CN102530911A - Graphene fluoride preparation method - Google Patents
Graphene fluoride preparation method Download PDFInfo
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- CN102530911A CN102530911A CN2010106010121A CN201010601012A CN102530911A CN 102530911 A CN102530911 A CN 102530911A CN 2010106010121 A CN2010106010121 A CN 2010106010121A CN 201010601012 A CN201010601012 A CN 201010601012A CN 102530911 A CN102530911 A CN 102530911A
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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 the organic semiconductor material technical field, be specifically related to a kind of preparation method of fluorographite alkene.
[background technology]
Prepared grapheme material in 2004 since the strong K of the peace moral of Univ Manchester UK sea nurse (Andre K.Geim) waits, pay attention to widely owing to its particular structure and photoelectric property have received people.Mono-layer graphite is because its big specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1. HS, 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 the big specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.Yet, at present in the process through redox method mass preparation Graphene, reduction later prepared graphene also contain more a spot of-OH ,-C-O-C-and-oxygen-containing functional groups such as COOH.These functional groups just decompose generation gas (Nanohybrid Capacitor:The Next Generation Electrochemical Capacitors.FUEL CELLS 00 under less than the voltage of 4V; 0000; No.0; 1-9), thereby the restriction working voltage of Graphene electrodes material in lithium ion battery and ultracapacitor.
(fluorographite alkene is a kind of very thin isolator, and it is processed through around each carbon atom of Graphene, increasing a fluorine atom.It is first stoichiometric verivate of Graphene, and is a wide band gap semiconducter.Fluorographite alkene is all good compound of mechanical property, chemicalstability and a thermostability.The performance and the Teflon of this novel material are closely similar, are referred to as two-dimentional Teflon usually.) this section should delete betterly, our fluorographite alkene is reasonable semi-conductor, the isolator of saying above is just not right.
Traditional fluorographite alkene obtains after fluoridizing through Graphene, yet fluorine is a kind of highly active element, and it can react with nearly all material.In the process of traditional preparation process method, fluorine might destroy the original conjugated structure of Graphene, and the fluorographite alkene electric conductivity that causes preparing declines to a great extent.
[summary of the invention]
Based on this, be necessary to provide at least a preparation method who does not reduce the fluorographite alkene of electric conductivity.
A kind of preparation method of fluorographite alkene comprises the steps:
Step 1, use graphite are equipped with graphene oxide through improved Hummers legal system;
Step 2, use Hydrazine Hydrate 80 are reduced into Graphene with said graphene oxide; And
Step 3, with the reaction of said Graphene and fluorizating agent, obtain fluorographite alkene.
In a preferred embodiment, fluorizating agent described in the step 3 is N, N-diethylammonium-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4NF, (C
4H
9)
4NF, (CH
3)
4NHF
2In a kind of.
In a preferred embodiment, the mass ratio of Graphene described in the step 3 and said fluorizating agent is 1: 1～1: 10.
In a preferred embodiment, the purity 95～99.5% of graphite described in the step 1.
In a preferred embodiment, step 1 is:
With said graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in 60～80 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains mixture;
Said mixture and potassium permanganate are joined in the vitriol oil, and the temperature that keeps mixing solutions, adds deionized water and adds the hydrogen peroxide solution reaction, suction filtration, collection solid then 25 ℃～50 ℃ following oil baths 1～4 hour at 15 ℃～20 ℃; And
Said solid washs with Hydrogen chloride, and drying obtains said graphene oxide.
In a preferred embodiment, step 2 is:
Said graphene oxide and water are mixed with the suspension liquid of 1～5g/L, and use the ultrasonic equipment of 150～300W that said suspension liquid is carried out ultra-sonic dispersion;
Adding concentration is 98% Hydrazine Hydrate 80, is heated to 80～100 ℃ of reactions 24～48 hours; And
Filter, collect solid, washing, drying obtains Graphene.
In a preferred embodiment, step 3 is:
Said Graphene is joined in the anhydrous methylene chloride homodisperse;
In said Graphene: the fluorizating agent mass ratio be 1: 1～1: 10 ratio under the protection of rare gas element 20～40 ℃ of following stirring reactions 1～100 hour, obtain reaction product; And
Said reaction product is added to the water, and suction filtration is collected solid, water and methanol wash successively, and drying obtains said fluorographite alkene.
