CN102167314A - Method for preparing graphene - Google Patents
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- CN102167314A CN102167314A CN2011101327055A CN201110132705A CN102167314A CN 102167314 A CN102167314 A CN 102167314A CN 2011101327055 A CN2011101327055 A CN 2011101327055A CN 201110132705 A CN201110132705 A CN 201110132705A CN 102167314 A CN102167314 A CN 102167314A
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Abstract
The invention discloses a method for preparing graphene. The method comprises the following steps of: adding natural graphite, persulfate and phosphorus pentoxide into concentrated sulfuric acid, and reacting with stirring to obtain pre-oxidated graphite; adding pre-oxidated graphite, nitrate and potassium permanganate into concentrated sulfuric acid sequentially and reacting to obtain graphite oxide; and dissolving the graphite oxide in alcohol to prepare solution, performing ultrasonic dispersion, reacting in the sealed environment at the temperature of between 120 and 220 DEG C for 4 to 48houhrs, and then performing centrifugal washing until the pH is 6.5 to 7.5, and performing vacuum drying to obtain black graphene powder. No reducing agent is adopted in the method, the reducing capacity of a solvent is used to reduce the graphite oxide, and the method has the advantages of low cost, and light pollution, and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation field of Graphene, be specifically related to a kind of pure thermal reduction preparation method of Graphene.
Background technology
Graphene (graphene) is owing to have unique two dimensional crystal structure, high electronic conductivity, high thermal conductivity and high physical strength and high chemical stability, in a lot of fields, have broad application prospects as fields such as photoelectron, magnetic energy, energy storage, catalysis.Since 2004 are found first, more and more be subjected to the attention of scientific circles, cause the climax of research Graphene in the world, find that the earliest two scientists of Graphene obtain the Nobel Prize in physics in 2010 years.
The method for preparing at present Graphene has mechanically peel method, chemical Vapor deposition process and solution chemistry method.Mechanically peel method and chemical Vapor deposition process are not suitable for heavy industrialization and use because rate ratio is lower.The scale operation Graphene generally adopts the solution chemistry method, promptly earlier the natural graphite oxidation is prepared graphite oxide (graphene oxide), again graphite oxide is reduced into Graphene.Under liquid-phase condition, generally adopt hydrazine hydrate, NaBH
4Or KBH
4Deng reductive agent graphite oxide is reduced.Because this class reductive agent price is higher, and can pollute, and also is not suitable for large-scale industrial production.
For quality and the need of industrial production of taking into account Graphene, software engineering researchers invent many new preparation methods, as disclosing a kind of preparation method of graphene among the Chinese patent ZL200910077131.9: with sodium Metal 99.5 and halohydrocarbon is raw material, by carry out the prepared in reaction Graphene in solvent under inert environments.A kind of preparation method of graphene is disclosed among the Chinese patent ZL200810113596.0, this method is to adopt process for preparing graphenes by chemical vapour deposition, comprise: the substrate that will have catalyzer is put into the reactor of anaerobic, make substrate temperature reach 500～1200 ℃, in described reactor, feed carbonaceous material then, obtain Graphene; Wherein, described catalyzer is metal or metallic compound.
Summary of the invention
The invention provides a kind of pure thermal reduction preparation method of Graphene, this method does not adopt any reductive agent, but utilizes the reducing power of solvent self to come reduction-oxidation graphite, and it is low to have a cost, pollutes fewly, is fit to the advantage of large-scale industrial production.
A kind of preparation method of graphene comprises step:
1) natural graphite, persulphate and Vanadium Pentoxide in FLAKES are joined in the vitriol oil, adding deionized water 60 ℃～90 ℃ stirrings while stirring after 4 hours～10 hours makes it be cooled to 20 ℃～28 ℃, gained suspension cleans to pH=6.5～7.5 with the deionized water suction filtration, through vacuum-drying, obtain preoxidation graphite;
2) the preoxidation graphite, nitrate and the potassium permanganate that step 1) are obtained join in the vitriol oil successively, ice bath stirred 1 hour～3 hours down, being warming up to 30 ℃～40 ℃ again stirred 2 hours～4 hours, the warm water that adds 60 ℃～80 ℃ then, and temperature risen to 70 ℃～100 ℃ and kept 10 minutes～40 minutes, with 60 ℃～80 ℃ warm water dilution, add H more successively at last
2O
2And dilute hydrochloric acid, and solution centrifugal washed to pH=6.5～7.5, through vacuum-drying, obtain graphite oxide;
3) graphite oxide be dissolved in be configured to solution in the alcohol, through behind the ultra-sonic dispersion in sealed environment in 120 ℃～220 ℃ reactions 4 hours～48 hours down, centrifuge washing through vacuum-drying, obtains the graphene powder of black to pH=6.5～7.5 then.
