CN103626166A - Graphene preparation method - Google Patents
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- CN103626166A CN103626166A CN201210310392.2A CN201210310392A CN103626166A CN 103626166 A CN103626166 A CN 103626166A CN 201210310392 A CN201210310392 A CN 201210310392A CN 103626166 A CN103626166 A CN 103626166A
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Abstract
The invention relates to a graphene preparation method, which comprises: 1, preparing a working electrode, wherein graphite is pressed on a stainless steel current collector so as to be adopted as a working electrode of a three-electrode system, 2, preparing intercalation graphite, wherein the three-electrode system is adopted to prepare intercalation graphite, 3, washing, wherein deionized water is adopted to wash the intercalation graphite, 4, carrying out vacuum drying, 5, carrying out microwave stripping, wherein the dried intercalation graphite is taken and added to an ion liquid according to a certain mass volume ratio, and the obtained mixture is placed into a microwave oven to carry out stripping, 6, washing, wherein filtration is performed by using organic solvent, and washing is performed by using deionized water until the pH value is neutral, and 7, carrying out vacuum drying. According to the present invention, the graphene preparation method has characteristics of simple operation and easy industrialization achievement, the yield of the graphene prepared by using the graphene preparation method is high, and the single layer rate of the graphene is up to more than 60%.
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 productive rate is lower.
Summary of the invention
Given this, be necessary to provide a kind of method of the simple to operate and higher Graphene of productive rate.
A preparation method for Graphene, comprises the steps:
Step 1, the preparation of working electrode, suppresses graphite on stainless steel collector, as the working electrode of three-electrode system;
Step 2, the preparation of intercalated graphite, adopts three-electrode system to prepare intercalated graphite;
Step 3, cleans, and uses washed with de-ionized water intercalated graphite;
Step 4, vacuum-drying;
Step 5, microwave is peeled off, and gets dried intercalated graphite, by certain mass volume ratio, adds ionic liquid, puts in microwave oven and peels off;
Step 6, washing, after filtering, is neutral with washed with de-ionized water to pH value with organic solvent;
Step 7, vacuum-drying.
In an embodiment, described graphite is natural flake graphite or synthetic graphite therein.
In an embodiment, in described three-electrode system, to electrode, be stereotype therein, reference electrode is Hg/Hg
2sO
4, electrolytic solution is pure intercalator, in 5 hours ~ 20 hours reaction times, current density is 5mA/cm
2~ 20mA/cm
2;
In an embodiment, described pure intercalator is at least one in formic acid, acetic acid, propionic acid, concentrated nitric acid, the vitriol oil and Nitromethane 99Min. 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 or 1, 3-diethyl-5-Methylimidazole fluoroform sulfimide.
In an embodiment, described mass volume ratio is 1g:10mL ~ 100mL therein.
Therein in an embodiment, it is under 1000 watts ~ 2000 watts of power, to carry out microwave to peel off 1 minute ~ 10 minutes that described microwave is peeled off.
In an embodiment, described organic solvent is N-Methyl pyrrolidone or dimethyl formamide therein.
In an embodiment, in described step 4, vacuum-drying condition is to be dried 12 hours ~ 24 hours at 60 ℃ ~ 80 ℃ therein.
In an embodiment, in described step 7, vacuum-drying condition is to be dried 10 hours ~ 20 hours at 60 ℃ ~ 100 ℃ therein.
The preparation method of above-mentioned Graphene, adopts ionic liquid as the solvent of intercalated graphite, at room temperature carries out microwave peel off and just can prepare fast Graphene in 1 ~ 10 minute without heating, simple to operate, is easy to realize industrialization; And can being scattered in well in ionic liquid of the Graphene preparing, can not reunite again, and productive rate is higher, and the individual layer rate of Graphene is up to more than 60%.
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 S11 0: the preparation of working electrode, graphite is suppressed on stainless steel collector, as the working electrode of three-electrode system.
Graphite and binding agent are positioned on collector, then with mould, are pressed into the working electrode of three electricity grade systems.Collector preferably adopts stainless steel collector.
Graphite can, for the conventional graphite in this area, be preferably natural flake graphite or synthetic graphite.
Preferably, three-electrode system to electrode, be stereotype, reference electrode is Hg/Hg
2sO
4.
