CN104003373A - Graphene material and preparation method thereof - Google Patents
Graphene material and preparation method thereof Download PDFInfo
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- CN104003373A CN104003373A CN201310055736.4A CN201310055736A CN104003373A CN 104003373 A CN104003373 A CN 104003373A CN 201310055736 A CN201310055736 A CN 201310055736A CN 104003373 A CN104003373 A CN 104003373A
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Abstract
The invention discloses a preparation method of a graphene material. The preparation method includes the following steps that chloride intercalation graphite is collected, the chloride intercalation graphite is added into molten ionic liquid with the solid-to-liquid ratio being 1 g:10-100 mL, after even stirring, the mixture is placed into an alternating electric field, stripping is conducted for 10-300 minutes with the alternative frequency being 10-1000 Hz and the electric field intensity being 50-5000 V/m, and accordingly graphene suspension liquid is obtained; the graphene suspension liquid is filtered, organic solvent for filtering residues is collected for washing and filtering three to five times, then deionized water is used for conducting repeated washing and filtering until chloride ions do not exist in an eluate, filter objects are dried, and hence the graphene material is obtained. According to the preparation method of the graphene material, the chloride intercalation graphite is placed in the ionic liquid for stripping under the action of the alternating electric field, and therefore the graphene material which is high in monolayer rate and good in dispersity can be obtained on the premise that the graphene structure is not damaged; the preparation method is high in efficiency, the source of raw materials is wide, cost is low, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic field of grapheme material, especially a kind of grapheme material and preparation method thereof.
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.Due to its unique structure and good photoelectric property, Graphene has become one of the study hotspot in the fields such as carbon material, nanotechnology and functional materials at present.The method of preparing at present grapheme material is mainly oxidation reduction process, but in preparation process, the laminated structure of Graphene is very easily destroyed, between Graphene, reunites, and has had a strong impact on its conduction, heat conductivility.How to overcome above-mentioned technological deficiency, develop new graphene preparation method, become one of the study hotspot in current Graphene field.
Ionic liquid refers to the liquid being all made up of ion, is a kind of environmentally friendly solvent, and inorganics, organism and polymkeric substance are all possessed to good solubility or dispersiveness, is called as " green solvent ".In recent years, there is research (as patent 201210249137.1,201210135363.7) that Graphite Powder 99 or carbon nanotube are suspended in ionic liquid, then stir or ultrasonic or extrude, thereby make the grapheme material of good dispersity, but due to Graphite Powder 99 or comparatively compactness of carbon nanotube structure, peel off difficulty, the Graphene individual layer rate that adopts these class methods to make is low, and the performance of Graphene is restricted.
Summary of the invention
The object of the invention is to overcome above-mentioned technological deficiency, a kind of preparation method of grapheme material is provided, the method is placed in ionic liquid by muriate intercalated graphite and peels off under the effect of alternating electric field, thereby under the prerequisite of structure of not destroying Graphene, make individual layer rate high, the grapheme material of good dispersity.
On the one hand, the invention provides a kind of preparation method of grapheme material, comprise the steps:
Get muriate intercalated graphite, join in ionic liquid in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, after stirring, put into alternating electric field, with the alternative frequency of 10～1000Hz, the strength of electric field of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension;
Filter described graphene suspension, get filter residue with organic solvent washing filter 23～5 time, then with deionized water repeatedly rinse and filtration until elutant without chlorion, dry screening, obtains grapheme material.
Preferably, described muriate intercalated graphite adopts following steps to make: get graphite and muriate intercalator mixes 1:0.8～1.2 in mass ratio, be placed in airtight container with 460～550 DEG C of thermal treatments 2～6 hours, after reaction finishes, be cooled to room temperature, after cleaning-drying, obtain muriate intercalated graphite.
More preferably, described graphite is the one in natural scale graphite, synthetic graphite and expanded graphite.
More preferably, described muriate intercalator is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
More preferably, being operating as of described cleaning-drying: reactant is poured in deionized water, and leaching filter residue is placed in vacuum drying oven and is dried 4～6 hours in 80～100 DEG C.
Ionic liquid has good dispersiveness to Graphene, can prevent the reunion of lamella graphite in Graphene preparation filtration.Preferably, described ionic liquid is the ionic liquid at room temperature being in a liquid state under room temperature.More preferably, described ionic liquid at room temperature 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-dimethyl miaow fluoroform sulfimide, 1, 3-diethyl-4-methyl miaow fluoroform sulfimide and 1, at least one in 3-diethyl-5-methyl miaow fluoroform sulfimide.
