CN102530911B - Graphene fluoride preparation method - Google Patents
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- CN102530911B CN102530911B CN201010601012.1A CN201010601012A CN102530911B CN 102530911 B CN102530911 B CN 102530911B CN 201010601012 A CN201010601012 A CN 201010601012A CN 102530911 B CN102530911 B CN 102530911B
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Abstract
The invention relates to a graphene fluoride preparation method, which comprises the following steps of: 1) using graphite for preparing graphene oxide through an improved Hummers process; 2) using hydrazine hydrate for reducing the graphene oxide into graphene, and 3) enabling the graphene to react with fluorinating agent to obtain the graphene fluoride. The graphene fluoride which is prepared through the method has the advantages that the original conjugate structure of the graphene is not destroyed and the prepared graphene fluoride additionally has electric conductivity equivalent to the electric conductivity of the graphene.
Description
[technical field]
The invention belongs to organic semiconductor material technical field, be specifically related to a kind of preparation method of fluorinated graphene.
[background technology]
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Mono-layer graphite is due to its large specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1. high strength, Young's modulus, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm
2/ Vs); 4. high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.But, prepare on a large scale in the process of Graphene by redox method at present, reduction later prepared Graphene also contain small amount-OH ,-C-O-C-and-oxygen-containing functional groups such as COOH.These functional groups just decompose and produce gas (Nanohybrid Capacitor:The Next Generation Electrochemical Capacitors.FUEL CELLS 00 under the voltage less than 4V, 0000, No.0,1-9), thereby the use voltage of restriction Graphene electrodes material in lithium ion battery and ultracapacitor.
(fluorinated graphene is a kind of very thin isolator, and it is made by increase a fluorine atom around each carbon atom of Graphene.It is first stoichiometric derivative of Graphene, and is a wide band gap semiconducter.Fluorinated graphene is all good compounds of mechanical property, chemical stability and a thermostability.Performance and the Teflon of this novel material are closely similar, are conventionally referred to as two-dimentional Teflon.) this section should delete betterly, our fluorinated graphene is reasonable semi-conductor, above said isolator is just not right.
Traditional fluorinated graphene obtains after fluoridizing by Graphene, but fluorine is a kind of highly active element, and it can react with nearly all material.In tradition preparation method's process, fluorine likely can destroy the original conjugated structure of Graphene, causes the fluorinated graphene electric conductivity of preparation to decline to a great extent.
[summary of the invention]
Based on this, be necessary to provide at least one not reduce the preparation method of the fluorinated graphene of electric conductivity.
A preparation method for fluorinated graphene, comprises the steps:
Step 1, use graphite by improved Hummers legal system for graphene oxide;
Described graphene oxide is reduced into Graphene by step 2, use hydrazine hydrate; And
Step 3, described Graphene is reacted with fluorizating agent, obtain fluorinated graphene.
In a preferred embodiment, fluorizating agent described in step 3 is N, N-diethyl-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4nF, (C
4h
9)
4nF, (CH
3)
4nHF
2in one.
In a preferred embodiment, the mass ratio of Graphene described in step 3 and described fluorizating agent is 1: 1～1: 10.
In a preferred embodiment, the purity 95～99.5% of graphite described in step 1.
In a preferred embodiment, step 1 is:
By described graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in the vitriol oil of 60～80 ℃, naturally cooling after stirring, washing, to dry after neutral, obtains mixture;
Described mixture and potassium permanganate are joined in the vitriol oil, keep the temperature of mixing solutions at 15 ℃～20 ℃, then oil bath 1～4 hour at 25 ℃～50 ℃, adds deionized water and adds hydrogen peroxide solution reaction, suction filtration, collects solid; And
Described solid washs with dilute hydrochloric acid, dry, obtains described graphene oxide.
In a preferred embodiment, step 2 is:
Described graphene oxide and water are mixed with to the suspension liquid of 1～5g/L, and use the ultrasonic equipment of 150～300W to carry out ultrasonic dispersion to described suspension liquid;
Adding concentration is 98% hydrazine hydrate, is heated to 80～100 ℃ of reactions 24～48 hours; And
Filter, collect solid, washing, dry, obtain Graphene.
