CN104003373B - A kind of grapheme material and preparation method thereof - Google Patents
A kind of grapheme material and preparation method thereof Download PDFInfo
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- CN104003373B CN104003373B CN201310055736.4A CN201310055736A CN104003373B CN 104003373 B CN104003373 B CN 104003373B CN 201310055736 A CN201310055736 A CN 201310055736A CN 104003373 B CN104003373 B CN 104003373B
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Abstract
The preparation method that the invention discloses a kind of grapheme material, comprise the steps: to take chloride intercalated graphite, join in melted ionic liquid in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, put into after stirring in alternating electric field, alternative frequency with 10～1000Hz, the electric field intensity of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension；Filter described graphene suspension, take filtering residue organic solvent washing filter 23～5 time, then by deionized water washing and filtering repeatedly until eluate is without chloride ion, dry screening, obtain grapheme material.Chloride intercalated graphite is placed in ionic liquid under the effect of alternating electric field and peels off by the present invention, thus under not destroying the premise of structure of Graphene, preparing monolayer rate high, the grapheme material of good dispersion；Preparation method efficiency is high, and raw material sources are wide, and cost is low, is suitable for industrialized production.
Description
Technical field
The present invention relates to grapheme material synthesis field, especially a kind of grapheme material and preparation method thereof.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that peace moral strong K sea nurse (AndreK.Geim) of Univ Manchester UK in 2004 etc. finds, and obtains physics Nobel Prize in 2010.Due to structure and the good photoelectric property of its uniqueness, Graphene has become one of study hotspots in field such as material with carbon element, nanotechnology and functional material at present.The method preparing grapheme material at present is mainly oxidation-reduction method, but in preparation process, the lamellar structure of Graphene is very easily destroyed, reunites between Graphene, has had a strong impact on its conduction, heat conductivility.How to overcome above-mentioned technological deficiency, develop new graphene preparation method, have become as one of study hotspot of current field of graphene.
Ionic liquid refers to the liquid being composed entirely of ions, and is a kind of environmentally friendly solvent, inorganic matter, Organic substance and polymer are provided with good dissolubility or dispersibility, be referred to as " green solvent ".In recent years, research (such as patent 201210249137.1,201210135363.7) is had to be suspended in ionic liquid by graphite powder or CNT, then it is stirred or ultrasonic or extrusion, thus preparing the grapheme material of good dispersion, but owing to graphite powder or carbon nano tube structure are comparatively compact, peeling off difficulty, adopt the Graphene monolayer rate that this kind of method prepares low, the performance of Graphene is restricted.
Summary of the invention
It is an object of the invention to overcome above-mentioned technological deficiency, the preparation method that a kind of grapheme material is provided, chloride intercalated graphite is placed in ionic liquid under the effect of alternating electric field and peels off by the method, thus under not destroying the premise of structure of Graphene, prepare monolayer rate high, the grapheme material of good dispersion.
On the one hand, the preparation method that the invention provides a kind of grapheme material, comprise the steps:
Take chloride intercalated graphite, join in ionic liquid in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, put in alternating electric field after stirring, with the alternative frequency of 10～1000Hz, the electric field intensity of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension；
Filter described graphene suspension, take filtering residue organic solvent washing filter 23～5 time, more repeatedly rinse with deionized water and filter until eluate is without chloride ion, dry screening, obtain grapheme material.
Preferably, described chloride intercalated graphite adopts following steps to prepare: take graphite and chloride intercalator 1:0.8～1.2 in mass ratio mix, it is placed in airtight container with 460～550 DEG C of heat treatments 2～6 hours, reaction is cooled to room temperature after terminating, and cleaned obtains chloride intercalated graphite after drying.
It is highly preferred that described graphite is the one in natural scale graphite, Delanium and expanded graphite.
It is highly preferred that described chloride intercalator is at least one in iron chloride, Nickel dichloride., copper chloride, cobaltous chloride, potassium chloride, magnesium chloride, lead chloride, zinc chloride, calcium chloride and barium chloride.
It is highly preferred that the operation of described cleaning-drying is: poured into by reactant in deionized water, leaching filtering residue is placed in vacuum drying oven and dries 4～6 hours in 80～100 DEG C.
