CN103626164A - Graphene preparation method - Google Patents
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- CN103626164A CN103626164A CN201210310132.5A CN201210310132A CN103626164A CN 103626164 A CN103626164 A CN 103626164A CN 201210310132 A CN201210310132 A CN 201210310132A CN 103626164 A CN103626164 A CN 103626164A
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Abstract
The invention relates to a graphene preparation method, which comprises the following five steps: 1, mixing graphite and a chloride intercalation agent to obtain a reactant, and carrying out a reaction of the reactant at a temperature of 460-550 DEG C to obtain an intermediate product, 2, washing and drying the intermediate product to obtain pure intercalation graphite, 3, mixing the intercalation graphite and an ion liquid to form an intercalation graphite and ion liquid mixture, and placing the intercalation graphite and ion liquid mixture in a constant magnetic field to carry out a centrifugation treatment, 4, washing the precipitate obtained through the centrifugation treatment to obtain graphene, and 5, carrying out vacuum drying. The graphene preparation method has characteristics of simple operation, high production efficiency and easy industrialization achievement.
Description
Technical field
The present invention relates to the synthetic field of material, particularly a kind of 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.Graphene has good conduction, heat conductivility and low thermal expansivity, can be used for electrode materials, matrix material etc.In current preparation method, there is graphite oxide reduction method, but the destruction that this method can cause graphene-structured; Also have by pyrolytic decomposition carbon source and prepare Graphene, but this method production efficiency is lower.
Summary of the invention
Given this, be necessary to provide a kind of method of the simple to operate and Graphene that efficiency is higher.
A preparation method for Graphene, comprises the steps:
Step 1: graphite and muriate intercalator are mixed to get to reactant, the reaction at 460 ℃ ~ 550 ℃ of temperature of described reactant is obtained to intermediate product;
Step 2: obtain pure intercalated graphite after described intermediate product is cleaned, is dried;
Step 3: form the mixture of intercalated graphite and ionic liquid after intercalated graphite, ionic liquid are mixed, the mixture of described intercalated graphite and ionic liquid is placed in to stationary magnetic field, carry out centrifugal treating;
Step 4: the throw out obtaining after described centrifugal treating is cleaned, obtain Graphene;
Step 5: vacuum-drying.
In an embodiment, described graphite is natural flake graphite or synthetic graphite therein.
In an embodiment, described muriate intercalator is selected from least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride therein.
In an embodiment, the mass ratio of described graphite and described muriate intercalator is 1: 0.8 ~ 1: 1.2 therein, and the time of described insulation reaction is 2 hours ~ 6 hours.
In an embodiment, the magneticstrength of described stationary magnetic field is 0.01 tesla～1 tesla therein.
In an embodiment, described centrifugal treating condition is therein: 1000 revs/min～10000 revs/min of rotating speeds, 10 minutes～100 minutes treatment time.In an embodiment, described cleaning comprises organic solvent cleaning therein, and described organic solvent is N-Methyl pyrrolidone or dimethyl formamide.Therein in an embodiment, described ionic liquid is selected from 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 and 1, at least one of 3-diethyl-5-Methylimidazole fluoroform sulfimide.
In an embodiment, the mass volume ratio of described intercalated graphite and ionic liquid is 1g:10mL ~ 100mL therein.
In an embodiment, described vacuum-drying condition is therein: temperature 60 C ~ 100 ℃, 10 hours ~ 20 hours reaction times.
The preparation method of above-mentioned Graphene, adopt intercalator at high temperature to react preparation intercalated graphite with graphite, and intercalated graphite is scattered in ionic liquid, under magnetic field and centrifugation, peel off fast and prepare Graphene, simple to operate, production efficiency is higher, is easy to realize industrialization.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the Graphene of an embodiment;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the Graphene of embodiment 1 preparation.
Embodiment
Below mainly in conjunction with the drawings and the specific embodiments the preparation method of Graphene is described in further detail.
