CN103626162A - Preparation method of graphene - Google Patents
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- CN103626162A CN103626162A CN201210308054.5A CN201210308054A CN103626162A CN 103626162 A CN103626162 A CN 103626162A CN 201210308054 A CN201210308054 A CN 201210308054A CN 103626162 A CN103626162 A CN 103626162A
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Abstract
A preparation method of graphene comprises the steps of: dispersing the graphite in an ionic liquid to form a mixture of graphite and ionic liquid; placing the mixture of graphite and ionic liquid in a ball-milling container, adding milling balls to carry out ball-milling, so as to obtain a slurry; taking the slurry out of the ball-milling container, separating the milling balls and conducting centrifugation and separation to obtain a graphene solution; and carrying out filtering, washing and drying treatment on the graphene solution to obtain the graphene. The ball milling method uses the ion liquid as a solvent to prepare the graphene with good dispersion, effectively prevents re-agglomeration of the graphite, and realizes large reaction amount, high yield and high specific surface area of the obtained graphene.
Description
Technical field
The present invention relates to organic semiconductor material technical field, particularly relate to the preparation method of Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal of the discoveries such as the strong K sea nurse of the peace moral of Univ Manchester UK in 2004 (Andre K.Geim), and obtains the physics Nobel prize in 2010, again causes carbon material research boom.Because its unique structure and photoelectric property become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers have been attracted.Single-layer graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m2/g(A Peigney, Ch Laurent, et al.Carbon, 2001,39,507), can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.
The method of preparing at present Graphene mainly contains graphite breakaway, chemistry redox method, ultrasonic stripping method, chemical Vapor deposition process etc.The place that these methods come with some shortcomings at present, the theoretical specific surface area of Graphene can reach 2630m
2/ g, but the specific surface area of in fact prepared Graphene is well below this numerical value, and great majority only have 600m
2/ g left and right, this has restricted the application of Graphene greatly.And the productive rate of some acquisition Graphenes is only 10% left and right.The Graphene specific surface area prepared as chemical Vapor deposition process is high but productive rate is low, and Graphene productive rate prepared by oxidation reduction process is high but specific surface area is low.
Summary of the invention
Based on this, be necessary to provide the preparation method of the high and Graphene that specific surface area is higher of a kind of productive rate.
A preparation method for Graphene, comprising:
Graphite is dispersed in ionic liquid, forms graphite and ionic liquid mixture,
Described graphite and ionic liquid mixture are placed in to ball mill container, add ball milling ball, carry out ball milling, obtain slurry;
Described slurry is taken out from described ball mill container, isolate described ball milling ball, then centrifugation obtains graphene solution; And
By described graphene solution filter successively, washing and drying treatment, obtain Graphene.
In an embodiment, described graphite is natural flake graphite, synthetic graphite, agraphitic carbon or expanded graphite therein.
Therein in an embodiment, described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide, 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
In an embodiment, described ball mill container is stainless steel ball-milling container therein, and described ball milling ball is stainless steel hard ball abrading-ball.
In an embodiment, in described graphite and ionic liquid mixture, the concentration of graphite is 1 grams per liter ~ 200 grams per liter therein.
In an embodiment, the diameter of described ball milling ball is 5 millimeters ~ 20 millimeters therein, and the volume ratio of described ball milling ball and described graphite and ionic liquid mixture is 1:0.5 ~ 1:2.
In an embodiment, the speed of described ball milling is 200 revs/min ~ 800 revs/min therein, and Ball-milling Time is 2 hours ~ 12 hours.
In an embodiment, the centrifugal speed that described centrifugation obtains graphene solution is 1000 revs/min ~ 10000 revs/min therein, and the time of described centrifugation is 1 minute ~ 10 minutes.
In an embodiment, described washing step is therein: graphene solution is filtered to 1-Methyl-2-Pyrrolidone or the DMF washing for filter residue obtaining, then use respectively ethanol, acetone, washed with de-ionized water, filtration.
In an embodiment, described drying treatment is that the filter residue obtaining in described washing step is dried to 10 ~ 20 hours in the vacuum drying oven of 60 ~ 100 ℃ therein.