Step S120: the preparation of intercalated graphite, adopts three-electrode system to prepare intercalated graphite.
Adopt three-electrode system to prepare intercalated graphite.Preparation method, for electrode, reference electrode and working electrode being soaked in electrolytic solution jointly, filtering and obtains intercalated graphite after 5 hours ~ 20 hours in room temperature reaction.
Wherein, electrolytic solution is at least one in formic acid, acetic acid, propionic acid, concentrated nitric acid, the vitriol oil and Nitromethane 99Min..
This several electrolytic solution also plays the effect of intercalator simultaneously, and under electric field action, electrolytic solution forms potential difference at working electrode surface, constantly overcomes graphite layers reactive force under the driving of potential difference, is inserted into graphite layers, obtains intercalated graphite.
The step of preferably, reacting 5 hours ~ 20 hours is to be 5mA/cm in current density
2~ 20mA/cm
2condition under react.
Wherein, concentrated nitric acid is that mass percentage concentration is 68% nitric acid; The vitriol oil is that mass percentage concentration is 98% sulfuric acid.
Step S130: clean, use washed with de-ionized water intercalated graphite.
The intercalated graphite obtaining with deionized water cleaning step S120.
Step S140: vacuum-drying.
At 60 ℃ ~ 80 ℃, the intercalated graphite after cleaning up is carried out to vacuum-drying 12 hours ~ 24 hours.
Step S150: microwave is peeled off, gets dried intercalated graphite, by certain mass volume ratio, adds ionic liquid, puts in microwave oven and peels off.
Dried intercalated graphite is added in ionic liquid, then the mixture of intercalated graphite and ionic liquid is put into microwave oven and peel off, to obtain Graphene.
Preferably, it is to carry out under 1000 watts ~ 2000 watts of power that microwave is peeled off, and under this power, peels off, and electrolytic solution easily resolves into gas from each graphite layers of intercalated graphite, make intercalated graphite peel off into Graphene and be scattered in ionic liquid, improve the productive rate of Graphene.
For example, under microwave action, formic acid resolves into hydrogen G&W, and acetic acid resolves into carbonic acid gas and methane.
Peel off and can obtain Graphene in 1 minute ~ 10 minutes, preparation efficiency is high.
The ratio of the quality of intercalated graphite and ionic liquid volume is 1g:10mL ~ 100mL.
Wherein, ionic liquid is 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 (EtMeIm N (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) or 1,3-diethyl-5-Methylimidazole fluoroform sulfimide (1,3-Et
2-5-MeImN (CF
3sO
2)
2).
Above-mentioned ionic liquid is liquid at normal temperatures, so that intercalated graphite is dispersed in ionic liquid, is convenient to carry out microwave and peels off.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 microwave stripping process, filters and obtains filtrate, and ionic liquid can reclaim and again utilize, and is conducive to reduce preparation cost.
Step S1 60: washing, after filtering with organic solvent, is neutral with washed with de-ionized water to pH value.
Microwave is peeled off after end, with organic solvent, filters, and obtains filter residue.By filter residue to the pH value of washed with de-ionized water gained, be neutral.
Wherein, the step of cleaning filter residue comprises: filter residue, through organic solvent extraction filter 23 ~ 5 times, then is to neutrality by deionized water cleaning and filtering to the pH value of filtrate.Adopt organic solvent can remove the ionic liquid in filter residue.
Wherein, organic solvent is preferably N-Methyl pyrrolidone (NMP) or dimethyl formamide (DMF).
Step S170: vacuum-drying.
The filter residue that step S160 is cleaned up carries out vacuum-drying, obtains dry Graphene.
Wherein, the step of dry filter residue comprises: under vacuum condition, filter residue is dried to 10 hours ~ 20 hours at 60 ℃ ~ 100 ℃.
The preparation method of above-mentioned Graphene, adopts ionic liquid as the solvent of intercalated graphite, carries out at normal temperatures microwave peel off and just can prepare fast Graphene in 1 minute ~ 10 minutes without heating, simple to operate, is easy to realize industrialization; And the productive rate of the Graphene preparing is higher, the individual layer rate of Graphene is up to more than 60%.