Graphene is had good dispersibility by ionic liquid, it is possible to the reunion of Sheet Graphite in preventing Graphene preparation from filtering.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, at least one in 3-diethyl-4-methyl miaow fluoroform sulfimide and 1,3-diethyl-5-methyl miaow fluoroform sulfimide.
Preferably, in described alternating electric field stripping process, alternative frequency is 50～100Hz, and electric field intensity 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, being in that to remove the metal ion in screening and chloride ion by the purpose of deionized water washing and filtering, the chloride ion in described eluate can use AgNO3Detect.
Chloride intercalated graphite, cathode intercalation chloride, and the spacing of graphite layers is bigger, it is easy to peel off；Under action of alternative electric field, chloride is subject to the effect of electric field force and is peeling power, is peeled off layer by layer by graphite, is scattered in ionic liquid, not easily reunites after stripping, thus obtaining that lamellar structure is complete, monolayer rate high, the grapheme material of good dispersion；It is entrained in the ionic liquid in grapheme material and chloride can be filtered by follow-up organic solvent and deionized water wash and be removed, thus obtaining highly purified grapheme material.Preparation method preparation efficiency of the present invention is high, and peeling effect is good, is concentrated mainly on 1～10 layer, and monolayer rate is up to more than 75%, and raw material sources are wide, and cost is low, is suitable for industrialized production.
On the other hand, present invention also offers a kind of grapheme material, described grapheme material is prepared by above-mentioned preparation method.
Grapheme material lamellar structure of the present invention is complete, monolayer rate is high, good dispersion, is suitable for use in the electrode preparing electrochemical capacitor, can improve electrochmical power source energy density and power density.
Compared to prior art, grapheme material of the present invention and preparation method thereof has the advantages that
(1) preparation method preparation efficiency is high, and peeling effect is good, and raw material sources are wide, and cost is low, is suitable for industrialized production；
(2) the grapheme material lamellar structure prepared is complete, and the number of plies is concentrated mainly on 1～10 layer, and monolayer rate is high, and good dispersion is suitable for use in the electrode preparing electrochemical capacitor, can improve electrochmical power source energy density and power density.
Accompanying drawing explanation
In order to be illustrated more clearly that technical scheme, the accompanying drawing used required in embodiment will 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, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the grapheme material of the embodiment of the present invention one preparation SEM figure under scanning electron microscope.
Detailed description of the invention
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.
The preparation method of a kind of grapheme material, comprises the steps:
Take chloride intercalated graphite, join in ionic liquid in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, put in alternating electric field after stirring, with the alternative frequency of 10～1000Hz, the electric field intensity of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension；
Filter described graphene suspension, take filtering residue organic solvent washing filter 23～5 time, more repeatedly rinse with deionized water and filter until eluate is without chloride ion, dry screening, obtain grapheme material.
Described chloride intercalated graphite adopts following steps to prepare: take graphite and chloride intercalator 1:0.8～1.2 in mass ratio mix, it is placed in airtight container with 460～550 DEG C of heat treatments 2～6 hours, reaction is cooled to room temperature after terminating, and cleaned obtains chloride intercalated graphite after drying.
Described graphite is the one in natural scale graphite, Delanium and expanded graphite.
Described chloride intercalator is at least one in iron chloride, Nickel dichloride., copper chloride, cobaltous chloride, potassium chloride, magnesium chloride, lead chloride, zinc chloride, calcium chloride and barium chloride.
The operation of described cleaning-drying is: poured into by reactant in deionized water, and leaching filtering residue is placed in vacuum drying oven and dries 4～6 hours in 80～100 DEG C.
Graphene is had good dispersibility by ionic liquid, it is possible to the reunion of Sheet Graphite in preventing Graphene preparation from filtering.Described ionic liquid is the ionic liquid at room temperature being in a liquid state under room temperature.It is highly preferred that described ionic liquid at room temperature is 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF4), 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF3SO2)2), 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF3SO3), 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF3CO2), 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon [EtMeImC (CF3SO2)3], 1-ethyl-3-methylimidazole five acetyl fluoride imines [EtMeImN (C2F5SO2)2], 1-ethyl-3-methylimidazole two cyaniding nitrogen [EtMeImN (CN)2], 1-ethyl-3,5-dimethyl miaow fluoroform sulfimide [1-Et-3,5-Me2ImN(CF3SO2)2], 1,3-diethyl-4-methyl miaow fluoroform sulfimide [1,3-Et2-4-MeImN(CF3SO2)2] and 1,3-diethyl-5-methyl miaow fluoroform sulfimide [1,3-Et2-5-MeImN(CF3SO2)2] at least one.