According to the preparation method of above-mentioned Graphene, graphite is dispersed in ionic liquid, form graphite and ionic liquid mixture, adopt ball milled to obtain graphene solution; Pass through again centrifugal, filtration, washing and drying treatment, obtain Graphene.The method utilizes ionic liquid for solvent, and ionic liquid fusing point is low, is liquid under room temperature, does not need heating just can work as solvent, also more convenient in follow-up filtration treatment.The Graphene obtaining by ball milling has good dispersiveness, effectively prevents that Graphene from reuniting again, makes reacting weight large, and productive rate is high, and the specific surface area of the Graphene of acquisition is high.
Accompanying drawing explanation
Fig. 1 is preparation method's the schema of the Graphene of an embodiment;
Fig. 2 is the scanning electron microscope collection of illustrative plates of the Graphene of embodiment 1 preparation.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the preparation method of Graphene is described in further detail.
Refer to Fig. 1, the preparation method of the Graphene of an embodiment comprises the following steps:
Step S101, is dispersed in graphite in ionic liquid, forms graphite and ionic liquid mixture.
In the present embodiment, graphite is preferably natural flake graphite, synthetic graphite, agraphitic carbon or expanded graphite.Ionic liquid is preferably 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF
4), 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF
3sO
2)
2), 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF
3sO
3), 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF
3cO
2), 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon (EtMeImC (CF
3sO
2)
3), 1-ethyl-3-methylimidazole five acetyl fluoride imines (EtMeImN (C
2f
5sO
2)
2), 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN)
2), 1-ethyl-3,5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me
2imN (CF
3sO
2)
2), 1,3-diethyl-4-methylimidazole fluoroform sulfimide (1,3-Et
2-4-MeImN (CF
3sO
2)
2) 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2) at least one.
In graphite and ionic liquid mixture, the concentration of graphite is preferably 1g/L ~ 200g/L.If concentration is excessive, mechanical milling process is more difficult, if concentration is too small, Graphene yields poorly, and is therefore preferably the concentration range that this concentration is moderate.
Step S102, is placed in ball mill container by described graphite and ionic liquid mixture, adds ball milling ball, carries out ball milling, obtains slurry.
The ratio that can be 1:4 according to the volume of graphite and ionic liquid mixture and ball mill container volume ratio joins graphite and ionic liquid mixture in ball mill container.This ball mill container can be stainless steel ball-milling container.Ball milling ball is preferably stainless steel hard ball abrading-ball.Adopt stainless steel hard ball abrading-ball, stainless steel hard ball collision great efforts, can increase surface imperfection and the fold of Graphene, so can increase the specific surface area of Graphene after phase mutual friction.The diameter of ball milling ball is preferably 5mm ~ 20mm, and the ball milling ball adding and the volume ratio of graphite and ionic liquid mixture are preferably 1:0.5 ~ 1:2.Concrete ball milling step is: will add the ball mill container of graphite and ionic liquid mixture and ball milling ball to be installed in ball-grinding machine, setting ball milling speed is 200 revs/min ~ 800 revs/min, ball milling is arrestment after 2 ~ 12 hours, graphite is blended in ionic liquid, in mechanical milling process, after graphite is stripped from, be just distributed in ionic liquid, obtain slurry.
Step S103, takes out slurry from ball mill container, isolate ball milling ball, then centrifugation obtains graphene solution.
In the present embodiment, slurry is taken out from container, with screen cloth, ball milling ball is separated with graphene solution, then with whizzer, in centrifugal speed, be under the condition of 1000 revs/min ~ 10000 revs/min to graphene solution centrifugal 1 minute ~ 10 minutes, unstripped graphite is separated, obtain graphene solution.
Step S104, by graphene solution filter successively, washing and drying treatment, obtain Graphene.
In the present embodiment, first graphene solution is filtered to 1-Methyl-2-Pyrrolidone or N for the filter residue obtaining, the preliminary washing of dinethylformamide 3 times ~ 5 times, 1-Methyl-2-Pyrrolidone and DMF are aprotic polar solvent, ionic liquid can be washed off; Use respectively again ethanol, acetone, washed with de-ionized water, filtration.First with ethanol and acetone, 1-Methyl-2-Pyrrolidone or DMF are washed off, then with deionized water, excessive ethanol and acetone are washed off.Finally within 10 hours ~ 20 hours, can obtain Graphene by the filter residue of collecting is dry at the temperature of 60 ℃ ~ 100 ℃ in vacuum drying oven.