In a preferred embodiment, step 3 is:
Described Graphene is joined in anhydrous methylene chloride, dispersed;
In described Graphene: fluorizating agent mass ratio be the ratio of 1: 1～1: 10 under the protection of rare gas element at 20～40 ℃ stirring reaction 1～100 hour, obtain reaction product; And
Described reaction product is added to the water, and suction filtration, collects solid, and water and methanol wash is successively dry, obtains described fluorinated graphene.
Owing to having adopted 1,1,2,3,3,3-hexafluoro propyl group diethylamide and diethylin sulfur trifluoride are introduced fluorine, the fluorinated graphene of preparing by above-mentioned two kinds of modes can not destroy the original conjugated structure of Graphene, thereby prepared fluorinated graphene also has the specific conductivity suitable with Graphene.
[accompanying drawing explanation]
Fig. 1 is the preparation method's of the fluorinated graphene of an embodiment schema;
Fig. 2,3 is respectively the C1s of fluorinated graphene and the XPS collection of illustrative plates of F1s of an embodiment;
Fig. 4 is the SEM collection of illustrative plates of the fluorinated graphene of an embodiment.
[embodiment]
Below in conjunction with drawings and Examples, the preparation method of fluorinated graphene is described in further detail.
Refer to Fig. 1, the preparation method of the fluorinated graphene of an embodiment comprises following steps:
Step S110, provide graphite.Be preferably purity at 95～99.5% flaky graphite.
Step S120, use graphite by improved Hummers legal system for graphene oxide.Hummers method is a kind of method of preparing graphite oxide, be placed in same container water-bath or oil bath heating by graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid), until fully taking out after oxidation, first reduce potassium permanganate with hydrogen peroxide, with distilled water or hydrochloric acid washed product several, after being dried, obtain graphite oxide.Reference: Hummers W S, Offeman R E.J.Am.Chem.Soc., 1985,80 (6): 1339-1339.And also can directly prepare graphene oxide by improved Hummers method (modified Hummers).Reference: numb fine jade, the research of stannic oxide/graphene nano composite membrane, [master's Diplomarbeit]. the .2008 of chemical engineering institute of University Of Tianjin.In present embodiment, adopt and prepare with the following method graphene oxide:
Step S121, by the graphite of step S10, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in the vitriol oil of 80～120 ℃, naturally cooling after stirring, washing, to dry after neutral, obtains mixture.
Step S122, joins mixture and potassium permanganate in the vitriol oil, keeps the temperature of mixing solutions at 15～20 ℃, and then oil bath 1～4 hour at 25 ℃～50 ℃, adds deionized water and add hydrogen peroxide solution reaction, suction filtration, collects solid.
Step S123, described solid washs with dilute hydrochloric acid, dry, obtains graphene oxide.
Step S130, uses hydrazine hydrate that described graphene oxide is reduced into Graphene.Hydrazine hydrate claims again hydrazine hydrate, has extremely strong reductibility.In present embodiment, adopt reduced graphene with the following method.
Step S131, is mixed with described graphene oxide the aqueous solution of 1～5g/L, and uses the ultrasonic equipment of 150～300W to carry out ultrasonic dispersion.
Step S132, adding concentration is 98% hydrazine hydrate, is heated to 80～100 ℃ of reactions 24～48 hours.
Step S133, filters, and collects solid, and washing is dry, obtains Graphene.
Step S140, reacts Graphene with fluorizating agent, obtain fluorinated graphene.The reactive behavior of fluorizating agent is very high, therefore can replace in Graphene-O or-OH, reaction formula is:
This fluorizating agent is preferably N, N-diethyl-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4nF, (C
4h
9)
4nF, (CH
3)
4nHF
2in one.