In order to reach better invention effect, preferably:
In the step 1), described persulphate is selected Sodium Persulfate, Potassium Persulphate or ammonium persulphate for use.
In the step 1), the mass ratio of described natural graphite, persulphate, Vanadium Pentoxide in FLAKES and the vitriol oil is 1: 1～3: 1～3: 10～30.Wherein, natural graphite is as raw material, and persulphate and Vanadium Pentoxide in FLAKES are as oxygenant, and the adding of the vitriol oil can further strengthen the oxidation capacity of oxygenant.
Step 2) in, described nitrate is selected SODIUMNITRATE or saltpetre for use.
Step 2) in, the mass ratio of described preoxidation graphite, nitrate, potassium permanganate and the vitriol oil is 1: 1～3: 2～6: 20～50.Wherein, preoxidation graphite is as raw material, and nitrate and potassium permanganate are as oxygenant, and the adding of the vitriol oil can further strengthen the oxidation capacity of oxygenant.
Described warm water and step 2 before temperature being risen to 70 ℃～100 ℃ steps) described in the volume ratio of the vitriol oil be 1.9: 1～4: 1.
Described warm water and step 2 after temperature being risen to 70 ℃～100 ℃ steps) described in the volume ratio of the vitriol oil be 4: 1～8: 1.
Described H
2O
2(hydrogen peroxide) is used for some high price mn ions are reduced into soluble divalent manganesetion, and the preferred mass percentage concentration is the H of 10%-40%
2O
2
Described dilute hydrochloric acid is some metals or oxide precipitation dissolving just, and the preferred mass percentage concentration is the dilute hydrochloric acid of 3%-10%.
In the step 3), described alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol, propyl carbinol or isopropylcarbinol.
Consider the solubleness of graphite oxide in alcohol to avoid unnecessary waste, the concentration of graphite oxide is 0.1mg/mL～1mg/mL in the described solution.
Described vacuum-drying is 60 ℃～80 ℃ vacuum-dryings 6 hours～12 hours.
The described vitriol oil refers to that concentration expressed in percentage by weight more than or equal to 70% sulfuric acid, has implication sanctified by usage in this area.
Compared with prior art, the present invention has the following advantages:
1), the preparation of graphite oxide of the present invention carries out in two steps, promptly carries out preoxidation earlier and carries out deep oxidation again, Zhi Bei graphite oxide oxidation gets more fully, more thorough in this way, is easilier disperseed in solvent, for follow-up abundant reduction creates conditions.
2), the reduction of graphite oxide of the present invention adopts pure hot method, reduction-oxidation graphite need not any reductive agent such as hydrazine hydrate, NaBH in this way
4Or KBH
4, and utilize the reduction characteristic of solvent (alcohols) self to come reduction-oxidation graphite, the alcohols price of use is lower, so suitable low-cost, the large-scale industrial production of the present invention, and can reduce pollution.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained Graphene.
Fig. 2 is the stereoscan photograph of embodiment 1 gained Graphene.
Fig. 3 is the transmission electron microscope photo of embodiment 1 gained Graphene.
Fig. 4 is the X ray diffracting spectrum of embodiment 2 gained Graphenes.
Fig. 5 is the stereoscan photograph of embodiment 2 gained Graphenes.
Fig. 6 is the transmission electron microscope photo of embodiment 2 gained Graphenes.
Fig. 7 is the X ray diffracting spectrum of embodiment 3 gained Graphenes.
Fig. 8 is the stereoscan photograph of embodiment 3 gained Graphenes.
Fig. 9 is the transmission electron microscope photo of embodiment 3 gained Graphenes.