The preparation method's of above-mentioned Graphene advantage is: the ionic liquid fusing point of 1, selecting is low, is liquid under room temperature, does not need heating just can work as solvent, also more convenient in follow-up filtration treatment.The good dispersity of Graphene in ionic liquid, is difficult for again reuniting.2, preparation process is simple, only need simply graphite and ionic liquid to be carried out to ball milling in ball-grinding machine, then by simple separation, the dry preparation process that just completed.The productive rate of the product 3, obtaining is high and specific surface area is higher.4, the raw material of selecting can be all kinds of graphite, and raw material is easy to get.5, required equipment is all common chemical industry equipment, saves research and development equipment cost, is applicable to scale operation.
Below in conjunction with specific embodiment, describe.
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L natural flake graphite concentration is 1g/L natural flake graphite and 1-ethyl-3-methylimidazole Tetrafluoroboric acid mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 5mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:2, and the volume of ball milling ball is 2L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 200 revs/min, and ball milling is arrestment after 12 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 1000 revs/min centrifugal 10 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 3 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 20 hours at 60 ℃ of temperature in vacuum drying oven, obtains Graphene.
Refer to Fig. 2, be depicted as scanning electron microscope (scanning electron microscope, the SEM) collection of illustrative plates of the Graphene of embodiment 1 preparation, as can be seen from Figure 2, Graphene is successfully preparation.Graphene film layer thickness is about 0.5 nanometer ~ 3 nanometer, and graphene sheet layer is more concentrated, peels off respond wellly, and as calculated, the productive rate of the Graphene of the present embodiment is up to 88%, and the specific surface area of Graphene is 1866m
2/ g.
Embodiment 2
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L synthetic graphite concentration is 10g/L synthetic graphite and 1-ethyl-3-methylimidazole fluoroform sulfimide mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 10mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:1, and the volume of ball milling ball is 1L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 400 revs/min, and ball milling is arrestment after 10 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 2000 revs/min centrifugal 5 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered to DMF washing 4 times for the filter residue obtaining, again respectively with ethanol, acetone, each cleaning of deionized water once, filter, the filter residue of collecting is dried to 10 hours at 80 ℃ of temperature in vacuum drying oven, obtain Graphene.The productive rate of Graphene is 64%, and the specific surface area of Graphene is 1269m
2/ g.
Embodiment 3
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L decolorizing carbon concentration is 100g/L decolorizing carbon and 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 20mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:0.5, and the volume of ball milling ball is 0.5L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 600 revs/min, and ball milling is arrestment after 8 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 5000 revs/min centrifugal 2 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 3 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 15 hours at 100 ℃ of temperature in vacuum drying oven, obtains Graphene.The productive rate of Graphene is 69%, and the specific surface area of Graphene is 1365m
2/ g.
Embodiment 4
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L expanded graphite concentration is 200g/L expanded graphite and 1-ethyl-3-methylimidazole trifluoroacetic acid mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 10mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:1, and the volume of ball milling ball is 1L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 800 revs/min, and ball milling is arrestment after 6 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 10000 revs/min centrifugal 1 minute, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, the filter residue obtaining is again with DMF washing 5 times, again respectively with ethanol, acetone, each cleaning of deionized water once, filter, the filter residue of collecting is dried to 12 hours at 90 ℃ of temperature in vacuum drying oven, obtain Graphene.The productive rate of Graphene is 74%, and the specific surface area of Graphene is 1711m
2/ g.
Embodiment 5
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L natural flake graphite concentration is 50g/L natural flake graphite and 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 20mm, and the ball milling ball adding and the volume ratio of mixed solution are 1: 1.5, and the volume of ball milling ball is 1.5L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 500 revs/min, and ball milling is arrestment after 4 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 8000 revs/min centrifugal 4 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 4 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 18 hours at 70 ℃ of temperature in vacuum drying oven, obtains Graphene.The productive rate of Graphene is 62%, and the specific surface area of Graphene is 1436m
2/ g.