The Graphene that the preparation method of above-mentioned Graphene prepares has fine dispersiveness, and raw material sources 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: adopt stainless steel substrates as collector, about 2g natural flake graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, formic acid, as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 5mA/cm
2react 20 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 60 ℃, after dry 24 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:10mL joins EtMeImBF is housed by mass volume ratio
4in the container of ionic liquid, it is to peel off 1 minute in the microwave oven of 2000 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction again and filters 5 times, then is neutrality by deionized water cleaning and filtering to the pH value of filtrate; The filter residue cleaning up is dried to 20 hours at 60 ℃ in vacuum drying oven, obtains Graphene.
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 Graphene prepared by the present embodiment is about 0.5 nanometer ~ 3.5 nanometer, and graphene sheet layer is more concentrated, peels off respond well.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 2
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, acetic acid, as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 20mA/cm
2react 10 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 70 ℃, after dry 20 hours, obtain intercalated graphite.
(2) getting 1 g intercalated graphite, is that 1g:100mL has joined EtMeImN (CF by mass volume ratio
3sO
2)
2in the container of ionic liquid, it is to peel off 10 minutes in the microwave oven of 1000 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through dimethyl formamide (DMF) extraction filter 23 again, then is neutrality by the pH value that deionized water is filtered to filtrate; The filter residue cleaning up is dried to 10 hours at 80 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 3
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g natural flake graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, propionic acid, as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 5mA/cm
2react 20 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 80 ℃, after dry 12 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:50mL joins EtMeImCF is housed by quality volume
3sO
3in the container of ionic liquid, it is to peel off 5 minutes in the microwave oven of 1200 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction filter 23 again, then is neutrality by deionized water cleaning and filtering to the pH value of filtrate; The filter residue cleaning up is dried to 15 hours at 100 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 4
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, concentrated nitric acid (mass percentage concentration is 68%), as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 10mA/cm
2react 5 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 75 ℃, after dry 15 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:20mL joins dress EtMeImCF by quality volume
3cO
3in the container of ionic liquid, it is to peel off 8 minutes in the microwave oven of 1400 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through dimethyl formamide (DMF) extraction filter 23 again, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 12 hours at 90 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 5
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g natural flake graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, the vitriol oil (mass percentage concentration is 98%), as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 8mA/cm
2react 10 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 65 ℃, after dry 18 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:80mL joins dress EtMeImC (CF by quality volume
3sO
2)
3in the container of ionic liquid, it is to peel off 2 minutes in the microwave oven of 1500 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction again and filters 4 times, then is neutrality by deionized water cleaning and filtering to the pH value of filtrate; The filter residue cleaning up is dried to 18 hours at 70 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 6
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, Nitromethane 99Min., as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 5mA/cm
2react 15 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 60 ℃, after dry 20 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:60mL joins dress EtMeImN (C by quality volume
2f
5sO
2)
2in the container of ionic liquid, it is to peel off 4 minutes in the microwave oven of 1800 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through dimethyl formamide (DMF) extraction again and filters 4 times, then is neutrality by deionized water cleaning and filtering to the pH value of filtrate; The filter residue cleaning up is dried to 20 hours at 60 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 7
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g natural flake graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, the reaction solution of acetic acid and Nitromethane 99Min. is as electrolytic solution, and wherein, the volume ratio of acetic acid and Nitromethane 99Min. is 1:1, three electrodes is put into electrolyzer, and be fully immersed in electrolytic solution; Under room temperature, in current density, be 10mA/cm
2react 6 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 80 ℃, after dry 12 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:40mL joins dress EtMeImN (CN) by mass volume ratio
2in the container of ionic liquid, it is to peel off 3 minutes in the microwave oven of 1600 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction filter 23 again, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 10 hours at 100 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 8
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is pressed and is placed on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, the reaction solution of formic acid and the vitriol oil (mass percentage concentration of sulfuric acid is 98%) is as electrolytic solution, and wherein, the volume ratio of formic acid and sulfuric acid is 4:1, three electrodes is put into electrolyzer, and be fully immersed in electrolytic solution; Under room temperature, in current density, be 30mA/cm
2react 8 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 70 ℃, after dry 15 hours, obtain intercalated graphite.