Embodiment
Embodiment 1
1), with 5 gram Potassium Persulphate, it is in 98% the vitriol oil (71.8g) that 5 gram Vanadium Pentoxide in FLAKESs and 5 gram natural graphite powders join 39 milliliters of mass percentage concentration, stirred 6 hours at 80 ℃ of lower magnetic forces, adding deionized water then while stirring makes it be cooled to room temperature, suspension cleans to pH=7 with the deionized water suction filtration, obtains 5.3 gram preoxidation graphite in 10 hours 60 ℃ of following vacuum-dryings again;
2), with 2 gram preoxidation graphite, 2 gram SODIUMNITRATE, it is in 98% the vitriol oil (84.6g) that 6 gram potassium permanganate join 46 milliliters of mass percentage concentration, ice bath stirred 1 hour down, being warming up to 35 ℃ again stirred 2 hours, the warm water that adds 90 milliliters 70 ℃ then, and temperature risen to 98 ℃ and kept 15 minutes then adds 280 milliliters 70 ℃ warm water, 10 milliliters of mass percentage concentration and is 30% H successively
2O
2And 24 milliliters of mass percentage concentration are 5% dilute hydrochloric acid, to pH=7, and obtain the 4.3g graphite oxide in 10 hours 60 ℃ of following vacuum-dryings through abundant centrifuge washing;
3), the 0.05g graphite oxide is dissolved in the solution that is configured to 0.5mg/mL in the ethanol, through in autoclave, reacting 24 hours down behind the ultra-sonic dispersion in 200 ℃, after the cooling with the throw out centrifuge washing to pH=7, and obtained the graphene powder of 0.021g black in 10 hours 60 ℃ of following vacuum-dryings.
Adopt X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, X ray diffracting spectrum (XRD figure spectrum) is as Fig. 1, as can be seen from Figure 1: through pure thermal response, graphite oxide has been reduced into Graphene, is characterized as (002) diffraction peak that occurs about 25 degree.
Adopt scanning electron microscope and transmission electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph and transmission electron microscope photo can be found out from Fig. 2 and Fig. 3 respectively as Fig. 2 and Fig. 3: through pure thermal response, formed laminar ground Graphene.
Embodiment 2
1), with 15 gram Potassium Persulphate, it is in 90% the vitriol oil that 15 gram Vanadium Pentoxide in FLAKESs and 5 gram natural graphite powders join the 150g mass percentage concentration, stirred 4 hours at 90 ℃ of lower magnetic forces, adding deionized water then while stirring makes it be cooled to 28 ℃, suspension cleans to pH=6.5 with the deionized water suction filtration, obtains 5.5g preoxidation graphite in 6 hours 80 ℃ of following vacuum-dryings again;
2), with 2 gram preoxidation graphite, 6 gram SODIUMNITRATE, it is in 98% the vitriol oil that 4 gram potassium permanganate join the 40g mass percentage concentration, ice bath stirred 3 hours down, being warming up to 30 ℃ again stirred 4 hours, the warm water that adds 90 milliliters 60 ℃ then, and temperature risen to 70 ℃ and kept 40 minutes then adds 280 milliliters 60 ℃ warm water, 10 milliliters of mass percentage concentration and is 10% H successively
2O
2And 24 milliliters of mass percentage concentration are 10% dilute hydrochloric acid, to pH=6.5, and obtain the 4.5g graphite oxide in 6 hours 80 ℃ of following vacuum-dryings through abundant centrifuge washing;
3), the 0.01g graphite oxide is dissolved in the solution that is configured to 0.1mg/mL in the Virahol, through in autoclave, reacting 48 hours down behind the ultra-sonic dispersion in 120 ℃, after the cooling with the throw out centrifuge washing to pH=6.5, and obtained the graphene powder of 0.004g black in 6 hours 80 ℃ of following vacuum-dryings.
Adopt X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, the XRD figure spectrum shows as Fig. 4: through pure thermal response, graphite oxide has been reduced into Graphene, is characterized as (002) diffraction peak that occurs about 25 degree.
Adopt scanning electron microscope and transmission electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 5 and transmission electron microscope photo such as Fig. 6 show: through pure thermal response, formed laminar ground Graphene.