In described alternating electric field stripping process, alternative frequency is 50～100Hz, and electric field intensity 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, being in that to remove the metal ion in screening and chloride ion by the purpose of deionized water washing and filtering, the chloride ion in described eluate can use AgNO3Detect.
Chloride intercalated graphite, cathode intercalation chloride, and the spacing of graphite layers is bigger, it is easy to peel off；Under action of alternative electric field, chloride is subject to the effect of electric field force and is peeling power, is peeled off layer by layer by graphite, is scattered in ionic liquid, not easily reunites after stripping, thus obtaining that lamellar structure is complete, monolayer rate high, the grapheme material of good dispersion；It is entrained in the ionic liquid in grapheme material and chloride can be filtered by follow-up organic solvent and deionized water wash and be removed, thus obtaining highly purified grapheme material.Preparation method preparation efficiency of the present invention is high, and peeling effect is good, is concentrated mainly on 1～10 layer, and monolayer rate is up to more than 75%, and raw material sources are wide, and cost is low, is suitable for industrialized production.
Additionally, present invention also offers a kind of grapheme material, described grapheme material is prepared by above-mentioned preparation method.
Grapheme material lamellar structure of the present invention is complete, monolayer rate is high, good dispersion, is suitable for use in the electrode preparing electrochemical capacitor, can improve electrochmical power source energy density and power density.
Embodiment one
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:0.8 weighs natural scale graphite and iron chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 460 DEG C, insulation reaction 2 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 6 hours in 80 DEG C, obtains pure iron chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF4), take the EtMeImBF of 1L4Solvent is placed in beaker, adds the iron chloride intercalated graphite 100g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 50Hz, alternating electric field intensity be 1000V/m effect under peel off 100 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and iron chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the iron chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 20 hours with 60 DEG C, obtain grapheme material.
Embodiment two
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:0.9 weighs Delanium and copper chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 500 DEG C, insulation reaction 3 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses twice, then leaching filtering residue is put in vacuum drying oven and is dried 5 hours in 90 DEG C, obtains pure copper chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole fluoroform sulfimide (EtMeImN (CF3SO2)2), take the EtMeImN (CF of 1L3SO2)2Solvent is placed in beaker, adds the copper chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 10Hz, alternating electric field intensity be 2000V/m effect under peel off 50 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and copper chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in DMF (DMF), be again filtered after stirring, repeat to immerse DMF and filter operation 2 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the copper chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 10 hours with 80 DEG C, obtain grapheme material.
Embodiment three
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1.2 weighs expanded graphite and Nickel dichloride. mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 480 DEG C, insulation reaction 6 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 4 hours in 100 DEG C, obtains pure Nickel dichloride. intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF3SO3), take the EtMeImCF of 5.5L3SO3Solvent is placed in beaker, adds the Nickel dichloride. intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 500Hz, alternating electric field intensity be 5000V/m effect under peel off 300 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and Nickel dichloride..
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 2 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the Nickel dichloride. of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 15 hours with 100 DEG C, obtain grapheme material.
Embodiment four
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1 weighs Delanium and cobaltous chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 550 DEG C, insulation reaction 4 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 4.5 hours in 90 DEG C, obtains pure cobaltous chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF3CO2), take the EtMeImCF of 3.2L3CO2Solvent is placed in beaker, adds the cobaltous chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 1000Hz, alternating electric field intensity be 50V/m effect under peel off 200 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and cobaltous chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in DMF (DMF), be again filtered after stirring, repeat to immerse DMF and filter operation 2 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the cobaltous chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 12 hours with 90 DEG C, obtain grapheme material.
Embodiment five
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1.1 weighs natural scale graphite and potassium chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 520 DEG C, insulation reaction 5 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 5.5 hours in 85 DEG C, obtains pure potassium chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole fluoroform sulphonyl carbon [EtMeImC (CF3SO2)3], take the EtMeImC (CF of 6.8L3SO2)3Solvent is placed in beaker, adds the potassium chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 200Hz, alternating electric field intensity be 500V/m effect under peel off 20 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and potassium chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 3 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the potassium chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 18 hours with 70 DEG C, obtain grapheme material.