Embodiment 6
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L natural flake graphite concentration is 20g/L natural scale graphite and 1-ethyl-3-methylimidazole five acetyl fluoride imines mixed solutions.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 5mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:1.2, and the volume of ball milling ball is 1.2L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 300 revs/min, and ball milling is arrestment after 9 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 6000 revs/min centrifugal 3 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered to DMF washing 4 times for the filter residue obtaining, again respectively with ethanol, acetone, each cleaning of deionized water once, filter, the filter residue of collecting is dried to 20 hours at 60 ℃ of temperature in vacuum drying oven, obtain Graphene.The productive rate of Graphene is 71%, and the specific surface area of Graphene is 1228m
2/ g.
Embodiment 7
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L synthetic graphite concentration is 120g/L synthetic graphite and 1-ethyl-3-methylimidazole two cyaniding nitrogen mixed solutions.
(2) mixed solution is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 10mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:0.8, and the volume of ball milling ball is 0.8L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 500 revs/min, and ball milling is arrestment after 10 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 4000 revs/min centrifugal 6 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 3 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 10 hours at 100 ℃ of temperature in vacuum drying oven, obtains Graphene.The productive rate of Graphene is 66%, and the specific surface area of Graphene is 1632m
2/ g.
Embodiment 8
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L decolorizing carbon concentration is 5g/L decolorizing carbon and 1-ethyl-3,5-dimethyl miaow fluoroform sulfimide mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 20mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:2, and the volume of ball milling ball is 2L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 800 revs/min, and ball milling is arrestment after 2 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 3000 revs/min centrifugal 8 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered to DMF washing 5 times for the filter residue obtaining, again respectively with ethanol, acetone, each cleaning of deionized water once, filter, the filter residue of collecting is dried to 16 hours at 80 ℃ of temperature in vacuum drying oven, obtain Graphene.The productive rate of Graphene is 85%, and the specific surface area of Graphene is 1815m
2/ g.
Embodiment 9
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L expanded graphite concentration is 150g/L expanded graphite and 1,3-diethyl-4-methyl miaow fluoroform sulfimide mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 5mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:1, and the volume of ball milling ball is 1L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 400 revs/min, and ball milling is arrestment after 12 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 1000 revs/min centrifugal 10 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 5 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 12 hours at 90 ℃ of temperature in vacuum drying oven, obtains Graphene.The productive rate of Graphene is 76%, and the specific surface area of Graphene is 1674m
2/ g.
Embodiment 10
A preparation method for Graphene, its technical process is as follows:
(1) configuration 1L expanded graphite concentration is 200g/L expanded graphite and 1,3-diethyl-5-methyl miaow fluoroform sulfimide mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 5mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:0.5, and the volume of ball milling ball is 0.5L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 200 revs/min, and ball milling is arrestment after 8 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 1000 revs/min centrifugal 5 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered to DMF washing 4 times for the filter residue obtaining, again respectively with ethanol, acetone, each cleaning of deionized water once, filter, the filter residue of collecting is dried to 15 hours at 70 ℃ of temperature in vacuum drying oven, obtain Graphene.The productive rate of Graphene is 81%, and the specific surface area of Graphene is 1594m
2/ g.
Embodiment 11
A preparation method for Graphene, its technical process is as follows:
(1) the natural scale graphite concentration of configuration 1L is 50g/L natural scale graphite and 1-ethyl-3-methylimidazole Tetrafluoroboric acid mixed solution.
(2) mixed solution of configuration is placed in to the stainless steel ball-milling container of 4L, adding diameter is the ball milling ball of 20mm, and the ball milling ball adding and the volume ratio of mixed solution are 1:2, and the volume of ball milling ball is 2L, then seals.Stainless steel ball-milling container is installed in ball-grinding machine, and ball milling speed is set 500 revs/min, and ball milling is arrestment after 6 hours, obtains slurry.
(3) take out ball mill container, with screen cloth, by ball milling ball and solution separating, then use whizzer with the speed of 5000 revs/min centrifugal 7 minutes, unstripped graphite is separated, obtain graphene solution.
(4) graphene solution is filtered, for the filter residue obtaining, 1-Methyl-2-Pyrrolidone washing is 5 times, more respectively with ethanol, acetone, each cleaning of deionized water once, filters, the filter residue of collecting is dried to 12 hours at 100 ℃ of temperature in vacuum drying oven, obtains Graphene.The productive rate of Graphene is 73%, and the specific surface area of Graphene is 1672m
2/ g.