As shown in Figure 1, the preparation method of the Graphene of an embodiment, comprises the steps:
Step S110: graphite and muriate intercalator are mixed to get to reactant, reactant reaction at 460 ℃ ~ 550 ℃ of temperature is obtained to intermediate product.
Wherein, muriate intercalator is selected from least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
Under the high temperature of 460 ℃ ~ 550 ℃, these several muriate intercalators easily form fused salt and intercalation occur fast, improve preparation efficiency.
Wherein, graphite is the conventional graphite in this area, is preferably natural flake graphite or synthetic graphite.
The mass ratio of graphite and intercalator is preferably 1:0.8 ~ 1:1.2.Graphite reacts for some time and obtains intermediate product at 460 ℃ ~ 550 ℃ with muriate intercalator.Reaction time be preferably 2 hours ~ 6 hours.Intermediate product contains intercalated graphite.
Step S120: obtain pure intercalated graphite after intermediate product is cleaned, is dried.
The intermediate product that step S110 obtains contains intercalated graphite.In order to obtain pure intercalated graphite, after intermediate product is filtered, use washed with de-ionized water filter residue, and dry, that obtain being dried, pure intercalated graphite.
Dry condition is, under vacuum condition, at 80 ℃ ~ 100 ℃, to be dried 4 hours ~ 6 hours.
Step S130: form the mixture of intercalated graphite and ionic liquid after intercalated graphite, ionic liquid are mixed, the mixture of intercalated graphite and ionic liquid is placed in to stationary magnetic field, carry out centrifugal treating.
Wherein, stationary magnetic field is that the magnetic field that magneticstrength and direction remain unchanged is called Huo Heng magnetic field, stationary magnetic field.
Preferably, the magneticstrength of stationary magnetic field is tesla of 0.01 tesla (T)～1 (T).The condition of centrifugal treating, for being under 1000 revs/min～10000 revs/min at rotating speed, is carried out centrifugal treating 10 minutes～100 minutes.
In stationary magnetic field, with 1000 revs/min～10000 revs/min, carrying out high speed centrifugation is in order to make the ion in intercalated graphite be subject to lorentz's force and reach peeling off effect, the stressed opposite direction of negative ions and form peeling force and make intercalated graphite peel off into Graphene.
Wherein, ionic liquid is selected from 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
3), 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) and 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2) at least one.
Intercalated graphite is scattered in ionic liquid and is convenient to peel off, and the Graphene obtaining after peeling off is also scattered in ionic liquid.With ionic liquid, as dispersion liquid, can prevent Graphene reunion, thereby improve the productive rate of Graphene.The quality of intercalated graphite is 1g:10mL ~ 100mL with the ratio of the volume of ionic liquid, so that intercalated graphite and peel off the graphite obtaining and be well-dispersed in ionic liquid, improves the efficiency peeled off and the productive rate of Graphene.
The impurity that can not induce one in stripping process, filters and obtains filtrate, and ionic liquid can reclaim and again utilize, and is conducive to reduce preparation cost.
Step S140: the throw out obtaining after centrifugal treating is cleaned, obtain Graphene.
The throw out obtaining after step S 130 centrifugal treating is cleaned, obtain pure Graphene.
Adopt organic solvent to clean.By organic solvent extraction filter 23 for throw out ~ 5 times, then filter with deionized water, until filtrate is detected without chlorion with Silver Nitrate.
Organic solvent is preferably N-Methyl pyrrolidone (NMP) or dimethyl formamide (DMF).
Step S150: vacuum-drying.
Under vacuum condition, the throw out after cleaning is dried to 10 hours ~ 20 hours at 60 ℃ ~ 100 ℃, obtain dry Graphene.
The preparation method of above-mentioned Graphene, adopt muriate intercalator at high temperature to react preparation intercalated graphite with graphite, and intercalated graphite is scattered in ionic liquid, under magnetic field and centrifugation, peel off fast and prepare Graphene, simple to operate, production efficiency is higher, is easy to realize industrialization.