Preferably, in described alternating electric field stripping process, alternative frequency is 50～100Hz, and strength of electric field is 50～500V/m.
Wherein, described organic solvent is the organic solvent of solubilized ionic liquid.Preferably, described organic solvent is N, N-dimethyl pyrrolidone or DMF.
Wherein, be to remove metal ion and the chlorion in screening by the object of deionized water washing and filtering, the chlorion in described elutant can be used AgNO
3detect.
Muriate intercalated graphite, graphite layers is being mingled with muriate, and the spacing of graphite layers is larger, is easy to peel off; Under action of alternative electric field, muriate is subject to the effect of electrical forces and produces peeling force, and graphite is peeled off layer by layer, after peeling off, is scattered in ionic liquid, is difficult for reuniting, thereby obtains that laminated structure is complete, individual layer rate is high, the grapheme material of good dispersity; The ionic liquid and the muriate that are entrained in grapheme material can be filtered and be removed by follow-up organic solvent and deionized water wash, thereby obtain highly purified grapheme material.Preparation method's preparation efficiency of the present invention is high, peels off effectively, mainly concentrates on 1～10 layer, and individual layer rate is up to more than 75%, and raw material sources are wide, and cost is low, is applicable to suitability for industrialized production.
On the other hand, the present invention also provides a kind of grapheme material, and described grapheme material is made by above-mentioned preparation method.
Grapheme material laminated structure of the present invention is complete, individual layer rate is high, and good dispersity is suitable for use in the electrode of preparing electrochemical capacitor, can improve chemical power source energy density and power density.
Than prior art, grapheme material of the present invention and preparation method thereof has following beneficial effect:
(1) preparation method's preparation efficiency is high, peels off effectively, and raw material sources are wide, and cost is low, is applicable to suitability for industrialized production;
(2) the grapheme material laminated structure making is complete, and the number of plies mainly concentrates on 1～10 layer, and individual layer rate is high, and good dispersity is suitable for use in the electrode of preparing electrochemical capacitor, can improve chemical power source energy density and power density.
Brief description of the drawings
In order to be illustrated more clearly in technical scheme of the present invention, to the accompanying drawing of required use in embodiment be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the SEM figure of the grapheme material prepared of the embodiment of the present invention one under scanning electron microscope.
Embodiment
Below in conjunction with most preferred embodiment in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
A preparation method for grapheme material, comprises the steps:
Get muriate intercalated graphite, join in ionic liquid in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, after stirring, put into alternating electric field, with the alternative frequency of 10～1000Hz, the strength of electric field of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension;
Filter described graphene suspension, get filter residue with organic solvent washing filter 23～5 time, then with deionized water repeatedly rinse and filtration until elutant without chlorion, dry screening, obtains grapheme material.
Described muriate intercalated graphite adopts following steps to make: get graphite and muriate intercalator mixes 1:0.8～1.2 in mass ratio, be placed in airtight container with 460～550 DEG C of thermal treatments 2～6 hours, after reaction finishes, be cooled to room temperature, after cleaning-drying, obtain muriate intercalated graphite.
Described graphite is the one in natural scale graphite, synthetic graphite and expanded graphite.
Described muriate intercalator is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
Being operating as of described cleaning-drying: reactant is poured in deionized water, and leaching filter residue is placed in vacuum drying oven and is dried 4～6 hours in 80～100 DEG C.
Ionic liquid has good dispersiveness to Graphene, can prevent the reunion of lamella graphite in Graphene preparation filtration.Described ionic liquid is the ionic liquid at room temperature being in a liquid state under room temperature.More preferably, described ionic liquid at room temperature 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
2), 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-dimethyl miaow fluoroform sulfimide [1-Et-3,5-Me
2imN (CF
3sO
2)
2], 1,3-diethyl-4-methyl miaow fluoroform sulfimide [1,3-Et
2-4-MeImN (CF
3sO
2)
2] and 1,3-diethyl-5-methyl miaow fluoroform sulfimide [1,3-Et
2-5-MeIm N (CF
3sO
2)
2] at least one.
In described alternating electric field stripping process, alternative frequency is 50～100Hz, and strength of electric field is 50～500V/m.
Wherein, described organic solvent is the organic solvent of solubilized ionic liquid.Described organic solvent is N, N-dimethyl pyrrolidone or DMF.