Owing to adopted 1,1,2; 3,3,3-hexafluoro propyl group DIETHANOL AMINE and diethylin sulfur trifluoride are introduced fluorine; Fluorographite alkene through above-mentioned prepared in one of two ways can not destroy the original conjugated structure of Graphene, thereby prepared fluorographite alkene also has the specific conductivity suitable with Graphene.
[description of drawings]
Fig. 1 is preparing method's the schema of the fluorographite alkene of an embodiment;
Fig. 2,3 is respectively C1s and the XPS collection of illustrative plates of F1s of the fluorographite alkene of an embodiment;
Fig. 4 is the SEM collection of illustrative plates of the fluorographite alkene of an embodiment.
[embodiment]
To combine accompanying drawing and embodiment that the preparation method of fluorographite alkene is done further detailed description below.
See also Fig. 1, the preparation method of the fluorographite alkene of an embodiment comprises following steps:
Step S110, graphite is provided.Be preferably purity at 95～99.5% flaky graphite.
Step S120, use graphite are equipped with graphene oxide through improved Hummers legal system.The Hummers method is a kind of method for preparing graphite oxide; Be about to graphite, potassium permanganate and high density acid with strong oxidizing property (sulfuric acid or nitric acid) and place same container water-bath or oil bath heating; Treat to take out after the abundant oxidation; Earlier reduce potassium permanganate,, obtain graphite oxide after the drying for several times with zero(ppm) water or hydrochloric acid washed product with ydrogen peroxide 50.Reference: Hummers W S, Offeman R E.J.Am.Chem.Soc., 1985,80 (6): 1339-1339.And also can directly prepare graphene oxide through improved Hummers method (modified Hummers).Reference: numb fine jade, the research of stannic oxide/graphene nano composite package, [master's Diplomarbeit]. the .2008 of chemical engineering institute of University Of Tianjin.In this embodiment, adopt following method to prepare graphene oxide:
Step S121, with graphite, Potassium Persulphate and the Vanadium Pentoxide in FLAKES of step S10 according to mass ratio 2～10: join at 1: 1 in 80～120 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains mixture.
Step S122 joins mixture and potassium permanganate in the vitriol oil, and the temperature that keeps mixing solutions, adds deionized water and adds the hydrogen peroxide solution reaction, suction filtration, collection solid then 25 ℃～50 ℃ following oil baths 1～4 hour at 15～20 ℃.
Step S123, said solid washs with Hydrogen chloride, and drying obtains graphene oxide.
Step S130 uses Hydrazine Hydrate 80 that said graphene oxide is reduced into Graphene.Hydrazine Hydrate 80 is claimed hydrazine hydrate again, has extremely strong reductibility.In this embodiment, adopt following method reduction Graphene.
Step S131 is mixed with the aqueous solution of 1～5g/L with said graphene oxide, and uses the ultrasonic equipment of 150～300W to carry out ultra-sonic dispersion.
Step S132, adding concentration is 98% Hydrazine Hydrate 80, is heated to 80～100 ℃ of reactions 24～48 hours.
Step S133 filters, and collects solid, washing, and drying obtains Graphene.
Step S140 with Graphene and fluorizating agent reaction, obtains fluorographite alkene.The reactive behavior of fluorizating agent is very high, therefore can replace in the Graphene-O or-OH, reaction formula is:
This fluorizating agent is preferably N, N-diethylammonium-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4NF, (C
4H
9)
4NF, (CH
3)
4NHF
2In a kind of.
N, N-diethylammonium-1,1,2,3,3,3-hexafluoro propylamine are called Ishikawa reagent (Ishikawa ' s reagent) again, and molecular formula is:
Diethylin sulfur trifluoride (DAST) also is a kind of fluorination reagent commonly used, and its molecular formula is:
In this embodiment, adopt following method to prepare fluorographite alkene:
Step S141 joins anhydrous methylene chloride (CH with Graphene
2Cl
2) in, homodisperse.
Step S142, in Graphene: the fluorizating agent mass ratio is that 1: 1～1: 10 ratio adds fluorizating agent, and under the protection of rare gas element 20～40 ℃ of following stirring reactions 1～100 hour, obtain reactant.
Step S143 is added to the water said reactant, and suction filtration is collected solid, water and methanol wash successively, and drying obtains fluorographite alkene.