Embodiment six
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:0.8 weighs expanded graphite and sodium chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 530 DEG C, insulation reaction 2 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 6 hours in 95 DEG C, obtains pure sodium chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole five acetyl fluoride imines [EtMeImN (C2F5SO2)2], take the EtMeImN (C of 10L2F5SO2)2Solvent is placed in beaker, adds the sodium chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 800Hz, alternating electric field intensity be 100V/m effect under peel off 40 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and sodium chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in DMF (DMF), be again filtered after stirring, repeat to immerse DMF and filter operation 3 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the sodium chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 20 hours with 60 DEG C, obtain grapheme material.
Embodiment seven
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1.1 weighs natural scale graphite and magnesium chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 490 DEG C, insulation reaction 3 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 4 hours in 90 DEG C, obtains pure magnesium chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole two cyaniding nitrogen [EtMeImN (CN)2], take the EtMeImN (CN) of 4L2Solvent is placed in beaker, adds the magnesium chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 400Hz, alternating electric field intensity be 3000V/m effect under peel off 10 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and magnesium chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 2 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the magnesium chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 10 hours with 100 DEG C, obtain grapheme material.
Embodiment eight
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1 weighs Delanium and lead chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 540 DEG C, insulation reaction 6 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 5 hours in 100 DEG C, obtains pure lead chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3,5-dimethyl miaow fluoroform sulfimide [1-Et-3,5-Me2ImN(CF3SO2)2], take 1-Et-3, the 5-Me of 5L2ImN(CF3SO2)2Solvent is placed in beaker, adds the lead chloride intercalated graphite 100g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 100Hz, alternating electric field intensity be 4000V/m effect under peel off 80 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and lead chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in DMF (DMF), be again filtered after stirring, repeat to immerse DMF and filter operation 4 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the lead chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 16 hours with 80 DEG C, obtain grapheme material.
Embodiment nine
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:0.9 weighs natural scale graphite and zinc chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 520 DEG C, insulation reaction 5 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 6 hours in 80 DEG C, obtains pure zinc chloride intercalated graphite.
(2) ionic liquid selects 1,3-diethyl-4-methyl miaow fluoroform sulfimide [1,3-Et2-4-MeImN(CF3SO2)2], take the 1,3-Et of 1L2-4-MeImN(CF3SO2)2Solvent is placed in beaker, adds the zinc chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 80Hz, alternating electric field intensity be 800V/m effect under peel off 150 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and zinc chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the zinc chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 12 hours with 90 DEG C, obtain grapheme material.
Embodiment ten
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:1.1 weighs expanded graphite and barium chloride mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 550 DEG C, insulation reaction 4 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 4 hours in 90 DEG C, obtains pure barium chloride intercalated graphite.
(2) ionic liquid selects 1,3-diethyl-5-methyl miaow fluoroform sulfimide [1,3-Et2-5-MeImN(CF3SO2)2], take the 1,3-Et of 8L2-5-MeImN(CF3SO2)2Solvent is placed in beaker, adds the barium chloride intercalated graphite 10g that step (1) prepares, is uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 50Hz, alternating electric field intensity be 200V/m effect under peel off 200 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid and barium chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in DMF (DMF), be again filtered after stirring, repeat to immerse DMF and filter operation 3 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove the barium chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 15 hours with 70 DEG C, obtain grapheme material.
Embodiment 11
The preparation method of a kind of grapheme material, comprises the steps:
(1) 1:0.6:0.6 weighs Delanium, iron chloride and copper chloride and mixes in mass ratio, put into after mix homogeneously in quartz ampoule, after sealed silica envelope, quartz ampoule is put in high temperature furnace, it is warming up to 460 DEG C, insulation reaction 2 hours, reaction is cooled to room temperature after terminating, and is poured into by reactant in deionized water and rinses one time, then leaching filtering residue is put in vacuum drying oven and is dried 6 hours in 100 DEG C, obtains pure chloride intercalated graphite.