Wherein, be to remove metal ion and the chlorion in screening by the object of deionized water washing and filtering, the chlorion in described elutant can be used AgNO
3detect.
Muriate intercalated graphite, graphite layers is being mingled with muriate, and the spacing of graphite layers is larger, is easy to peel off; Under action of alternative electric field, muriate is subject to the effect of electrical forces and produces peeling force, and graphite is peeled off layer by layer, after peeling off, is scattered in ionic liquid, is difficult for reuniting, thereby obtains that laminated structure is complete, individual layer rate is high, the grapheme material of good dispersity; The ionic liquid and the muriate that are entrained in grapheme material can be filtered and be removed by follow-up organic solvent and deionized water wash, thereby obtain highly purified grapheme material.Preparation method's preparation efficiency of the present invention is high, peels off effectively, mainly concentrates on 1～10 layer, and individual layer rate is up to more than 75%, and raw material sources are wide, and cost is low, is applicable to suitability for industrialized production.
In addition, the present invention also provides a kind of grapheme material, and described grapheme material is made by above-mentioned preparation method.
Grapheme material laminated structure of the present invention is complete, individual layer rate is high, and good dispersity is suitable for use in the electrode of preparing electrochemical capacitor, can improve chemical power source energy density and power density.
Embodiment mono-
A preparation method for grapheme material, comprises the steps:
(1) 1:0.8 takes natural scale graphite and iron(ic) chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 460 DEG C, insulation reaction 2 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 80 DEG C dry 6 hours, obtain pure iron(ic) chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF
4), get the EtMeImBF of 1L
4solvent is placed in beaker, and the iron(ic) chloride intercalated graphite 100g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 50Hz, alternating electric field intensity is to peel off 100 minutes under the effect of 1000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and iron(ic) chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, in N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove iron(ic) chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 20 hours with 60 DEG C, obtains grapheme material.
Embodiment bis-
A preparation method for grapheme material, comprises the steps:
(1) 1:0.9 takes synthetic graphite and cupric chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 500 DEG C, insulation reaction 3 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed twice, then leaching filter residue put into vacuum drying oven in 90 DEG C dry 5 hours, obtain pure cupric chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF
3sO
2)
2), get the EtMeImN (CF of 1L
3sO
2)
2solvent is placed in beaker, and the cupric chloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 10Hz, alternating electric field intensity is to peel off 50 minutes under the effect of 2000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and cupric chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in DMF (DMF), after stirring, again filters, and repeats to immerse DMF and filter operation 2 times, removes the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove cupric chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 10 hours with 80 DEG C, obtains grapheme material.
Embodiment tri-
A preparation method for grapheme material, comprises the steps:
(1) 1:1.2 takes expanded graphite and nickelous chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 480 DEG C, insulation reaction 6 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 100 DEG C dry 4 hours, obtain pure nickelous chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF
3sO
3), get the EtMeImCF of 5.5L
3sO
3solvent is placed in beaker, and the nickelous chloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 500Hz, alternating electric field intensity is to peel off 300 minutes under the effect of 5000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and nickelous chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 2 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove nickelous chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 15 hours with 100 DEG C, obtains grapheme material.
Embodiment tetra-
A preparation method for grapheme material, comprises the steps:
(1) 1:1 takes synthetic graphite and cobalt chloride is mixed in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 550 DEG C, insulation reaction 4 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 90 DEG C dry 4.5 hours, obtain pure cobalt chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF
3cO
2), get the EtMeImCF of 3.2L
3cO
2solvent is placed in beaker, and the cobalt chloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 1000Hz, alternating electric field intensity is to peel off 200 minutes under the effect of 50V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and cobalt chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in DMF (DMF), after stirring, again filters, and repeats to immerse DMF and filter operation 2 times, removes the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove cobalt chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 90 DEG C, obtains grapheme material.
Embodiment five
A preparation method for grapheme material, comprises the steps:
(1) 1:1.1 takes natural scale graphite and Repone K mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 520 DEG C, insulation reaction 5 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 85 DEG C dry 5.5 hours, obtain pure Repone K intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon [EtMeImC (CF
3sO
2)
3], get the EtMeImC (CF of 6.8L
3sO
2)
3solvent is placed in beaker, and the Repone K intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 200Hz, alternating electric field intensity is to peel off 20 minutes under the effect of 500V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and Repone K.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 3 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove Repone K residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 18 hours with 70 DEG C, obtains grapheme material.