Wherein, the mass percent of the F in the gained fluorographite alkene is 0～10.5%, and the mass percent of C is 89.5%～100%.
Above-mentioned preparing method's advantage is: the fluorographite alkene of preparation can not destroy the original conjugated structure of Graphene by the way, thereby prepared fluorographite alkene also has the specific conductivity suitable with Graphene.In addition, the radius of fluorine atom is little, is the strongest element of electronegativity, and this utmost point intensive electronegativity has increased the avidity of fluorine and carbon.Therefore their formed C-F keys can be much bigger than c h bond, significantly strengthened the stability of fluorinated organic compound.The oxygen that replaces in the Graphene through fluorine can significantly improve the stability of fluorographite alkene electrode materials under high-voltage.Prepared fluorographite alkene can be used as electrode materials and is applied in ultracapacitor and the lithium ion battery electrode material.
Below with specific embodiment the present invention is described, yet the following example does not limit the present invention in any way.
Embodiment 1
A kind of preparation method of fluorographite alkene comprises:
(1) purity being provided is 99.5% Graphite Powder 99.
(2) 20g 50 purpose Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃ of capacities, stir, more than the cooling 6h, washing is to neutrality, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 25 ℃ oil bath, behind the maintenance 2h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% Hydrogen chloride washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL, this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.Then to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 100 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h obtains Graphene in 80 ℃ of following vacuum drying ovens.
(4) with resulting Graphene in (3) through with 1,1,2,3,3, the reaction of 3-hexafluoro propyl group DIETHANOL AMINE obtains fluorographite alkene.Be specially 1g Graphene and the anhydrous CH of 300mL that drying is being got well
2Cl
2Join successively in the reaction flask, dispersed with stirring evenly after at room temperature to wherein slowly adding 1g 1,1,2,3,3,3-hexafluoro propyl group DIETHANOL AMINE.Under the protection of rare gas element at 20～40 ℃ of following stirring reaction 48h.Stopped reaction is poured reaction product in the 100mL water into, suction filtration, and with gained solid water 200mL successively and methyl alcohol 200mL washing, dry 48h promptly obtains fluorographite alkene in 80 ℃ of following vacuum drying ovens.
Fig. 2 and Fig. 3 are respectively C1s and the XPS collection of illustrative plates of F1s of the fluorographite alkene of embodiment 1.Fig. 2 is positioned at the 284.8eV place has very strong peak value, and carbon bond structure is C-C (284.8eV) in the corresponding fluorographite alkene; Fig. 3 is positioned at the 689.5eV place has very strong peak value, and carbon bond structure is C-F (689.5eV) in the corresponding fluorographite alkene.
Fig. 4 is the SEM Electronic Speculum picture of the fluorographite alkene of embodiment 1.As can be seen from Figure 4 prepared fluorographite alkene surface is a corrugated, thereby this gauffer helps improving the specific surface area raising energy density of material.
But the electric conductivity by table 1 knowledge capital embodiment fluorographite alkene is 1.25 * 10
3S/m.
Embodiment 2
A kind of preparation method of fluorographite alkene comprises:
(1) purity being provided is 99.5% Graphite Powder 99.
(2) 40g 50 purpose Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 90 ℃ of capacities, stir, more than the cooling 6h, washing is to neutrality, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 15 ℃, in 35 ℃ oil bath, behind the maintenance 3h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% hydrochloric acid washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL, this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 200W disperseed.Then to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 120 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h obtains Graphene in 80 ℃ of following vacuum drying ovens.
(4) gained Graphene in (3) is obtained fluorographite alkene through reacting with the diethylin sulfur trifluoride.Be specially under protection of inert gas 1g Graphene and the anhydrous CH of 300mL that drying has been got well
2Cl
2Join successively in the reaction flask, after dispersed with stirring is cooled to-10 ℃ evenly and with reactant to wherein slowly dripping 3g diethylin sulfur trifluoride.After dropwising, with reactant at 0～40 ℃ of following stirring reaction 24h, stopped reaction.Reaction product is poured in the 200g trash ice, suction filtration, with gained solid water 200mL successively and methyl alcohol 200mL washing, dry 48h promptly obtains fluorographite alkene in 80 ℃ of following vacuum drying ovens.