(2) ionic liquid selects 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF4) and 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid (EtMeImCF3SO3) by the mixture of 1:1 composition, take the above-mentioned ionic liquid of 6.5L and be placed in beaker, add the chloride intercalated graphite 10g that step (1) prepares, be uniformly mixing to obtain mixed solution；Take the above-mentioned mixed solution of 1L and be placed in the beaker of 2L, then beaker is placed between two-plate, start alternating source and produce alternating electric field, with frequency for 200Hz, alternating electric field intensity be 1000V/m effect under peel off 100 minutes, obtaining graphene suspension, described graphene suspension includes Graphene, ionic liquid, iron chloride and copper chloride.
(3) graphene suspension that step (2) obtains is filtered, takes filtering residue and be immersed in N, N-dimethyl pyrrolidone, again it is filtered after stirring, repeat to immerse N, N-dimethyl pyrrolidone and filter operation 4 times, remove the ionic liquid in graphene suspension；Take filtering residue and be immersed in deionized water, be filtered with buchner funnel after stirring, then repeatedly rinse screening to remove iron chloride and the copper chloride of residual in grapheme material using deionized water as cleaning mixture, until eluate AgNO3Carry out detecting do not produce precipitation till, obtain Graphene filtering residue.
(4) the Graphene filtering residue that step (3) obtains is put in vacuum drying oven and dry 12 hours with 100 DEG C, obtain grapheme material.
Effect example
Adopting each 100 parts of grapheme materials that embodiment one～11 is prepared by atomic force microscope (AFM) to be observed, observe its number of plies, result is as shown in table 1.
| Embodiment | One | Two | Three | Four | Five | Six | Seven | Eight | Nine | Ten | 11 |
| Monolayer rate | 87% | 83% | 81% | 78% | 80% | 81% | 76% | 82% | 75% | 86% | 76% |
Wherein, monolayer 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.From table 1 it follows that the monolayer rate of Graphene/ionic liquid composite material that the embodiment of the present invention prepares is higher, it is up to 87%.
The sign of the grapheme material that employing sem observation embodiment one prepares, shooting SEM figure, result is as shown in Figure 1, as can be seen from Figure 1, the grapheme material thickness that the embodiment of the present invention prepares is about 0.35～2nm, namely 1～6 layer, number of plies Relatively centralized, 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 making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a grapheme material, it is characterised in that comprise the steps:
Take chloride intercalated graphite, join in melted ionic liquid in the ratio of solid-to-liquid ratio 1g:10～100mL, put into after stirring in alternating electric field, with the alternative frequency of 10～1000Hz, the electric field intensity of 50～5000V/m is peeled off 10～300 minutes, obtains graphene suspension；
Filter described graphene suspension, take filtering residue organic solvent washing filter 23～5 time, more repeatedly rinse with deionized water and filter until eluate is without chloride ion, dry screening, obtain grapheme material.
2. the preparation method of grapheme material as claimed in claim 1, it is characterized in that, described chloride intercalated graphite adopts following steps to prepare: take graphite and chloride intercalator 1:0.8～1.2 in mass ratio mix, it is placed in airtight container with 460～550 DEG C of heat treatments 2～6 hours, reaction is cooled to room temperature after terminating, and cleaned obtains chloride intercalated graphite after drying.
3. the preparation method of grapheme material as claimed in claim 2, it is characterised in that described graphite is the one in natural scale graphite, Delanium and expanded graphite.
4. the preparation method of grapheme material as claimed in claim 2, it is characterised in that described chloride intercalator is at least one in iron chloride, Nickel dichloride., copper chloride, cobaltous chloride, potassium chloride, magnesium chloride, lead chloride, zinc chloride, calcium chloride and barium chloride.
5. the preparation method of grapheme material as claimed in claim 2, it is characterised in that the operation of described cleaning-drying is: poured into by reactant in deionized water, leaching filtering residue is placed in vacuum drying oven and dries 4～6 hours in 80～100 DEG C.
6. the preparation method of grapheme material as claimed in claim 1, it is characterised 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, it is characterised in that in described alternating electric field stripping process, alternative frequency is 50～100Hz, and electric field intensity is 50～500V/m.
9. the preparation method of grapheme material as claimed in claim 1, it is characterised in that described organic solvent is N, N-dimethyl pyrrolidone or DMF.
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