In addition, the preparation method of above-mentioned Graphene, utilizes ionic liquid to make solution, and prepares Graphene under magnetic field and centrifugation, and the Graphene obtaining has good dispersiveness, and individual layer rate can reach more than 60%, and the number of plies concentrates between 1 ~ 5 layer.Preparation method's raw material sources of above-mentioned Graphene are wide, and solvent can reuse, and cost is low.
Be below specific embodiment part:
Embodiment 1
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:0.8 in mass ratio by natural flake graphite and iron(ic) chloride, natural flake graphite and iron(ic) chloride are placed in to sealed silica envelope, be warming up to 460 ℃, insulation reaction 2 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 80 ℃ dry 6 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:10ml, intercalated graphite is joined EtMeImBF is housed
4in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 1T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 10 minutes so that the speed of 1000 revs/min is centrifugal, the centrifugal N-Methyl pyrrolidone for throw out (NMP) obtaining is filtered 5 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 20 hours at 60 ℃, obtain the Graphene of the present embodiment.
Fig. 2 represents is the scanning electron microscope (SEM) photograph (SEM) of the Graphene prepared of the present embodiment.From Fig. 2, can learn, the thickness of the lamella of Graphene prepared by the present embodiment is about 0.5 nanometer ~ 2 nanometer, and graphene sheet layer is more concentrated, peels off respond well.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 2
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:0.9 in mass ratio by synthetic graphite and cupric chloride, synthetic graphite and iron(ic) chloride are placed in to sealed silica envelope, be warming up to 500 ℃, insulation reaction 3 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 90 ℃ dry 5 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:100ml, intercalated graphite joined in the container that ionic liquid mixed solution is housed, ionic liquid mixed solution is EtMeImBF
4and EtMeImN (CF
3sO
2)
2mixed solution, EtMeImBF
4and EtMeImN (CF
3sO
2)
2volume ratio be 1:1, EtMeImBF
4and EtMeImN (CF
3sO
2)
2volume sum be 100ml.The mixture of getting the mixed solution of 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.5T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 50 minutes so that the speed of 2000 revs/min is centrifugal, by centrifugal dimethyl formamide for throw out (DMF) filter 23 obtaining, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 10 hours at 80 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 3
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.2 in mass ratio by natural flake graphite and nickelous chloride, natural flake graphite and nickelous chloride are placed in to sealed silica envelope, be warming up to 480 ℃, insulation reaction 6 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 100 ℃ dry 4 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:50ml, intercalated graphite joined in the container that ionic liquid mixed solution is housed, ionic liquid mixed solution is EtMeImCF
3cO
3, EtMeImBF
4and EtMeImCF
3sO
3mixed solution, EtMeImCF
3cO
3, EtMeImBF
4and EtMeImCF
3sO
3volume ratio be 1:1:2, EtMeImCF
3cO
3, EtMeImBF
4and EtMeImCF
3sO
3volume sum be 50ml.The mixture of getting the mixed solution of 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.1T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 30 minutes so that the speed of 5000 revs/min is centrifugal, by centrifugal N-Methyl pyrrolidone for thing (NMP) filter 23 that is precipitated, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 15 hours at 100 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 4
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.0 in mass ratio by synthetic graphite and cobalt chloride, synthetic graphite and cobalt chloride are placed in to sealed silica envelope, be warming up to 550 ℃, insulation reaction 4 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 90 ℃ dry 4.5 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:20ml, intercalated graphite is joined EtMeImCF is housed
3cO
3in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.05T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 10 minutes so that the speed of 8000 revs/min is centrifugal, by centrifugal dimethyl formamide for throw out (DMF) filter 23 obtaining, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 12 hours at 90 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 5
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by natural flake graphite and Repone K, natural flake graphite and Repone K are placed in to sealed silica envelope, be warming up to 520 ℃, insulation reaction 5 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 85 ℃ dry 5.5 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:80ml, intercalated graphite is joined EtMeImC (CF is housed
3sO
2)
