CN103626163A - Graphene preparation method - Google Patents
Graphene preparation method Download PDFInfo
- Publication number
- CN103626163A CN103626163A CN201210310131.0A CN201210310131A CN103626163A CN 103626163 A CN103626163 A CN 103626163A CN 201210310131 A CN201210310131 A CN 201210310131A CN 103626163 A CN103626163 A CN 103626163A
- Authority
- CN
- China
- Prior art keywords
- graphite
- graphene
- preparation
- intercalated graphite
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
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 carrying out an ultrasonic treatment on the mixture, 4, filtering and washing the ultrasonically-treated mixture 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 production 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: will intercalated graphite, ionic liquid forms the mixture of intercalated graphite and ionic liquid after mixing, mixture described in supersound process;
Step 4: the mixture through supersound process is filtered, cleaned, obtain Graphene;
Step 5: vacuum-drying.
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 described reaction times is 2 hours ~ 6 hours.
In an embodiment, described supersound process condition is therein: 400 watts ~ 800 watts of power, the treatment time is 0.5 hour ~ 24 hours.
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 in 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.
Therein in an embodiment, in described step 3, before the mixture of intercalated graphite and ionic liquid, also add water described in supersound process, the volume ratio of described water and ionic liquid is 10 ~ 90:90 ~ 10.
In an embodiment, the mass volume ratio of the mixture of described intercalated graphite and ionic liquid and water is 1g:10mL ~ 100mL therein.
In an embodiment, described cleaning comprises organic solvent cleaning therein, and described organic solvent is N-Methyl pyrrolidone or dimethyl formamide.
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 water, under supersound process effect, 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 muriate intercalator is preferably 1:0.8 ~ 1:1.2.The time of the reactant that graphite and muriate intercalator are mixed to get insulation reaction at 460 ℃ ~ 550 ℃ is 2 hours ~ 6 hours.
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, supersound process mixture.
Hyperacoustic power is preferably 400 watts ~ 800 watts, under the ultrasonic wave of this power, peels off, and to avoid the structure generation destruction to graphite, makes the electroconductibility of the Graphene for preparing higher.
The time of supersound process is preferably 0.5 hour ~ and 24 hours.
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 solid-to-liquid ratio of intercalated graphite and ionic liquid is 1g:10mL ~ 100mL, so that intercalated graphite and peel off the Graphene obtaining and be well-dispersed in ionic liquid, improves the efficiency peeled off and the productive rate of Graphene.
Preferably, the feelings carrying out the mixture of supersound process intercalated graphite and ionic liquid formation add water in the mixture of intercalated graphite and ionic liquid.The volume ratio of water and ionic liquid is 10 ~ 90:90 ~ 10, and the ratio of the volume of the mixed solution of the quality of intercalated graphite and ionic liquid and water is 1g:10mL ~ 100mL.
The Graphene that intercalated graphite and intercalated graphite obtain after peeling off also has good dispersiveness at the mixed solution of water and ionic liquid, the productive rate of the Graphene obtaining after can improving charge stripping efficiency and peeling off.And adding of water can reduce the consumption of ionic liquid, thereby reduce preparation cost.
The impurity that can not induce one in ultrasonic stripping process, filters and obtains filtrate, and ionic liquid can reclaim and again utilize, and is conducive to reduce preparation cost.
Step S140: the mixture through supersound process is filtered, cleaned, obtain Graphene.
The filter residue obtaining after the intercalated graphite of supersound process and the mixture of ionic liquid filter is Graphene.
In other embodiment, the filter residue obtaining after the intercalated graphite of supersound process and the mixture of ionic liquid and water filter is Graphene.
This filter residue is cleaned, to obtain pure Graphene.The method of cleaning be by organic solvent extraction filter 23 for filter residue ~ 5 times, then filters with deionized water, until filtrate with Silver Nitrate detection without chlorion.Adopt organic solvent to remove the ionic liquid in filter residue.
Organic solvent is preferably N-Methyl pyrrolidone (NMP) or dimethyl formamide (DMF).
Step S150: vacuum-drying.
