CN104003372A - Graphene material and preparation method thereof - Google Patents
Graphene material and preparation method thereof Download PDFInfo
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- CN104003372A CN104003372A CN201310055678.5A CN201310055678A CN104003372A CN 104003372 A CN104003372 A CN 104003372A CN 201310055678 A CN201310055678 A CN 201310055678A CN 104003372 A CN104003372 A CN 104003372A
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Abstract
The invention discloses a preparation method of a graphene material. The preparation method includes the following steps that (1) after graphite and alkali metal are evenly mixed, vacuumizing and heat treatment are carried out, so that alkali metal intercalation graphite is obtained; (2) the alkali metal intercalation graphite is collected to be added into molten ionic liquid, after even stirring is conducted, the mixture is placed into an ultrasonic pulverizer, ultrasonic treatment is performed, and accordingly graphene suspension liquid is obtained; (3) the graphene suspension liquid is filtered, organic solvent for filtering residues is collected for washing and filtering, then, deionized water is used for conducting repeated washing and filtering until an eluate is neutral, filter objects are dried, and hence the graphene material is obtained. The invention further discloses the graphene material obtained through the preparation method. According to the graphene material and the preparation method thereof, the graphite and the alkali metal are mixed to be subjected to heat treatment first, the alkali metal intercalation graphite is obtained and then is dispersed into the ionic liquid, and after ultrasonic treatment is completed, the graphene material which is complete in laminated structure, high in monolayer rate and good in dispersity can be obtained; the method is simple, cost is low, efficiency is high, and the graphene material and the preparation method thereof are suitable for industrial production.
Description
Technical field
The present invention relates to the synthetic field of Graphene, 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 comprised 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 because Graphite Powder 99 or carbon nanotube structure are comparatively compact, 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
For overcoming above-mentioned technological deficiency, the invention provides a kind of grapheme material and preparation method thereof, the method is first processed graphite and basic metal mixture heat, after making basic metal intercalated graphite, redispersion is in ionic liquid, after supersound process, make laminated structure complete, individual layer rate is 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:
(1) under atmosphere of inert gases, by graphite and basic metal in molar ratio the ratio of 1～5:1 after mixing, be encased in sealed vessel, be evacuated to 10～1000Pa, then, with 200～1000 ℃ of thermal treatments 12～120 hours, obtain basic metal intercalated graphite;
(2) get basic metal intercalated graphite, in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, join in the ionic liquid of melting, after stirring, put into ultrasonic disintegrator, with the power ultrasonic of 2～10kW, process 0.5～100 minute, obtain graphene suspension;
(3) filter described graphene suspension, get filter residue and filter with organic solvent washing, and then washing and filtering is until elutant is neutral repeatedly with deionized water, dry screening, obtains grapheme material.
Preferably, described atmosphere of inert gases is nitrogen, argon gas or helium.
Preferably, described graphite is a kind of in natural scale graphite, synthetic graphite and expanded graphite.
Preferably, described basic metal is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium.
Preferably, described ionic liquid is gel or the ionic liquid that solidifies shape; Described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-Methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate.
Preferably, melt temperature during described ionic liquid melting is 150 ~ 300 ℃.
Preferably, described supersound process, ultrasonic power is 5～8kW, the supersound process time is 20～50 minutes.
Wherein, described organic solvent is the organic solvent of solubilized ionic liquid.Preferably, described organic solvent N, N-dimethyl pyrrolidone or DMF.
Preferably, being operating as of described dry screening: the filter residue after cleaning up is put in vacuum drying oven, is dried 10～20 hours with 60～100 ℃.
The present invention first processes graphite and basic metal mixture heat, and basic metal is inserted between graphite flake layer, has increased the spacing of graphite layers, thereby has made the basic metal intercalated graphite making be easy to peel off; Basic metal intercalated graphite is suspended in ionic liquid, by ultrasonic wave, is peeled off, and under the prerequisite of structure of not destroying Graphene, makes the high grapheme material of individual layer rate; Ionic liquid has good dispersiveness, and in preparation process, Graphene is dispersed in ionic liquid all the time, and agglomeration does not occur, thereby the grapheme material good conductivity making, and specific conductivity can be up to 10
6more than S/m.Preparation method's technique is simple, peels off effectively, 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) basic metal is inserted between graphite flake layer, has increased the spacing of graphite layers, reduced the follow-up difficulty of peeling off, to make the grapheme material of high individual layer rate;
(2) utilize ionic liquid to make solvent, can avoid the quick heat release of basic metal and the danger that produces, improve preparation security; And using heating and melting state ionic liquid as preparing platform, carry out ultrasonic peeling off, can fast basic metal intercalated graphite be peeled off into Graphene, improved the preparation efficiency of grapheme material, can make the Graphene making be dispersed in ionic liquid simultaneously, prevent its reunion, improved specific surface area and the electroconductibility of grapheme material;
(3) the grapheme material laminated structure that makes is complete, individual layer rate is high, good dispersity, and method is simple, and cost is low, and efficiency is high, is applicable to suitability for industrialized production.
