Graphene
s,G≈ 70mJ m
-2, in order to make to peel off required energy minimum, require the condition by changing water that the surface of water can be approached with the surface of Graphene, reach the object of the enthalpy of mixing minimum of Graphene and solvent.Can predict roughly hydrothermal condition in enclosed system through Theoretical Calculation, when temperature is within the scope of 180～300 ℃, the surface tension of water is 35-45mJ m
-2, the surface of water can be 64-76mJ m
-2.
The present invention has following advantage and effect with respect to prior art:
(1) to prepare Graphene productive rate high for the inventive method, and the Graphene defect obtaining is few, and oxygen level is extremely low.
(2) can obtain more single-layer graphene by adjusting reaction conditions, especially peel off through secondary, can obtain the Graphene product that individual layer amount exceedes 50%, is no more than 10 layers.
(3) Graphene that prepared by employing the inventive method, with respect to the graphite before peeling off, does not almost carry out any destruction to the lamella of graphite, has kept the original electrical properties of graphite.
(4) the present invention adopts water as solvent, has overcome high, the toxic and difficult removal of organic solvent boiling point or hansen solubility parameter and has not met the lower deficiency of concentration that Graphene solubility parameter causes dispersion liquid.
(5) method of the present invention is simple to operate, convenient for production, and energy consumption is low, low for equipment requirements, is more suitable for industrial production.Especially liquid phase reaction course is simple, processes easily, and whole experimentation is short.
Accompanying drawing explanation
Fig. 1: the scanning electron microscope diagram of powdered graphite before preparation;
Fig. 2: the scanning electron microscope diagram of preparing gained Graphene;
Fig. 3: prepare gained Graphene transmission electron microscope figure;
Fig. 4: atomic power (AFM) figure for preparing gained Graphene.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 100 microns, is placed in closed reactor, stirs, and be heated to 240 ℃ with 600rpm, keeps within 5 hours, carrying out hydro-thermal and peels off.After cooling, the centrifugal 60min of rotating speed by solution with 1000rpm, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 15min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 4.1% through the output that weighs Graphene.
Powdered graphite before the present embodiment preparation is detected, and scanning electron microscope diagram as shown in Figure 1;
The Graphene of being prepared by the present embodiment to gained carries out every detection, and as shown in Figure 2, as shown in Figure 3, AFM schemes as shown in Figure 4 transmission electron microscope figure scanning electron microscope diagram.
Embodiment 2
In the water of 120mL, add 1g Graphite Powder 99, powdered graphite is of a size of 10 microns, is placed in closed reactor, stirs, and be heated to 300 ℃ with 500rpm, keeps within 3 hours, carrying out hydro-thermal and peels off.After cooling, solution is carried out to the centrifugal 30min of 10000rpm rotating speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 5min with 10000rpm, obtain lower floor's solid and be Graphene.Be about 3.2% through the output that weighs Graphene.
Embodiment 3
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 500 microns, is placed in closed reactor, stirs, and be heated to 180 ℃ with 1500rpm, keeps within 6 hours, carrying out hydro-thermal and peels off.After cooling, solution is carried out to the centrifugal 90min of 500rpm rotating speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 2.4% through the output that weighs Graphene.
Embodiment 4
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 2g Triton X-100 (Triton X-100) simultaneously, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 90min of 500rpm rotating speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 50min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 6.3% through the output that weighs Graphene.
Embodiment 5
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.2g CoCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 80min of 500rpm rotating speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 7.4% through the output that weighs Graphene.
Embodiment 6
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g FeCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 90min of 500rpm centrifugal rotational speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 10% through the output that weighs Graphene.
Embodiment 7
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 2g FeCl2 simultaneously, is placed in closed reactor, stirs, and be heated to 240 ℃ with 600rpm, keeps within 3 hours, carrying out hydro-thermal and peels off.After cooling, solution is carried out to the centrifugal 90min of 500rpm rotating speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 8.6% through the output that weighs Graphene.
Embodiment 8
In the water of 120mL, add the complete powdered graphite of unreacted in embodiment 6, add 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g FeCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 90min of 500rpm centrifugal rotational speed, get the supernatant liquid after centrifugation with transfer pipet, obtain homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Through weighing Graphene, the output that 6 conversion calculations obtain Graphene is in conjunction with the embodiments about 35%.
Embodiment 9
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.2g polyaniline, 0.2g butyrolactone (GBL) and 0.5g FeCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 90min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 8.9% through the output that weighs Graphene.
Embodiment 10
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g Rb simultaneously, is placed in closed reactor, stirs, and be heated to 240 ℃ with 600rpm, keeps within 3 hours, carrying out hydro-thermal and peels off.After cooling, solution is carried out to the centrifugal 90min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 90min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 9.5% through the output that weighs Graphene.
Embodiment 11
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.2g Mn simultaneously, is placed in closed reactor, stirs, and be heated to 240 ℃ with 600rpm, keeps within 3 hours, carrying out hydro-thermal and peels off.After cooling, solution is carried out to the centrifugal 70min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 4.5% through the output that weighs Graphene.
Embodiment 12
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.2g IBr simultaneously, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 80min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 20min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 5.1% through the output that weighs Graphene.
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 300 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g FeCl simultaneously
3, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 50min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 6.2% through the output that weighs Graphene.
Embodiment 14
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 100 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g CoCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 50min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 5.5% through the output that weighs Graphene.
Embodiment 15
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 100 microns, adds 0.4g polypyrrole and 0.4g n-propyl alcohol (1-Pro) and 0.5g CuCl simultaneously
2, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 50min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 6.8% through the output that weighs Graphene.