Under vacuum condition, the filter residue 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 supersound process effect, 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 the mixed solution of ionic liquid or ionic liquid and water to make dispersion liquid, and prepare Graphene under supersound process, and the Graphene obtaining has good dispersiveness, and individual layer rate can reach more than 60%.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) getting the dried intercalated graphite of 1g, is that 1g:10ml joins 10mlEtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, obtain mixture.Container is placed on to the ultrasonic 0.5h of peeling off in the ultrasonic instrument that power is 400w, the mixture through supersound process is filtered and obtains filter residue, N-Methyl pyrrolidone for filter residue (NMP) 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 ~ 3 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 cupric 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) getting the dried intercalated graphite of 1g, is that 1g:100ml joins 100mlEtMeImBF is housed by mass volume ratio
4, EtMeImN (CF
3sO
2)
2with in the container of the mixed solution of water, obtain mixture, wherein, water and EtMeImBF
4, EtMeImN (CF
3sO
2)
2volume ratio be 10:80:10, water, EtMeImBF
4and EtMeImN (CF
3sO
2)
2volume sum be 100ml.Container is placed on to the ultrasonic 24h of peeling off in the ultrasonic instrument that power is 500w, the mixture through supersound process is filtered and obtains filter residue, by dimethyl formamide for filter residue (DMF) filter 23, 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) getting the dried intercalated graphite of 1g, is that 1g:50ml joins 50mlEtMeImCF is housed by mass volume ratio
3sO
3with in the container of the mixed solution of water, obtain mixture, wherein, water and EtMeImCF
3sO
3volume ratio be 80:20, water and EtMeImCF
3sO
3volume sum be 50ml.Container is placed on to the ultrasonic 18h of peeling off in the ultrasonic instrument that power is 600w, the mixture through supersound process is filtered and obtains filter residue, by N-Methyl pyrrolidone for filter residue (NMP) filter 23, 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) getting the dried intercalated graphite of 1g, is that 1g:20ml joins 20mlEtMeImCF is housed by mass volume ratio
3cO
3, EtMeImBF
4, EtMeImCF
3sO
3with in the container of the mixed solution of water, obtain mixture, wherein, water and EtMeImCF
3cO
3, EtMeImBF
4, EtMeImCF
3sO
3volume ratio be 20:50:20:10, water and EtMeImCF
3cO
3, EtMeImBF
4, EtMeImCF
3sO
3volume sum be 20ml.Container is placed on to the ultrasonic 15h of peeling off in the ultrasonic instrument that power is 700w, the mixture through supersound process is filtered and obtains filter residue, by dimethyl formamide for filter residue (DMF) filter 23, 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) getting the dried intercalated graphite of 1g, is that 1g:80ml joins 80mlEtMeImC (CF is housed by mass volume ratio
3sO
2)
3with in the container of the mixed solution of water, obtain mixture, wherein, water and EtMeImC (CF
3sO
2)
3volume ratio be 60:40, water and EtMeImC (CF
3sO
2)
3volume sum be 80ml.Container is placed on to the ultrasonic 12h of peeling off in the ultrasonic instrument that power is 800w, the mixture through supersound process is filtered and obtains filter residue, N-Methyl pyrrolidone for filter residue (NMP) 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) getting the dried intercalated graphite of 1g, is that 1g:60ml joins 60mlEtMeImN (C is housed by mass volume ratio
2f
5sO
2) 2 with the container of the mixed solution of water in obtain mixture, wherein, water and EtMeImN (C
2f
5sO
2) 2 volume ratio is 50:50, water and EtMeImN (C
2f
5sO
2)
2volume sum be 60ml.Container is placed on to the ultrasonic 16h of peeling off in the ultrasonic instrument that power is 600w, the mixture through supersound process is filtered and obtains filter residue, dimethyl formamide for filter residue (DMF) 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 4 hours, obtain pure intercalated graphite.