But the electric conductivity by table 1 knowledge capital embodiment fluorographite alkene is 1.51 * 10
3
Embodiment 3
A kind of preparation method of fluorographite alkene comprises:
(1) purity being provided is 99.5% Graphite Powder 99.
(2) 60g 50 purpose Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 100 ℃ of capacities, stir, more than the cooling 6h, washing is to neutrality, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 40 ℃ oil bath, behind the maintenance 3h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% Hydrogen chloride washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL, this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 250W disperseed.Then to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 130 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h obtains Graphene in 80 ℃ of following vacuum drying ovens.
(4) with resulting Graphene in (3) through with (CH
3)
4The NF reaction obtains fluorographite alkene.1g Graphene and the anhydrous CH of 300mL that drying is being got well
2Cl
2Join successively in the reaction flask, dispersed with stirring evenly after at room temperature to wherein slowly adding 5g (CH
3)
4NF.Under the protection of rare gas element at 20～40 ℃ of following stirring reaction 36h.Stopped reaction is poured reaction product in the 100mL water into, suction filtration, and with gained solid water 200mL successively and methyl alcohol 200mL washing, dry 48h promptly obtains fluorographite alkene in 80 ℃ of following vacuum drying ovens.
But the electric conductivity by table 1 knowledge capital embodiment fluorographite alkene is 1.32 * 10
3
Embodiment 4
A kind of preparation method of fluorographite alkene comprises:
(1) purity being provided is 99.5% Graphite Powder 99.
(2) 80g 50 purpose Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 110 ℃ of capacities, stir, more than the cooling 6h, washing is to neutrality, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 45 ℃ oil bath, behind the maintenance 4h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% Hydrogen chloride washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL, this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 300W disperseed.Then to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 140 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h obtains Graphene in 80 ℃ of following vacuum drying ovens.
(4) with resulting Graphene in (3) through with (C
4H
9)
4The NF reaction obtains fluorographite alkene.1g Graphene and the anhydrous CH of 300mL that drying is being got well
2Cl
2Join successively in the reaction flask, dispersed with stirring evenly after at room temperature to wherein slowly adding 7g (C
4H
9)
4NF.Under the protection of rare gas element at 20～40 ℃ of following stirring reaction 72h.Stopped reaction is poured reaction product in the 100mL water into, suction filtration, and with gained solid water 200mL successively and methyl alcohol 200mL washing, dry 48h promptly obtains fluorographite alkene in 80 ℃ of following vacuum drying ovens.
But the electric conductivity by table 1 knowledge capital embodiment fluorographite alkene is 1.20 * 10
3
Embodiment 5
A kind of preparation method of fluorographite alkene comprises:
(1) purity being provided is 99.5% Graphite Powder 99.
(2) 100g 50 purpose Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 120 ℃ of capacities, stir, more than the cooling 6h, washing is to neutrality, drying.In the vitriol oil with 0 ℃ of dried sample adding, 230mL, add 60g potassium permanganate again, the temperature of mixture remains on below 20 ℃, in 50 ℃ oil bath, behind the maintenance 1h, slowly adds the 920mL deionized water then.Behind the 15min; Add 2.8L hydrogen peroxide solution (wherein contain 50mL concentration be 30% ydrogen peroxide 50) again; The mixture color becomes glassy yellow afterwards, and suction filtration while hot uses that 5L concentration is that 10% Hydrogen chloride washs again, suction filtration, promptly obtains graphene oxide at 60 ℃ of vacuum-drying 48h.
(3) 100mg graphene oxide and 100mL deionized water are joined in the round-bottomed flask of 250mL, this moment, solution was brown xanchromatic suspension liquid.Then the ultrasonic echography of suspension liquid with 150W disperseed.Then to wherein adding Hydrazine Hydrate 80 (1mL, 98%) and being heated to 150 ℃ of reaction 24h.Water 300mL and methyl alcohol 300mL washing successively after the gained Graphene filters, dry 48h obtains Graphene in 80 ℃ of following vacuum drying ovens.
(4) with resulting Graphene in (3) through with (CH
3)
4NHF
2Reaction obtains fluorographite alkene.1g Graphene and the anhydrous CH of 300mL that drying is being got well
2Cl
2Join successively in the reaction flask, dispersed with stirring evenly after at room temperature to wherein slowly adding 10g (CH
3)
4NHF
2Under the protection of rare gas element at 20～40 ℃ of following stirring reaction 100h.Stopped reaction is poured reaction product in the 100mL water into, suction filtration, and with gained solid water 200mL successively and methyl alcohol 200mL washing, dry 48h promptly obtains fluorographite alkene in 80 ℃ of following vacuum drying ovens.