Accompanying drawing explanation
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 skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the grapheme material of the embodiment of the present invention one preparation SEM figure 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:
(1) under atmosphere of inert gases, by graphite and basic metal in molar ratio the ratio of 1～5:1 after mixing, be encased in sealed vessel, be evacuated to 10～1000Pa, then, with 200～1000 ℃ of thermal treatments 12～120 hours, obtain basic metal intercalated graphite;
(2) get basic metal intercalated graphite, in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, join in the ionic liquid of melting, after stirring, put into ultrasonic disintegrator, with the power ultrasonic of 2～10kW, process 0.5～100 minute, obtain graphene suspension;
(3) filter described graphene suspension, get filter residue and filter with organic solvent washing, and then washing and filtering is until elutant is neutral repeatedly with deionized water, dry screening, obtains grapheme material.
Described atmosphere of inert gases is nitrogen, argon gas or helium.
Described graphite is a kind of in natural scale graphite, synthetic graphite and expanded graphite.
Described basic metal is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium.
Described ionic liquid is gel or the ionic liquid that solidifies shape; Described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-Methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate.
Melt temperature during described ionic liquid melting is 150 ~ 300 ℃.
Described supersound process, ultrasonic power is 5～8kW, the supersound process time is 20～50 minutes.
Wherein, described organic solvent is the organic solvent of solubilized ionic liquid.Described organic solvent N, N-dimethyl pyrrolidone or DMF.
Being operating as of described dry screening: the filter residue after cleaning up is put in vacuum drying oven, is dried 10～20 hours with 60～100 ℃.
The present invention first processes graphite and basic metal mixture heat, and basic metal is inserted between graphite flake layer, has increased the spacing of graphite layers, thereby has made the basic metal intercalated graphite making be easy to peel off; Basic metal intercalated graphite is suspended in ionic liquid, by ultrasonic wave, is peeled off, and under the prerequisite of structure of not destroying Graphene, makes the high grapheme material of individual layer rate; Ionic liquid has good dispersiveness, and in preparation process, Graphene is dispersed in ionic liquid all the time, and agglomeration does not occur, thereby the grapheme material good conductivity making, and specific conductivity can be up to 10
6more than S/m.Preparation method's technique is simple, peels off effectively, 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) be full of under the environment of helium, by natural scale graphite and potassium metal in molar ratio 5:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 10Pa, be heated to 200 ℃, heat preservation hot is processed 12 hours, obtains potassium metal intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole bromine salt (EtMeImBr), its fusing is obtained to the EtMeImBr solvent of 1L in beaker, the temperature that maintains EtMeImBr solvent is 150 ℃, the potassium metal intercalated graphite that adds therein 100g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 10kW is processed 1 minute, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove potassium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 20 hours with 60 ℃, obtains grapheme material.
Embodiment bis-
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of nitrogen, by synthetic graphite and metallic lithium in molar ratio 2:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 100Pa, be heated to 250 ℃, heat preservation hot is processed 20 hours, obtains metallic lithium intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole villaumite (EtMeImCl), its fusing is obtained to the EtMeImCl solvent of 1L in beaker, the temperature that maintains EtMeImCl solvent is 180 ℃, the metallic lithium intercalated graphite that adds therein 10g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 10kW is processed 0.5 minute, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove lithium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 10 hours with 80 ℃, obtains grapheme material.
Embodiment tri-
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of argon gas, by expanded graphite and sodium Metal 99.5 in molar ratio 1:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 500Pa, be heated to 300 ℃, heat preservation hot is processed 36 hours, obtains sodium Metal 99.5 intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole salt compounded of iodine (EtMeImI), its fusing is obtained to the EtMeImI solvent of 5L in beaker, the temperature that maintains EtMeImI solvent is 160 ℃, the sodium Metal 99.5 intercalated graphite that adds therein 100g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 8kW is processed 10 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove sodium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 15 hours with 100 ℃, obtains grapheme material.