Embodiment six
A preparation method for grapheme material, comprises the steps:
(1) 1:0.8 takes expanded graphite and sodium-chlor mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 530 DEG C, insulation reaction 2 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 95 DEG C dry 6 hours, obtain pure sodium-chlor intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole five acetyl fluoride imines [EtMeIm N (C
2f
5sO
2)
2], get the EtMeIm N (C of 10L
2f
5sO
2)
2solvent is placed in beaker, and the sodium-chlor intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 800Hz, alternating electric field intensity is to peel off 40 minutes under the effect of 100V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and sodium-chlor.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in DMF (DMF), after stirring, again filters, and repeats to immerse DMF and filter operation 3 times, removes the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove sodium-chlor residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 20 hours with 60 DEG C, obtains grapheme material.
Embodiment seven
A preparation method for grapheme material, comprises the steps:
(1) 1:1.1 takes natural scale graphite and magnesium chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 490 DEG C, insulation reaction 3 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 90 DEG C dry 4 hours, obtain pure magnesium chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole two cyaniding nitrogen [EtMeImN (CN)
2], get the EtMeImN (CN) of 4L
2solvent is placed in beaker, and the magnesium chloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 400Hz, alternating electric field intensity is to peel off 10 minutes under the effect of 3000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and magnesium chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 2 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove magnesium chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 10 hours with 100 DEG C, obtains grapheme material.
Embodiment eight
A preparation method for grapheme material, comprises the steps:
(1) 1:1 takes synthetic graphite and lead chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 540 DEG C, insulation reaction 6 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 100 DEG C dry 5 hours, obtain pure lead chloride intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3,5-dimethyl miaow fluoroform sulfimide [1-Et-3,5-Me
2imN (CF
3sO
2)
2], get the 1-Et-3 of 5L, 5-Me
2imN (CF
3sO
2)
2solvent is placed in beaker, and the lead chloride intercalated graphite 100g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 100Hz, alternating electric field intensity is to peel off 80 minutes under the effect of 4000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and lead chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in DMF (DMF), after stirring, again filters, and repeats to immerse DMF and filter operation 4 times, removes the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove lead chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 16 hours with 80 DEG C, obtains grapheme material.
Embodiment nine
A preparation method for grapheme material, comprises the steps:
(1) 1:0.9 takes natural scale graphite and zinc chloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 520 DEG C, insulation reaction 5 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 80 DEG C dry 6 hours, obtain pure zinc chloride intercalated graphite.
(2) ionic liquid is selected 1,3-diethyl-4-methyl miaow fluoroform sulfimide [1,3-Et
2-4-MeImN (CF
3sO
2)
2], get 1 of 1L, 3-Et
2-4-MeImN (CF
3sO
2)
2solvent is placed in beaker, and the zinc chloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 80Hz, alternating electric field intensity is to peel off 150 minutes under the effect of 800V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and zinc chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove zinc chloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 90 DEG C, obtains grapheme material.
Embodiment ten
A preparation method for grapheme material, comprises the steps:
(1) 1:1.1 takes expanded graphite and bariumchloride mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 550 DEG C, insulation reaction 4 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 90 DEG C dry 4 hours, obtain pure bariumchloride intercalated graphite.
(2) ionic liquid is selected 1,3-diethyl-5-methyl miaow fluoroform sulfimide [1,3-Et
2-5-MeImN (CF
3sO
2)
2], get 1 of 8L, 3-Et
2-5-MeIm N (CF
3sO
2)
2solvent is placed in beaker, and the bariumchloride intercalated graphite 10g that adds step (1) to make, stirs and obtain mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 50Hz, alternating electric field intensity is to peel off 200 minutes under the effect of 200V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid and bariumchloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in DMF (DMF), after stirring, again filters, and repeats to immerse DMF and filter operation 3 times, removes the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove bariumchloride residual in grapheme material, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 15 hours with 70 DEG C, obtains grapheme material.
Embodiment 11
A preparation method for grapheme material, comprises the steps:
(1) 1:0.6:0.6 takes synthetic graphite, iron(ic) chloride and cupric chloride and mixes in mass ratio, after mixing, put into silica tube, after sealed silica envelope, silica tube is put into High Temperature Furnaces Heating Apparatus, be warming up to 460 DEG C, insulation reaction 2 hours, is cooled to room temperature after reaction finishes, and reactant is poured in deionized water and rinsed one time, then leaching filter residue put into vacuum drying oven in 100 DEG C dry 6 hours, obtain pure muriate intercalated graphite.