3in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.01T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 20 minutes so that the speed of 10000 revs/min is centrifugal, the centrifugal throw out N-Methyl pyrrolidone (NMP) obtaining is filtered 4 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 18 hours at 70 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 6
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:0.8 in mass ratio by synthetic graphite and sodium-chlor, synthetic graphite and sodium-chlor are placed in to sealed silica envelope, be warming up to 530 ℃, insulation reaction 2 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 95 ℃ dry 6 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:60ml, intercalated graphite is joined EtMeImN (C is housed
2f
5sO
2)
2in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.2T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 40 minutes so that the speed of 2000 revs/min is centrifugal, the centrifugal dimethyl formamide for throw out (DMF) obtaining is filtered 4 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 20 hours at 60 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 7
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by natural flake graphite and magnesium chloride, natural flake graphite and magnesium chloride are placed in to sealed silica envelope, be warming up to 490 ℃, insulation reaction 3 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 90 ℃ dry 3 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:40ml, intercalated graphite is joined EtMeImN (CN) is housed
2in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.4T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 60 minutes so that the speed of 2500 revs/min is centrifugal, by centrifugal N-Methyl pyrrolidone for throw out (NMP) filter 23 obtaining, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 10 hours at 100 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 8
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.0 in mass ratio by synthetic graphite and lead chloride, synthetic graphite and lead chloride are placed in to sealed silica envelope, be warming up to 540 ℃, insulation reaction 6 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 100 ℃ dry 5 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:30ml, intercalated graphite joined 1-Et-3 is housed, 5-Me
2imN (CF
3sO
2)
2in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.8T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 80 minutes so that the speed of 1000 revs/min is centrifugal, the centrifugal dimethyl formamide for throw out (DMF) obtaining is filtered 5 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 16 hours at 80 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 9
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:0.9 in mass ratio by natural flake graphite and zinc chloride, natural flake graphite and zinc chloride are placed in to sealed silica envelope, be warming up to 520 ℃, insulation reaction 5 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 80 ℃ dry 6 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:100ml, intercalated graphite is joined 1,3-Et is housed
2-4-MeImN (CF
3sO
2)
2in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 1T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 50 minutes so that the speed of 3000 revs/min is centrifugal, the centrifugal N-Methyl pyrrolidone for throw out (NMP) obtaining is filtered 5 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 12 hours at 90 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 10
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by synthetic graphite and bariumchloride, natural flake graphite and bariumchloride are placed in to sealed silica envelope, be warming up to 550 ℃, insulation reaction 4 hours, is cooled to room temperature after reaction finishes, and obtains intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 90 ℃ dry 4 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:10ml, intercalated graphite is joined 1,3-Et is housed
2-5-MeImN (CF
3sO
2)
2in the container of ionic liquid, the mixture of getting 1L intercalated graphite and ionic liquid joins in the supercentrifuge that capacity is 2L and builds, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.1T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 10 minutes so that the speed of 5000 revs/min is centrifugal, the centrifugal dimethyl formamide for throw out (DMF) obtaining is filtered 4 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 14 hours at 70 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
Embodiment 11
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: be 50% iron(ic) chloride by synthetic graphite and mass ratio: the mixture of 50% cupric chloride is 1:1.2 in mass ratio, natural flake graphite and iron(ic) chloride and cupric chloride are placed in to sealed silica envelope, be warming up to 460 ℃, insulation reaction 2 hours, after reaction finishes, be cooled to room temperature, obtain intercalated graphite.By intercalated graphite with after washed with de-ionized water, then in vacuum drying oven in 100 ℃ dry 6 hours, obtain pure intercalated graphite.