Embodiment tetra-
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of helium, by natural flake graphite and metal rubidium in molar ratio 3:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 1000Pa, be heated to 220 ℃, heat preservation hot is processed 50 hours, obtains metal rubidium intercalated graphite;
(2) ionic liquid is selected 1-ethyl-2,3-methylimidazole fluoroform sulphonate (1-Et-2,3-Me
2imCF
3sO
3), its fusing is obtained to the 1-Et-2 of 2L, 3-Me in beaker
2imCF
3sO
3solvent, maintains 1-Et-2,3-Me
2imCF
3sO
3the temperature of solvent is 200 ℃, and the metal rubidium intercalated graphite that adds therein 100g step (1) to make, puts into ultrasonic disintegrator by beaker after stirring, and with the power ultrasonic of 6kW, processes 20 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove rubidium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 90 ℃, obtains grapheme material.
Embodiment five
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of nitrogen, by synthetic graphite and MAGNESIUM METAL in molar ratio 5:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 200Pa, be heated to 800 ℃, heat preservation hot is processed 80 hours, obtains MAGNESIUM METAL intercalated graphite;
(2) ionic liquid is selected 1,2-diethyl-3-Methylimidazole fluoroform sulphonate (1,2-Et
2-3-MeImCF
3sO
3), in beaker, its fusing is obtained to 1 of 8L, 2-Et
2-3-MeImCF
3sO
3solvent, maintains 1,2-Et
2-3-MeImCF
3sO
3the temperature of solvent is 220 ℃, and the MAGNESIUM METAL intercalated graphite that adds therein 100g step (1) to make, puts into ultrasonic disintegrator by beaker after stirring, and with the power ultrasonic of 5kW, processes 40 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove magnesium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 18 hours with 70 ℃, obtains grapheme material.
Embodiment six
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of argon gas, by expanded graphite and calcium metal in molar ratio 1:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 600Pa, be heated to 900 ℃, heat preservation hot is processed 100 hours, obtains calcium metal intercalated graphite;
(2) ionic liquid is selected 1,2-dimethyl-3-ethyl imidazol(e) bromine salt (1,2-Me
2-3-EtImBr), in beaker, its fusing is obtained to 1 of 6L, 2-Me
2-3-EtImBr solvent, maintains 1,2-Me
2the temperature of-3-EtImBr solvent is 250 ℃, and the calcium metal intercalated graphite that adds therein 100g step (1) to make, puts into ultrasonic disintegrator by beaker after stirring, and with the power ultrasonic of 3kW, processes 60 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove calcium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 20 hours with 60 ℃, obtains grapheme material.
Embodiment seven
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of nitrogen, by natural scale graphite and barium metal in molar ratio 4:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 800Pa, be heated to 1000 ℃, heat preservation hot is processed 120 hours, obtains barium metal intercalated graphite;
(2) ionic liquid is selected 1,2-dimethyl-3-ethyl imidazol(e) villaumite (1,2-Me
2-3-EtImCl), in beaker, its fusing is obtained to 1 of 4L, 2-Me
2-3-EtImCl solvent, maintains 1,2-Me
2the temperature of-3-EtImCl solvent is 280 ℃, and the barium metal intercalated graphite that adds therein 100g step (1) to make, puts into ultrasonic disintegrator after stirring, and with the power ultrasonic of 2kW, processes 100 minutes, obtains graphene suspension;
(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 2 times, remove the ionic liquid in graphene suspension; Get filter residue and be immersed in deionized water, after stirring, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove barium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 10 hours with 100 ℃, obtains grapheme material.
Embodiment eight
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of helium, by synthetic graphite and Preparation of Metallic Strontium in molar ratio 5:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 100Pa, be heated to 950 ℃, heat preservation hot is processed 60 hours, obtains Preparation of Metallic Strontium intercalated graphite;
(2) ionic liquid is selected 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate (1,2-Me
2-3-EtImBF
4), in beaker, its fusing is obtained to 1 of 3L, 2-Me
2-3-EtImBF
4solvent, maintains 1,2-Me
2-3-EtImBF
4the temperature of solvent is 300 ℃, and the Preparation of Metallic Strontium intercalated graphite that adds therein 100g step (1) to make, puts into ultrasonic disintegrator by beaker after stirring, and with the power ultrasonic of 5kW, processes 50 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove strontium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 16 hours with 80 ℃, obtains grapheme material.