(2) ionic liquid is selected 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF
4) and 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF
3sO
3) press the mixture that 1:1 forms, get the above-mentioned ionic liquid of 6.5L and be placed in beaker, the muriate intercalated graphite 10g that adds step (1) to make, stirs and obtains mixing solutions; Get the beaker that the above-mentioned mixing solutions of 1L is placed in 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, taking frequency as 200Hz, alternating electric field intensity is to peel off 100 minutes under the effect of 1000V/m, obtain graphene suspension, described graphene suspension comprises Graphene, ionic liquid, iron(ic) chloride and cupric chloride.
(3) graphene suspension step (2) being obtained filters, and gets filter residue and is immersed in N, N-dimethyl pyrrolidone, after stirring, again filter, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, filter with Büchner funnel, then repeatedly rinse screening using deionized water as washings to remove iron(ic) chloride residual in grapheme material and cupric chloride, until elutant AgNO
3till detecting and not producing precipitation, obtain Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 100 DEG C, obtains grapheme material.
Effect embodiment
The each 100 parts of grapheme materials that adopt atomic force microscope (AFM) to make embodiment mono-～11 are observed, and observe its number of plies, and result is as shown in table 1.
| Embodiment | One | Two | Three | Four | Five | Six | Seven | Eight | Nine | Ten | 11 |
| Individual layer rate | 87% | 83% | 81% | 78% | 80% | 81% | 76% | 82% | 75% | 86% | 76% |
Wherein, individual layer rate is that in 100 parts of observing samples, the quantity of single-layer graphene accounts for the ratio of the total quantity of single-layer graphene and Multi-layer graphite.As can be seen from Table 1, the individual layer rate of Graphene/ionic liquid composite material that the embodiment of the present invention makes is higher, is up to 87%.
The sign of the grapheme material that employing sem observation embodiment mono-makes, take SEM figure, result as shown in Figure 1, as can be seen from Figure 1, the grapheme material thickness that the embodiment of the present invention makes is about 0.35～2nm, 1～6 layer, the number of plies is relatively concentrated, and the size of Graphene is about 1～10um.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for grapheme material, is characterized in that, comprises the steps:
Get muriate intercalated graphite, join in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL in the ionic liquid of melting, after stirring, put into alternating electric field, with the alternative frequency of 10～1000Hz, the strength of electric field of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension;
Filter described graphene suspension, get filter residue with organic solvent washing filter 23～5 time, then with deionized water repeatedly rinse and filtration until elutant without chlorion, dry screening, obtains grapheme material.
2. the preparation method of grapheme material as claimed in claim 1, it is characterized in that, described muriate intercalated graphite adopts following steps to make: get graphite and muriate intercalator mixes 1:0.8～1.2 in mass ratio, be placed in airtight container with 460～550 DEG C of thermal treatments 2～6 hours, after reaction finishes, be cooled to room temperature, after cleaning-drying, obtain muriate intercalated graphite.
3. the preparation method of grapheme material as claimed in claim 2, is characterized in that, described graphite is the one in natural scale graphite, synthetic graphite and expanded graphite.
4. the preparation method of grapheme material as claimed in claim 2, it is characterized in that, described muriate intercalator is at least one in iron(ic) chloride, nickelous chloride, cupric chloride, cobalt chloride, Repone K, magnesium chloride, lead chloride, zinc chloride, calcium chloride and bariumchloride.
5. the preparation method of grapheme material as claimed in claim 2, is characterized in that, being operating as of described cleaning-drying: reactant is poured in deionized water, leaching filter residue be placed in vacuum drying oven in 80～100 DEG C dry 4～6 hours.
6. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described ionic liquid is the ionic liquid at room temperature being in a liquid state under room temperature.
7. the preparation method of grapheme material as claimed in claim 6, it is characterized in that, described ionic liquid at room temperature 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-dimethyl miaow fluoroform sulfimide, 1, 3-diethyl-4-methyl miaow fluoroform sulfimide and 1, at least one in 3-diethyl-5-methyl miaow fluoroform sulfimide.
8. the preparation method of grapheme material as claimed in claim 1, is characterized in that, in described alternating electric field stripping process, alternative frequency is 50～100Hz, and strength of electric field is 50～500V/m.
9. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described organic solvent is N, N-dimethyl pyrrolidone or DMF.
10. a grapheme material, is characterized in that, described grapheme material is made by preparation method described in any one in claim 1～9.
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