Embodiment 3
1), with 10 gram Potassium Persulphate, it is in 70% the vitriol oil that 10 gram Vanadium Pentoxide in FLAKESs and 5 gram natural graphite powders join the 50g mass percentage concentration, stirred 10 hours at 60 ℃ of lower magnetic forces, adding deionized water then while stirring makes it be cooled to 20 ℃, suspension cleans to pH=7.5 with the deionized water suction filtration, obtains 5.2g preoxidation graphite in 12 hours 70 ℃ of following vacuum-dryings again;
2), with 2 gram preoxidation graphite, 4 gram SODIUMNITRATE, it is in 98% the vitriol oil that 12 gram potassium permanganate join the 100g mass percentage concentration, ice bath stirred 2 hours down, being warming up to 40 ℃ again stirred 3 hours, the warm water that adds 400 milliliters 80 ℃ then, and temperature risen to 100 ℃ and kept 10 minutes then adds 400 milliliters 80 ℃ warm water, 10 milliliters of mass percentage concentration and is 40% H successively
2O
2And 24 milliliters of mass percentage concentration are 3% dilute hydrochloric acid, to pH=7.5, and obtain the 4.7g graphite oxide in 12 hours 70 ℃ of following vacuum-dryings through abundant centrifuge washing;
3), the 0.1g graphite oxide is dissolved in the solution that is configured to 1mg/mL in the methyl alcohol, through in autoclave, reacting 4 hours down behind the ultra-sonic dispersion in 220 ℃, after the cooling with the throw out centrifuge washing to pH=7.5, and obtained the graphene powder of 0.046g black in 12 hours 70 ℃ of following vacuum-dryings.
Adopt X ray polycrystalline diffractometer that the final reacting product of gained is carried out material phase analysis, the XRD figure spectrum shows as Fig. 7: through pure thermal response, graphite oxide has been reduced into Graphene, is characterized as (002) diffraction peak that occurs about 25 degree.
Adopt scanning electron microscope and transmission electron microscope that the final reacting product of gained is analyzed, its stereoscan photograph such as Fig. 8 and transmission electron microscope photo such as Fig. 9 show:: through pure thermal response, formed laminar ground Graphene.
Claims (10)
1. a preparation method of graphene is characterized in that, comprises step:
1) natural graphite, persulphate and Vanadium Pentoxide in FLAKES are joined in the vitriol oil, adding deionized water 60 ℃～90 ℃ stirrings while stirring after 4 hours～10 hours makes it be cooled to 20 ℃～28 ℃, gained suspension cleans to pH=6.5～7.5 with the deionized water suction filtration, through vacuum-drying, obtain preoxidation graphite;
2) the preoxidation graphite, nitrate and the potassium permanganate that step 1) are obtained join in the vitriol oil successively, ice bath stirred 1 hour～3 hours down, being warming up to 30 ℃～40 ℃ again stirred 2 hours～4 hours, the warm water that adds 60 ℃～80 ℃ then, and temperature risen to 70 ℃～100 ℃ and kept 10 minutes～40 minutes, with 60 ℃～80 ℃ warm water dilution, add H more successively at last
2O
2And dilute hydrochloric acid, and solution centrifugal washed to pH=6.5～7.5, through vacuum-drying, obtain graphite oxide;
3) graphite oxide is dissolved in is configured to the solution that graphite oxide concentration is 0.1mg/mL～1mg/mL in the alcohol, through in sealed environment, reacting 4 hours～48 hours down behind the ultra-sonic dispersion in 120 ℃～220 ℃, centrifuge washing is to pH=6.5～7.5 then, through vacuum-drying, obtain the graphene powder of black.
2. preparation method of graphene according to claim 1 is characterized in that, in the step 1), described persulphate is Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
3. preparation method of graphene according to claim 1 is characterized in that, in the step 1), the mass ratio of described natural graphite, persulphate, Vanadium Pentoxide in FLAKES and the vitriol oil is 1: 1～3: 1～3: 10～30.
4. preparation method of graphene according to claim 1 is characterized in that step 2) in, described nitrate is SODIUMNITRATE or saltpetre.
5. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that step 2) in, the mass ratio of described preoxidation graphite, nitrate, potassium permanganate and the vitriol oil is 1: 1～3: 2～6: 20～50.
6. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that, described warm water and step 2 before temperature being risen to 70 ℃～100 ℃ steps) described in the volume ratio of the vitriol oil be 1.9: 1～4: 1.
7. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that, described warm water and step 2 after temperature being risen to 70 ℃～100 ℃ steps) described in the volume ratio of the vitriol oil be 4: 1～8: 1.
8. preparation method of graphene according to claim 1 is characterized in that, in the step 3), described alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, ethylene glycol, propyl carbinol or isopropylcarbinol.
9. preparation method of graphene according to claim 1 is characterized in that, described vacuum-drying is 60 ℃～80 ℃ vacuum-dryings 6 hours～12 hours.
10. the preparation method of bow tie antimonous oxide according to claim 1 is characterized in that, the concentration expressed in percentage by weight of the described vitriol oil is at least 70%;
Described H
2O
2Mass percentage concentration be 10%-40%;
The mass percentage concentration of described dilute hydrochloric acid is 3%-10%.
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