(2) according to mass volume ratio, be 1g:50ml, intercalated graphite is joined EtMeImCF is housed
3cO
3in the container of ionic liquid, the mixture of getting 1L intercalated graphite waters ionic liquid joins in the supercentrifuge that capacity is 2L to be built, at whizzer top base two ends, add that magneticstrength is the stationary magnetic field of 0.01T, start magnetic field, whizzer, allow whizzer peel off intercalated graphite 100 minutes so that the speed of 8000 revs/min is centrifugal, the centrifugal N-Methyl pyrrolidone for throw out (NMF) obtaining is filtered 5 times, then filter until filtrate AgNO with deionized water
3detection is without chlorion; Filter residue after cleaning is put in vacuum drying oven and is dried 12 hours at 100 ℃, obtain the Graphene of the present embodiment.
After tested, obtain the individual layer rate of the present embodiment Graphene, in Table 1.
What table 1 represented is the individual layer rate of the Graphene of embodiment 1 ~ embodiment 11 preparations.
Table 1
From table 1, can learn, the individual layer rate of the Graphene of embodiment 1 ~ embodiment 11 preparations is all more than 60%.And being about 18% left and right by the standby Graphene individual layer rate of chemistry redox legal system, the quality of the Graphene that embodiment 1 ~ embodiment 11 prepares is higher.
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, comprises the steps:
Step 1: graphite and muriate intercalator are mixed to get to reactant, the reaction at 460 ℃ ~ 550 ℃ of temperature of described reactant is obtained to intermediate product;
Step 2: obtain pure intercalated graphite after described intermediate product is cleaned, is dried;
Step 3: form the mixture of intercalated graphite and ionic liquid after intercalated graphite, ionic liquid are mixed, the mixture of described intercalated graphite and ionic liquid is placed in to stationary magnetic field, carry out centrifugal treating;
Step 4: the throw out obtaining after described centrifugal treating is cleaned, obtain Graphene;
Step 5: vacuum-drying.
2. the preparation method of Graphene according to claim 1, is characterized in that, described graphite is natural flake graphite or synthetic graphite.
3. the preparation method of Graphene according to claim 1, it is characterized in that, described muriate intercalator is selected from least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
4. according to the preparation method of the Graphene described in claim 1 or 3, it is characterized in that, the mass ratio of described graphite and described muriate intercalator is 1:0.8 ~ 1:1.2, and the described reaction times is 2 hours ~ 6 hours.
5. the preparation method of Graphene according to claim 1, is characterized in that, the magneticstrength of described stationary magnetic field is 0.01 tesla～1 tesla.
6. the preparation method of Graphene according to claim 1, is characterized in that, described centrifugal treating condition is: 1000 revs/min～10000 revs/min of rotating speeds, 10 minutes～100 minutes treatment time.
7. the preparation method of Graphene according to claim 1, is characterized in that, described cleaning comprises organic solvent cleaning, and described organic solvent is N-Methyl pyrrolidone or dimethyl formamide.
8. the preparation method of Graphene according to claim 1, it is characterized in that, described ionic liquid is selected from 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 and 1, at least one of 3-diethyl-5-Methylimidazole fluoroform sulfimide.
9. according to the preparation method of the Graphene described in claim 1 or 8, it is characterized in that, the mass volume ratio of described intercalated graphite and ionic liquid is 1g:10mL ~ 100mL.
10. the preparation method of Graphene according to claim 1, is characterized in that, described vacuum-drying condition is: temperature 60 C ~ 100 ℃, 10 hours ~ 20 hours reaction times.
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| CN105314628A (en) * | 2015-11-09 | 2016-02-10 | 新乡远东电子科技有限公司 | Graphene and preparation method thereof, as well as application to lithium battery cathode conductive agent |
| CN105776187A (en) * | 2016-01-27 | 2016-07-20 | 复旦大学 | Method for green environmental-protection preparation of high-concentration ultra-clean graphene dispersion liquid |
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