(2) getting the dried intercalated graphite of 1g, is that 1g:40ml joins 40mlEtMeImN (CN) is housed by mass volume ratio
2with in the container of the mixed solution of water, obtain mixture, wherein, water and EtMeImN (CN)
2volume ratio be 40:60, water and EtMeImN (CN)
2volume sum be 40ml.Container is placed on to the ultrasonic 8h of peeling off in the ultrasonic instrument that power is 400w, the mixture through supersound process is filtered and obtains filter residue, by N-Methyl pyrrolidone for filter residue (NMP) filter 23, 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) getting the dried intercalated graphite of 1g, is that 1g:30ml joins and 30ml1-Et-3 is housed, 5-Me by mass volume ratio
2imN (CF
3sO
2)
2with in the container of the mixed solution of water, obtain mixture, wherein, water and 1-Et-3,5-Me
2imN (CF
3sO
2)
2volume ratio be 30:70, water and 1-Et-3,5-Me
2imN (CF
3sO
2)
2volume sum be 30ml.Container is placed on to the ultrasonic 5h of peeling off in the ultrasonic instrument that power is 500w, the mixture through supersound process is filtered and obtains filter residue, dimethyl formamide for filter residue (DMF) 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) getting the dried intercalated graphite of 1g, is that 1g:100ml joins and 100ml1 is housed, 3-Et by mass volume ratio
2-4-MeImN (CF
3sO
2)
2with in the container of the mixed solution of water, obtain mixture, wherein, water and 1,3-Et
2-4-MeImN (CF
3sO
2)
2volume ratio be 20:80, water and 1,3-Et
2-4-MeImN (CF
3sO
2)
2volume sum be 100ml.Container is placed on to the ultrasonic 2h of peeling off in the ultrasonic instrument that power is 700w, the mixture through supersound process is filtered and obtains filter residue, N-Methyl pyrrolidone for filter residue (NMP) 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, synthetic 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) getting the dried intercalated graphite of 1g, is that 1g:10ml joins and 10ml1 is housed, 3-Et by mass volume ratio
2-5-MeImN (CF
3sO
2)
2with in the container of the mixed solution of water, obtain mixture, wherein, water and 1,3-Et
2-5-MeImN (CF
3sO
2)
2volume ratio be 10:90, water and 1,3-Et
2-5-MeImN (CF
3sO
2)
2volume sum be 10ml.Container is placed on to the ultrasonic 10h of peeling off in the ultrasonic instrument that power is 800w, the mixture filtering reacting liquid through supersound process is obtained to filter residue, dimethyl formamide for filter residue (DMF) 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 15 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, synthetic 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) getting the dried intercalated graphite of 1g, is that 1g:50ml joins 50mlEtMeImCF is housed by mass volume ratio
3cO
3in the container of ionic liquid, obtain mixture.Container is placed on to the ultrasonic 0.5h of peeling off in the ultrasonic instrument that power is 550w, the mixture through supersound process is filtered and obtains filter residue, N-Methyl pyrrolidone for filter residue (NMP) 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.
Table 1 represents is the individual layer rate of Graphene of embodiment 1 ~ embodiment 11 preparations and the productive rate of Graphene.
Table 1
From table 1, can learn, the individual layer rate of the Graphene of embodiment 1 ~ embodiment 11 preparations is for all more than 60%, and quality 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: will intercalated graphite, ionic liquid forms the mixture of intercalated graphite and ionic liquid after mixing, mixture described in supersound process;
Step 4: the mixture through supersound process is filtered, 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. the preparation method of Graphene according to claim 1, 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, described supersound process condition is: 400 watts ~ 800 watts of power, the treatment time is 0.5 hour ~ 24 hours.
6. 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 in 3-diethyl-5-Methylimidazole fluoroform sulfimide.
7. the preparation method of Graphene according to claim 1, is characterized in that, the mass volume ratio of described intercalated graphite and ionic liquid is 1g:10mL ~ 100mL.
8. the preparation method of Graphene according to claim 1, is characterized in that, in described step 3, before the mixture of intercalated graphite and ionic liquid, also adds water described in supersound process, and the volume ratio of described water and ionic liquid is 10 ~ 90:90 ~ 10.
9. the preparation method of Graphene according to claim 8, is characterized in that, the mass volume ratio of the mixed solution of described intercalated graphite and ionic liquid and water is 1g:10mL ~ 100mL.
10. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210310131.0A CN103626163A (en) | 2012-08-28 | 2012-08-28 | Graphene preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210310131.0A CN103626163A (en) | 2012-08-28 | 2012-08-28 | Graphene preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103626163A true CN103626163A (en) | 2014-03-12 |
Family
ID=50207670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210310131.0A Pending CN103626163A (en) | 2012-08-28 | 2012-08-28 | Graphene preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626163A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104176730A (en) * | 2014-08-14 | 2014-12-03 | 新疆中泰化学股份有限公司 | Preparation method of in-situ-polymerization graphene microemulsion |
| CN104817074A (en) * | 2015-04-20 | 2015-08-05 | 德阳烯碳科技有限公司 | Process for preparing graphite intercalation compound |
| CN105129755A (en) * | 2015-09-01 | 2015-12-09 | 南方科技大学 | Method for preparing single-layer metal phosphate and application thereof |
| CN105668530A (en) * | 2016-01-14 | 2016-06-15 | 苏州微格纳米科技有限公司 | Preparation method of two-dimensional nanomaterial |
| TWI562959B (en) * | 2014-06-05 | 2016-12-21 | Univ Nat Kaohsiung Applied Sci | A method of producing a graphene material, a graphite material, and a micro-actuator which has the graphite material |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
| CN108467031A (en) * | 2018-04-24 | 2018-08-31 | 盐城师范学院 | A kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type |
| CN108516540A (en) * | 2018-04-24 | 2018-09-11 | 盐城师范学院 | A kind of preparation method of dispersible graphene intercalation compound |
-
2012
- 2012-08-28 CN CN201210310131.0A patent/CN103626163A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI562959B (en) * | 2014-06-05 | 2016-12-21 | Univ Nat Kaohsiung Applied Sci | A method of producing a graphene material, a graphite material, and a micro-actuator which has the graphite material |
| CN104176730A (en) * | 2014-08-14 | 2014-12-03 | 新疆中泰化学股份有限公司 | Preparation method of in-situ-polymerization graphene microemulsion |
| CN104817074A (en) * | 2015-04-20 | 2015-08-05 | 德阳烯碳科技有限公司 | Process for preparing graphite intercalation compound |
| CN105129755A (en) * | 2015-09-01 | 2015-12-09 | 南方科技大学 | Method for preparing single-layer metal phosphate and application thereof |
| CN105129755B (en) * | 2015-09-01 | 2017-07-25 | 南方科技大学 | Prepare the phosphatic method and its application of single-layer metal |
| CN105668530A (en) * | 2016-01-14 | 2016-06-15 | 苏州微格纳米科技有限公司 | Preparation method of two-dimensional nanomaterial |
| CN105668530B (en) * | 2016-01-14 | 2018-01-19 | 苏州微格纳米科技有限公司 | A kind of preparation method of two-dimension nano materials |
| CN108314025A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of preparation method of bilayer graphene intercalation compound |
| CN108467031A (en) * | 2018-04-24 | 2018-08-31 | 盐城师范学院 | A kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type |
| CN108516540A (en) * | 2018-04-24 | 2018-09-11 | 盐城师范学院 | A kind of preparation method of dispersible graphene intercalation compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103626163A (en) | Graphene preparation method | |
| CN102464313B (en) | Preparation method of graphene | |
| CN102942177B (en) | Method for preparing graphene sheet | |
| CN102320598A (en) | Preparation method of graphene | |
| CN103588195A (en) | Preparation method of graphene | |
| CN102464315A (en) | Preparation method of graphene | |
| CN103408000A (en) | Preparation method for oxidized grapheme in large sheet | |
| CN103112844B (en) | Macro preparation method for mesoporous ordered graphene | |
| CN103626166A (en) | Graphene preparation method | |
| CN102757035B (en) | Preparation method of graphene | |
| CN103553030A (en) | Preparation method of few-layer graphene | |
| CN102786045A (en) | Method for preparing oxidized graphene | |
| CN102583338A (en) | High-quality graphene powder and preparation method thereof | |
| CN105752969A (en) | Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables | |
| CN103569992A (en) | Preparation method of carbon nanotube | |
| CN103387223A (en) | Preparation method of graphite | |
| CN103935982B (en) | The preparation method of graphene nanobelt | |
| CN102464312A (en) | Preparation method of graphene | |
| CN103241734A (en) | Reduction method of graphene oxide | |
| CN104003373A (en) | Graphene material and preparation method thereof | |
| CN103626164A (en) | Graphene preparation method | |
| CN108046242A (en) | A kind of preparation method of poroid graphene | |
| CN103359714A (en) | Preparation method of graphene | |
| CN108622887A (en) | A kind of swollen quick-fried method for preparing graphene of microwave | |
| CN103449414A (en) | Preparation method of graphene having porous structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140312 |