But the electric conductivity by table 1 knowledge capital embodiment fluorographite alkene is 1.46 * 10
3
The electric conductivity of table 1 embodiment of the invention fluorographite alkene
| Numbering | Embodiment one | Embodiment two | Embodiment three | Embodiment four | 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 kinds of embodiments of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (8)
1. the preparation method of a fluorographite alkene is characterized in that, comprises the steps:
Step 1, use graphite are equipped with graphene oxide through improved Hummers legal system;
Step 2, use Hydrazine Hydrate 80 are reduced into Graphene with said graphene oxide; And
Step 3, with the reaction of said Graphene and fluorizating agent, obtain fluorographite alkene.
2. the preparation method of fluorographite alkene according to claim 1 is characterized in that, fluorizating agent described in the step 3 is N, N-diethylammonium-1,1,2,3,3,3-hexafluoro propylamine, diethylin sulfur trifluoride, SF
4, (CH
3)
4NF, (C
4H
9)
4NF, (CH
3)
4NHF
2In a kind of.
3. the preparation method of fluorographite alkene according to claim 1 is characterized in that, the mass ratio of Graphene described in the step 3 and said fluorizating agent is 1: 1～1: 10.
4. the rare preparation method of fluorographite according to claim 3 is characterized in that the mass ratio of said Graphene and said fluorizating agent is 1: 1～1: 5
5. the preparation method of fluorographite alkene according to claim 1 is characterized in that, the purity of graphite described in the step 1 is 95～99.5%.
6. the preparation method of fluorographite alkene according to claim 1 is characterized in that, step 1 is:
With said graphite, Potassium Persulphate and Vanadium Pentoxide in FLAKES according to mass ratio 2～10: join at 1: 1 in 80～120 ℃ the vitriol oil, the back naturally cooling that stirs, washing to neutral after drying obtains mixture;
Said mixture and potassium permanganate are joined in the vitriol oil, and the temperature that keeps mixing solutions, adds deionized water and adds the hydrogen peroxide solution reaction, suction filtration, collection solid then 25 ℃～50 ℃ following oil baths 1～4 hour at 15 ℃～20 ℃; And
Said solid washs with Hydrogen chloride, and drying obtains said graphene oxide.
7. the preparation method of fluorographite alkene according to claim 1 is characterized in that, step 2 is:
Said graphene oxide and water are mixed with the suspension liquid of 1～5g/L, and use the ultrasonic equipment of 150～300W that said suspension liquid is carried out ultra-sonic dispersion;
Adding concentration is 98% Hydrazine Hydrate 80, is heated to 80～100 ℃ of reactions 24～48 hours; And
Filter, collect solid, washing, drying obtains Graphene.
8. select the preparation method of a described fluorographite alkene according to claim 3 or 4, it is characterized in that step 3 is:
Said Graphene is joined in the anhydrous methylene chloride homodisperse;
By said Graphene and fluorizating agent mass ratio 1: 1～1: 10, under the protection of rare gas element,, obtain reaction product 20～40 ℃ of following stirring reactions 1～100 hour; And
Said reaction product is added to the water, and suction filtration is collected solid, water and methanol wash successively, and drying obtains said fluorographite alkene.
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| CN104211048A (en) * | 2013-06-05 | 2014-12-17 | 中国科学院上海有机化学研究所 | Preparation method of fluorinated graphene |
| CN104211048B (en) * | 2013-06-05 | 2019-03-15 | 中国科学院上海有机化学研究所 | A kind of preparation method of fluorinated graphene |
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| CN109095463A (en) * | 2018-05-09 | 2018-12-28 | 东莞理工学院 | Improved graphene oxide/nanometer copper oxide composite material preparation method |
| CN109095463B (en) * | 2018-05-09 | 2020-09-04 | 东莞理工学院 | Improved preparation method of graphene oxide/nano copper oxide composite material |
| CN108516542A (en) * | 2018-06-27 | 2018-09-11 | 叶荣森 | A kind of preparation method of high fluorinated volume nanometer fluorinated graphene |
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