N, N-diethyl-1,1,2,3,3,3-hexafluoro propylamine is called again Ishikawa reagent (Ishikawa ' s reagent), and molecular formula is:
Diethylin sulfur trifluoride (DAST) is also a kind of conventional fluorination reagent, and its molecular formula is:
In present embodiment, adopt and prepare with the following method fluorinated graphene:
Step S141, joins anhydrous methylene chloride (CH by Graphene
2cl
2) in, dispersed.
Step S142, in Graphene: fluorizating agent mass ratio is that the ratio of 1: 1～1: 10 adds fluorizating agent, and under the protection of rare gas element at 20～40 ℃ stirring reaction 1～100 hour, obtain reactant.
Step S143, is added to the water described reactant, and suction filtration is collected solid, and water and methanol wash is successively dry, obtains fluorinated graphene.
Wherein, the mass percent that the mass percent of the F in gained fluorinated graphene is 0～10.5%, C is 89.5%～100%.
Above-mentioned preparation method's advantage is: the fluorinated graphene of preparation can not destroy the original conjugated structure of Graphene by the way, thereby prepared fluorinated graphene also has the specific conductivity suitable with Graphene.In addition, the radius of fluorine atom is little, is the element that electronegativity is the strongest, and this extremely strong strong electronegativity has increased the avidity of fluorine and carbon.Therefore the C-F key that they form can be much bigger than c h bond, significantly strengthened the stability of fluorinated organic compound.The oxygen replacing in Graphene by fluorine can significantly improve the stability of fluorinated graphene electrode materials under high-voltage.Prepared fluorinated graphene can be used as electrode materials and is applied in ultracapacitor and lithium ion battery electrode material.
With specific embodiment, the present invention is described below, but the following example does not limit the present invention in any way.
Embodiment 1
A preparation method for fluorinated graphene, comprising:
(1) providing purity is 99.5% Graphite Powder 99.
(2) 20g 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of enough 80 ℃, stir, more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 25 ℃, keep after 2h, slowly add 920mL deionized water.After 15min, add again 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 ℃ of vacuum-drying 48h with the dilute hydrochloric acid that 5L concentration is 10%.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL to the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Then add wherein hydrazine hydrate (1mL, 98%) and be heated to 100 ℃ of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, and at 80 ℃, in vacuum drying oven, dry 48h obtains Graphene.
(4) by the Graphene obtaining in (3) by with 1,1,2,3,3, the reaction of 3-hexafluoro propyl group diethylamide obtains fluorinated graphene.Be specially by dried 1g Graphene and the anhydrous CH of 300mL
2cl
2join successively in reaction flask, after dispersed with stirring is even, at room temperature slowly add wherein 1g 1,1,2,3,3,3-hexafluoro propyl group diethylamide.Under the protection of rare gas element at 20～40 ℃ stirring reaction 48h.Stopped reaction, pours reaction product in 100mL water into, suction filtration, and by gained solid successively water 200mL and methyl alcohol 200mL washing, at 80 ℃, in vacuum drying oven, dry 48h obtains fluorinated graphene.
Fig. 2 and Fig. 3 are respectively the C1s of fluorinated graphene and the XPS collection of illustrative plates of F1s of embodiment 1.Fig. 2 is positioned at 284.8eV place very strong peak value, and in corresponding fluorinated graphene, carbon bond structure is C-C (284.8eV); Fig. 3 is positioned at 689.5eV place very strong peak value, and in corresponding fluorinated graphene, carbon bond structure is C-F (689.5eV).
Fig. 4 is the SEM Electronic Speculum picture of the fluorinated graphene of embodiment 1.As can be seen from Figure 4 prepared fluorinated graphene surface is gauffer shape, thereby this gauffer is conducive to improve the specific surface area raising energy density of material.
The electric conductivity of the present embodiment fluorinated graphene is 1.25 × 10 as shown in Table 1
3s/m.
Embodiment 2
A preparation method for fluorinated graphene, comprising:
(1) providing purity is 99.5% Graphite Powder 99.