(2) getting 1 g intercalated graphite, is that 1 g:30mL joins and 1-Et-3 is housed, 5-Me by mass volume ratio
2imN (CF
3sO
2)
2in the container of ionic liquid, it is to peel off 6 minutes in the microwave oven of 1200 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through dimethyl formamide (DMF) extraction again and filters 5 times, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 16 hours at 80 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 9
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g natural flake graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, the mixed solution of propionic acid and concentrated nitric acid (volume ratio is 1:1) (mass percentage concentration of nitric acid is 68%), as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 5mA/cm
2react 15 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 80 ℃, after dry 20 hours, obtain the third intercalated graphite.
(2) getting 1g intercalated graphite, is that 1g:100mL joins 1,3-Et is housed by mass volume ratio
2-4-MeImN (CF
3sO
2)
2in the container of ionic liquid, it is to peel off 8 minutes in the microwave oven of 1000 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction again and filters 5 times, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 12 hours at 90 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 10
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, acetic acid solution, as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 20mA/cm
2react 5 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 60 ℃, after dry 18 hours, obtain intercalated graphite.
(2) getting 1 g intercalated graphite, is that 1g:10mL joins 1,3-Et is housed by mass volume ratio
2-5-MeImN (CF
3sO
2)
2in the container of ionic liquid, it is to peel off 2 minutes in the microwave oven of 2000 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through dimethyl formamide (DMF) extraction again and filters 4 times, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 15 hours at 70 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
Embodiment 11
Being prepared as follows of the Graphene of the present embodiment:
(1) preparation of intercalated graphite: adopt stainless steel substrates as collector, about 2g synthetic graphite is positioned on collector, obtain working electrode with mould compacting, it is 75 * 40 * 7mm that graphite is pressed into specification
3graphite flake, using stereotype as to electrode, Hg/Hg
2sO
4as reference electrode, Nitromethane 99Min., as electrolytic solution, is put into electrolyzer by three electrodes, and is fully immersed in electrolytic solution; Under room temperature, in current density, be 5mA/cm
2react 20 hours, after filtration, adopt washed with de-ionized water, through vacuum drying oven, in 80 ℃, after dry 20 hours, obtain intercalated graphite.
(2) getting 1g intercalated graphite, is that 1 g:50mL joins 1,3-Et is housed by mass volume ratio
2-4-MeImN (CF
3sO
2)
2in the container of ionic liquid, it is to peel off 1 minute in the microwave oven of 1500 watts that container is placed on to power, obtains reaction solution, by reacting liquid filtering, the filter residue obtaining passes through N-Methyl pyrrolidone (NMP) extraction again and filters 5 times, then is neutral by deionized water cleaning and filtering to filtrate pH value; The filter residue cleaning up is dried to 12 hours at 100 ℃ in vacuum drying oven, obtains Graphene.
After testing, the productive rate of the present embodiment Graphene and individual layer rate, in Table 1.
What table 1 represented is productive rate, individual layer rate and the number of plies distribution of the Graphene of embodiment 1 ~ embodiment 11 preparations.
Table 1
From table 1, can learn, the productive rate of the Graphene of embodiment 1 ~ embodiment 11 preparations is at least 75%, higher than traditional graphite oxide reduction method.Wherein, the individual layer rate of Graphene is at least 60%, prepares the good Graphene of quality.
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, the preparation of working electrode, suppresses graphite on stainless steel collector, as the working electrode of three-electrode system;
Step 2, the preparation of intercalated graphite, adopts three-electrode system to prepare intercalated graphite;
Step 3, cleans, and uses washed with de-ionized water intercalated graphite;
Step 4, vacuum-drying;
Step 5, microwave is peeled off, and gets dried intercalated graphite, by certain mass volume ratio, adds ionic liquid, puts in microwave oven and peels off;
Step 6, washing, after filtering, is neutral with washed with de-ionized water to pH value with organic solvent;
Step 7, 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, is characterized in that, in described three-electrode system, to electrode, is stereotype, and reference electrode is Hg/Hg
2sO
4, electrolytic solution is pure intercalator, in 5 hours ~ 20 hours reaction times, current density is 5mA/cm
2~ 20mA/cm
2.