Embodiment 16
In the water of 120mL, add 1g powdered graphite, powdered graphite is of a size of 100 microns, adds 0.4g hexadecyl benzene sulfonic acid sodium salt and 0.5g FeCl simultaneously
2with 0.5g Fe, be placed in closed reactor, stir with 600rpm, and be heated to 240 ℃, keep within 3 hours, carrying out hydro-thermal and peel off.After cooling, solution is carried out to the centrifugal 50min of 500rpm rotating speed, centrifugal rear lower floor solid is the complete powdered graphite of unreacted, gets the supernatant liquid after centrifugation with transfer pipet, obtains homodisperse graphene dispersing solution in mixed solvent.Graphene dispersing solution is carried out to high speed centrifugation 60min with 8000rpm, obtain lower floor's solid and be Graphene.Be about 10.8% through the output that weighs Graphene.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. prepare a method for Graphene, it is characterized in that comprising the steps:
(1) powdered graphite and water are added in reactor;
(2) after closed reactor, stir and heat, being heated to constant temperature after temperature of reaction and continuing stirring reaction;
(3) reaction finishes rear coolingly, after cooling mixing solutions in reactor is taken out and carries out centrifugation, and centrifugal rear lower floor solid is the complete powdered graphite of unreacted, and supernatant liquid is graphene dispersing solution;
(4) get the described graphene dispersing solution of step (3) and carry out high speed centrifugation separation, separating obtained solids is Graphene.
2. a kind of method of preparing Graphene according to claim 1, it is characterized in that: the described powdered graphite of step (1) is any one powdered graphite made in natural flake graphite, highly oriented pyrolytic graphite or expanded graphite, and described powdered graphite is of a size of 10～500 microns.
3. a kind of method of preparing Graphene according to claim 1, is characterized in that: the stir speed (S.S.) of the described stirring reaction of step (2) is 500～1500rpm, and temperature of reaction is 180～300 ℃, and the reaction times is 180～360 minutes.
4. a kind of method of preparing Graphene according to claim 1, is characterized in that: the rotating speed of the described centrifugation of step (3) is 500～10000rpm, and centrifugation time is 30～90 minutes.
5. a kind of method of preparing Graphene according to claim 1, is characterized in that: the rotating speed that the described high speed centrifugation of step (4) separates is 500～10000rpm, and centrifugation time is 5～90 minutes.
6. a kind of method of preparing Graphene according to claim 1, is characterized in that: step (1) is described adds tensio-active agent and/or intercalator when powdered graphite and water are added in reactor.
7. a kind of method of preparing Graphene according to claim 6, is characterized in that: the mass ratio of described powdered graphite and described tensio-active agent is 1:(0～2); The mass ratio of described powdered graphite and described intercalator is 1:(0～2).
8. a kind of method of preparing Graphene according to claim 6, is characterized in that: described tensio-active agent is more than one in sodium laurylsulfonate, hexadecyl benzene sulfonic acid sodium salt, Triton X-100, polystyrene, sodium polystyrene sulfonate, polyaniline, polyamine base benzene sulfonic acid sodium salt, polypyrrole, Polythiophene, poly-ethylenedioxy thiophene, butyrolactone, n-propyl alcohol or Virahol; Described intercalator is more than one in basic metal, alkaline-earth metal, transition metal, halogen simple substance, interhalogen compounds or transition metal chloride.
9. a kind of method of preparing Graphene according to claim 6, is characterized in that: described intercalator is K, Rb, Cs, Ba, Ca, Mn, Fe, Co, Ni, Br
2, ICl, IBr, MnCl
2, CoCl
2, FeCl
2, FeCl
3, CuCl
2or NiCl
2in more than one.
10. according to a kind of method of preparing Graphene described in claim 1 to 9 any one, it is characterized in that: described step (4) also comprises before the complete powdered graphite of the described unreacted of step (3) is repeated to the step of step (1) to step (3).
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| CN110577197A (en) * | 2018-06-11 | 2019-12-17 | 中国科学院深圳先进技术研究院 | Preparation method of boron nitride nanosheet |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7785492B1 (en) * | 2006-09-26 | 2010-08-31 | Nanotek Instruments, Inc. | Mass production of nano-scaled platelets and products |
| CN102013477A (en) * | 2010-11-10 | 2011-04-13 | 河北力滔电池材料有限公司 | Method for preparing lithium iron phosphate/carbon composite material of lithium ion battery |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
| CN102583335A (en) * | 2012-01-19 | 2012-07-18 | 常州大学 | Preparation method of graphene uniform dispersion |
| CN103112848A (en) * | 2013-03-08 | 2013-05-22 | 厦门大学 | Method for preparing graphene |
-
2013
- 2013-12-30 CN CN201310747304.XA patent/CN103771402A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7785492B1 (en) * | 2006-09-26 | 2010-08-31 | Nanotek Instruments, Inc. | Mass production of nano-scaled platelets and products |
| CN102013477A (en) * | 2010-11-10 | 2011-04-13 | 河北力滔电池材料有限公司 | Method for preparing lithium iron phosphate/carbon composite material of lithium ion battery |
| CN102167310A (en) * | 2011-01-30 | 2011-08-31 | 黑龙江大学 | Method for preparing nitrogen-doped graphene material with hydrothermal process |
| CN102583335A (en) * | 2012-01-19 | 2012-07-18 | 常州大学 | Preparation method of graphene uniform dispersion |
| CN103112848A (en) * | 2013-03-08 | 2013-05-22 | 厦门大学 | Method for preparing graphene |
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| CN105253862A (en) * | 2014-07-15 | 2016-01-20 | 中国科学院过程工程研究所 | Method for large-scale preparation of graphene-like boron nitride nano-sheets through high temperature liquid-phase peeling |
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