(2) 40g 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of enough 90 ℃, stir, more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 15 ℃, then in the oil bath of 35 ℃, keep after 3h, slowly add 920mL deionized water.After 15min, add again 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 ℃ of vacuum-drying 48h with the hydrochloric acid that 5L concentration is 10%.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL to the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 200W.Then add wherein hydrazine hydrate (1mL, 98%) and be heated to 120 ℃ of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, and at 80 ℃, in vacuum drying oven, dry 48h obtains Graphene.
(4) by gained Graphene in (3) by reacting and obtain fluorinated graphene with diethylin sulfur trifluoride.Be specially under protection of inert gas, by dried 1g Graphene and the anhydrous CH of 300mL
2cl
2join successively in reaction flask, dispersed with stirring evenly and after reactant being cooled to-10 ℃ slowly drips 3g diethylin sulfur trifluoride wherein.After dropwising, by reactant stirring reaction 24h at 0～40 ℃, stopped reaction.Reaction product is poured in 200g trash ice, suction filtration, by gained solid successively water 200mL and methyl alcohol 200mL washing, at 80 ℃, in vacuum drying oven, dry 48h obtains fluorinated graphene.
The electric conductivity of the present embodiment fluorinated graphene is 1.51 × 10 as shown in Table 1
3.
Embodiment 3
A preparation method for fluorinated graphene, comprising:
(1) providing purity is 99.5% Graphite Powder 99.
(2) 60g 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of enough 100 ℃, stir, more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 40 ℃, keep after 3h, slowly add 920mL deionized water.After 15min, add again 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 ℃ of vacuum-drying 48h with the dilute hydrochloric acid that 5L concentration is 10%.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL to the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 250W.Then add wherein hydrazine hydrate (1mL, 98%) and be heated to 130 ℃ of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, and at 80 ℃, in vacuum drying oven, dry 48h obtains Graphene.
(4) by the Graphene obtaining in (3) by with (CH
3)
4nF reaction obtains fluorinated graphene.By dried 1g Graphene and the anhydrous CH of 300mL
2cl
2join successively in reaction flask, after dispersed with stirring is even, at room temperature slowly add wherein 5g (CH
3)
4nF.Under the protection of rare gas element at 20～40 ℃ stirring reaction 36h.Stopped reaction, pours reaction product in 100mL water into, suction filtration, and by gained solid successively water 200mL and methyl alcohol 200mL washing, at 80 ℃, in vacuum drying oven, dry 48h obtains fluorinated graphene.
The electric conductivity of the present embodiment fluorinated graphene is 1.32 × 10 as shown in Table 1
3.
Embodiment 4
A preparation method for fluorinated graphene, comprising:
(1) providing purity is 99.5% Graphite Powder 99.
(2) 80g 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of enough 110 ℃, stir, more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 45 ℃, keep after 4h, slowly add 920mL deionized water.After 15min, add again 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 ℃ of vacuum-drying 48h with the dilute hydrochloric acid that 5L concentration is 10%.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL to the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 300W.Then add wherein hydrazine hydrate (1mL, 98%) and be heated to 140 ℃ of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, and at 80 ℃, in vacuum drying oven, dry 48h obtains Graphene.
(4) by the Graphene obtaining in (3) by with (C
4h
9)
4nF reaction obtains fluorinated graphene.By dried 1g Graphene and the anhydrous CH of 300mL
2cl
2join successively in reaction flask, after dispersed with stirring is even, at room temperature slowly add wherein 7g (C
4h
9)
4nF.Under the protection of rare gas element at 20～40 ℃ stirring reaction 72h.Stopped reaction, pours reaction product in 100mL water into, suction filtration, and by gained solid successively water 200mL and methyl alcohol 200mL washing, at 80 ℃, in vacuum drying oven, dry 48h obtains fluorinated graphene.
The electric conductivity of the present embodiment fluorinated graphene is 1.20 × 10 as shown in Table 1
3.
Embodiment 5
A preparation method for fluorinated graphene, comprising:
(1) providing purity is 99.5% Graphite Powder 99.