4. the preparation method of Graphene according to claim 3, is characterized in that, described pure intercalator is at least one in formic acid, acetic acid, propionic acid, concentrated nitric acid, the vitriol oil and Nitromethane 99Min..
5. 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 or 1, 3-diethyl-5-Methylimidazole fluoroform sulfimide.
6. the preparation method of Graphene according to claim 1 or 5, is characterized in that, described mass volume ratio is 1g:10mL ~ 100mL.
7. the preparation method of Graphene according to claim 6, is characterized in that, it is under 1000 watts ~ 2000 watts of power, to carry out microwave to peel off 1 minute ~ 10 minutes that described microwave is peeled off.
8. the preparation method of Graphene according to claim 1, is characterized in that, described organic solvent is N-Methyl pyrrolidone or dimethyl formamide.
9. the preparation method of Graphene according to claim 1, is characterized in that, in described step 4, vacuum-drying condition is to be dried 12 hours ~ 24 hours at 60 ℃ ~ 80 ℃.
10. the preparation method of Graphene according to claim 1, is characterized in that, in described step 7, vacuum-drying condition is to be dried 10 hours ~ 20 hours at 60 ℃ ~ 100 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118865A (en) * | 2014-05-09 | 2014-10-29 | 湖北大学 | Method for preparing graphene based on ion liquid crystal exfoliated graphite |
| CN104388814A (en) * | 2014-09-12 | 2015-03-04 | 济南圣泉集团股份有限公司 | Graphene modified steel |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| 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 |
| CN107429070A (en) * | 2015-03-18 | 2017-12-01 | 株式会社Adeka | Bedded substance contains liquid and its manufacture method |
| CN107827098A (en) * | 2017-11-22 | 2018-03-23 | 合肥开尔纳米能源科技股份有限公司 | The preparation method of graphene |
| CN114105135A (en) * | 2021-12-24 | 2022-03-01 | 湖南大学 | Method for electrochemically assisting preparation of low-defect expanded graphite paper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2281779A2 (en) * | 2009-08-05 | 2011-02-09 | Samsung Electronics Co., Ltd. | Graphene base and method of preparing the same |
| CN102583351A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of fewer-layer graphene |
-
2012
- 2012-08-28 CN CN201210310392.2A patent/CN103626166A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2281779A2 (en) * | 2009-08-05 | 2011-02-09 | Samsung Electronics Co., Ltd. | Graphene base and method of preparing the same |
| CN102583351A (en) * | 2012-02-29 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of fewer-layer graphene |
Non-Patent Citations (2)
| Title |
|---|
| WANG, XIQING等: "Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids", 《CHEMICAL COMMUNICATIONS》 * |
| 陈志刚等: "膨胀石墨的制备、结构和应用", 《江苏大学学报（自然科学版）》 * |
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|---|---|---|---|---|
| CN104118865A (en) * | 2014-05-09 | 2014-10-29 | 湖北大学 | Method for preparing graphene based on ion liquid crystal exfoliated graphite |
| CN104118865B (en) * | 2014-05-09 | 2016-08-24 | 湖北大学 | The method peeling off preparing graphite alkene based on ion liquid crystal |
| CN104388814A (en) * | 2014-09-12 | 2015-03-04 | 济南圣泉集团股份有限公司 | Graphene modified steel |
| CN104477892A (en) * | 2014-12-12 | 2015-04-01 | 盐城市新能源化学储能与动力电源研究中心 | Preparation method of flake graphene and flake graphene device prepared by same |
| CN104477892B (en) * | 2014-12-12 | 2016-08-24 | 盐城市新能源化学储能与动力电源研究中心 | Flaky graphite alkene device prepared by the preparation method of a kind of flaky graphite alkene and use the method |
| CN107429070A (en) * | 2015-03-18 | 2017-12-01 | 株式会社Adeka | Bedded substance contains liquid and its manufacture method |
| 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 |
| CN107827098A (en) * | 2017-11-22 | 2018-03-23 | 合肥开尔纳米能源科技股份有限公司 | The preparation method of graphene |
| CN114105135A (en) * | 2021-12-24 | 2022-03-01 | 湖南大学 | Method for electrochemically assisting preparation of low-defect expanded graphite paper |
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