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 (10)
1. a preparation method for Graphene, is characterized in that, comprising:
Graphite is dispersed in ionic liquid, forms graphite and ionic liquid mixture;
Described graphite and ionic liquid mixture are placed in to ball mill container, add ball milling ball, carry out ball milling, obtain slurry;
Described slurry is taken out from described ball mill container, separated described ball milling ball, then centrifugation obtains graphene solution; And
By described graphene solution filter successively, washing and drying treatment, obtain Graphene.
2. the preparation method of Graphene according to claim 1, is characterized in that, described graphite is natural flake graphite, synthetic graphite, agraphitic carbon or expanded graphite.
3. the preparation method of Graphene according to claim 1, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methylimidazole two cyaniding nitrogen, 1-ethyl-3, 5-methylimidazole fluoroform sulfimide, 1, 3-diethyl-4-methylimidazole fluoroform sulfimide, 1, at least one in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
4. the preparation method of Graphene according to claim 1, is characterized in that, described ball mill container is stainless steel ball-milling container, and described ball milling ball is stainless steel hard ball abrading-ball.
5. the preparation method of Graphene according to claim 1, is characterized in that, in described graphite and ionic liquid mixture, the concentration of graphite is 1 grams per liter ~ 200 grams per liter.
6. the preparation method of Graphene according to claim 1, is characterized in that, the diameter of described ball milling ball is 5 millimeters ~ 20 millimeters, and the volume ratio of described ball milling ball and described graphite and ionic liquid mixture is 1:0.5 ~ 1:2.
7. the preparation method of Graphene according to claim 1, is characterized in that, the speed of described ball milling is 200 revs/min ~ 800 revs/min, and Ball-milling Time is 2 hours ~ 12 hours.
8. the preparation method of Graphene according to claim 1, is characterized in that, the centrifugal speed that described centrifugation obtains graphene solution is 1000 revs/min ~ 10000 revs/min, and the time of described centrifugation is 1 minute ~ 10 minutes.
9. the preparation method of Graphene according to claim 1, it is characterized in that, described washing step is: graphene solution is filtered to 1-Methyl-2-Pyrrolidone or the DMF washing for filter residue obtaining, then use respectively ethanol, acetone, washed with de-ionized water, filtration.
10. the preparation method of Graphene according to claim 1, is characterized in that, described drying treatment is that the filter residue obtaining in described washing step is dried to 10 ~ 20 hours in the vacuum drying oven of 60 ~ 100 ℃.
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| CN106829941A (en) * | 2017-04-07 | 2017-06-13 | 厦门大学 | A kind of preparation method of Graphene |
| CN108314022A (en) * | 2018-03-27 | 2018-07-24 | 广东聚石化学股份有限公司 | A kind of method that the direct stripping of ionic liquid prepares graphene |
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| US10322935B2 (en) | 2014-06-06 | 2019-06-18 | Nanoxplore Inc. | Large scale production of thinned graphite, graphene, and graphite-graphene composites |
| US9469542B2 (en) | 2014-06-06 | 2016-10-18 | Group Nanoxplore Inc. | Large scale production of thinned graphite, graphene, and graphite-graphene composites |
| US11367540B2 (en) | 2014-06-06 | 2022-06-21 | Nanoxplore Inc. | Large scale production of thinned graphite, graphene, and graphite-graphene composites |
| EP3152346A4 (en) * | 2014-06-06 | 2018-03-28 | NanoXplore Inc. | Large scale production of thinned graphite, graphene, and graphite-graphene composites |
| WO2016063036A1 (en) * | 2014-10-21 | 2016-04-28 | 2-Dtech Limited | Methods for the production of 2-d materials |
| CN105694594A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | An aqueous graphene conductive printing ink suitable for screen printing and a preparing method thereof |
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| CN106009424B (en) * | 2016-05-26 | 2018-03-09 | 航天材料及工艺研究所 | A kind of preparation method of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification |
| CN106009424A (en) * | 2016-05-26 | 2016-10-12 | 航天材料及工艺研究所 | Preparation method of grapheme/fluoroether rubber modified by covalent bond of fluorine-containing ionic liquid |
| CN106829941A (en) * | 2017-04-07 | 2017-06-13 | 厦门大学 | A kind of preparation method of Graphene |
| CN108586737A (en) * | 2018-03-19 | 2018-09-28 | 厦门理工学院 | A kind of conducting polymer/graphene complex and preparation method thereof |
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