(2) 100g 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of enough 120 ℃, stir, more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 50 ℃, keep after 1h, slowly add 920mL deionized water.After 15min, add again 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% hydrogen peroxide), mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, obtain graphene oxide at 60 ℃ of vacuum-drying 48h with the dilute hydrochloric acid that 5L concentration is 10%.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL to the suspension liquid that now solution is brown color.Then suspension liquid is disperseed with the ultrasonic echography of 150W.Then add wherein hydrazine hydrate (1mL, 98%) and be heated to 150 ℃ of reaction 24h.Gained Graphene is water 300mL and methyl alcohol 300mL washing successively after filtering, and at 80 ℃, in vacuum drying oven, dry 48h obtains Graphene.
(4) by the Graphene obtaining in (3) by with (CH
3)
4nHF
2reaction obtains fluorinated graphene.By dried 1g Graphene and the anhydrous CH of 300mL
2cl
2join successively in reaction flask, after dispersed with stirring is even, at room temperature slowly add wherein 10g (CH
3)
4nHF
2.Under the protection of rare gas element at 20～40 ℃ stirring reaction 100h.Stopped reaction, pours reaction product in 100mL water into, suction filtration, and by gained solid successively water 200mL and methyl alcohol 200mL washing, at 80 ℃, in vacuum drying oven, dry 48h obtains fluorinated graphene.
The electric conductivity of the present embodiment fluorinated graphene is 1.46 × 10 as shown in Table 1
3
The electric conductivity of table 1 embodiment of the present invention fluorinated graphene
| Numbering | Embodiment mono- | Embodiment bis- | Embodiment tri- | Embodiment tetra- | Embodiment five |
| Electric conductivity (S/m) | 1.25×10 3 | 1.51×10 3 | 1.32×10 3 | 1.20×10 3 | 1.46×10 3 |
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (5)
1. a preparation method for fluorinated graphene, is characterized in that, comprises the steps:
Step 1, use graphite by improved Hummers legal system for graphene oxide;
Described graphene oxide is reduced into Graphene by step 2, use hydrazine hydrate; And
Step 3, described Graphene is reacted with fluorizating agent, obtain fluorinated graphene;
Described Graphene is joined in anhydrous methylene chloride, dispersed;
By described Graphene and fluorizating agent mass ratio 1:1～1:10, under the protection of rare gas element, at 20～40 ℃, stirring reaction 1～100 hour, obtains reaction product; And
Described reaction product is added to the water, and suction filtration, collects solid, and water and methanol wash is successively dry, obtains described fluorinated graphene;
Fluorizating agent described in step 3 is N, N-diethyl-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4nF, (C
4h
9)
4nF, (CH
3)
4nHF
2in one.
2. the rare preparation method of fluorographite according to claim 1, is characterized in that, the mass ratio of described Graphene and described fluorizating agent is 1:1～1:5.
3. the preparation method of fluorinated graphene according to claim 1, is characterized in that, the purity of graphite described in step 1 is 95～99.5%.
4. the preparation method of fluorinated graphene according to claim 1, is characterized in that, step 1 is:
Described graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES are joined according to mass ratio 2～10:1:1 in the vitriol oil of 80～120 ℃, naturally cooling after stirring, washing, to dry after neutral, obtains mixture;
Described mixture and potassium permanganate are joined in the vitriol oil, keep the temperature of mixing solutions at 15 ℃～20 ℃, then oil bath 1～4 hour at 25 ℃～50 ℃, adds deionized water and adds hydrogen peroxide solution reaction, suction filtration, collects solid; And
Described solid washs with dilute hydrochloric acid, dry, obtains described graphene oxide.
5. the preparation method of fluorinated graphene according to claim 1, is characterized in that, step 2 is:
Described graphene oxide and water are mixed with to the suspension liquid of 1～5g/L, and use the ultrasonic equipment of 150～300W to carry out ultrasonic dispersion to described suspension liquid;
Adding concentration is 98% hydrazine hydrate, is heated to 80～100 ℃ of reactions 24～48 hours; And
Filter, collect solid, washing, dry, obtain Graphene.
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