Embodiment nine
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of nitrogen, by expanded graphite and potassium metal in molar ratio 1:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 50Pa, be heated to 500 ℃, heat preservation hot is processed 30 hours, obtains potassium metal intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole bromine salt (EtMeImBr) and 1-ethyl-3-methylimidazole villaumite (EtMeImCl) mixture that 1:1 forms in mass ratio, its fusing is obtained to the ionic liquid of 10L in beaker, the temperature that maintains ionic liquid is 200 ℃, the potassium metal intercalated graphite that adds therein 100g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 8kW is processed 20 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove potassium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 90 ℃, obtains grapheme material.
Embodiment ten
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of argon gas, by synthetic graphite and sodium Metal 99.5 in molar ratio 4:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 10Pa, be heated to 400 ℃, heat preservation hot is processed 12 hours, obtains sodium Metal 99.5 intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole villaumite (EtMeImCl), its fusing is obtained to the EtMeImCl solvent of 1L in beaker, the temperature that maintains EtMeImCl solvent is 210 ℃, the sodium Metal 99.5 intercalated graphite that adds therein 100g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 10kW is processed 5 minutes, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove sodium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 15 hours with 70 ℃, obtains grapheme material.
Embodiment 11
A preparation method for grapheme material, comprises the steps:
(1) be full of under the environment of helium, by expanded graphite and calcium metal in molar ratio 2:1 mix, after mixing, pack in heat-resistant glass tube, then by the thermal glass seal of tube and be evacuated to 1000Pa, be heated to 1000 ℃, heat preservation hot is processed 100 hours, obtains calcium metal intercalated graphite;
(2) ionic liquid is selected 1-ethyl-3-methylimidazole salt compounded of iodine (EtMeImI), its fusing is obtained to the EtMeImI solvent of 5L in beaker, the temperature that maintains EtMeImI solvent is 230 ℃, the calcium metal intercalated graphite that adds therein 100g step (1) to make, after stirring, beaker is put into ultrasonic disintegrator, power ultrasonic with 8kW is processed 0.5 minute, obtains graphene suspension;
(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, with Büchner funnel, filter, the deionized water of then usining rinses screening to remove calcium ion residual in grapheme material repeatedly as washings, until the pH of elutant is neutral, obtains Graphene filter residue.
(4) Graphene filter residue step (3) being obtained is put into vacuum drying oven and is dried 12 hours with 100 ℃, obtains grapheme material.
Effect embodiment
The specific conductivity of Graphene/ionic liquid combined electrode that employing four probe method test implementation example one～11 makes, test result is as shown in table 2.
As can be seen from Table 2, the specific conductivity of Graphene/ionic liquid combined electrode that the embodiment of the present invention makes is higher, is up to 4.1 * 10
6s/m.
The sign of the grapheme material that employing sem observation embodiment mono-makes, takes SEM figure, and 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 0.5～3nm, and the number of plies is relatively concentrated, peels off effective.
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:
(1) under atmosphere of inert gases, by graphite and basic metal in molar ratio the ratio of 1～5:1 after mixing, be encased in sealed vessel, be evacuated to 10～1000Pa, then, with 200～1000 ℃ of thermal treatments 12～120 hours, obtain basic metal intercalated graphite;
(2) get basic metal intercalated graphite, in the ratio of solid-to-liquid ratio 1g:10 ~ 100mL, join in the ionic liquid of melting, after stirring, put into ultrasonic disintegrator, with the power ultrasonic of 2～10kW, process 0.5～100 minute, obtain graphene suspension;
(3) filter described graphene suspension, get filter residue and filter with organic solvent washing, and then washing and filtering is until elutant is neutral repeatedly with deionized water, dry screening, obtains grapheme material.
2. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described atmosphere of inert gases is nitrogen, argon gas or helium.
3. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described graphite is a kind of in natural scale graphite, synthetic graphite and expanded graphite.
4. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described basic metal is at least one in lithium, sodium, magnesium, potassium, calcium, rubidium, strontium and barium.
5. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described ionic liquid is gel or the ionic liquid that solidifies shape; Described ionic liquid is 1-ethyl-3-methylimidazole bromine salt, 1-ethyl-3-methylimidazole villaumite, 1-ethyl-3-methylimidazole salt compounded of iodine, 1-ethyl-2,3-methylimidazole fluoroform sulphonate, 1,2-diethyl-3-Methylimidazole fluoroform sulphonate, 1,2-dimethyl-3-ethyl imidazol(e) bromine salt, 1, at least one in 2-dimethyl-3-ethyl imidazol(e) villaumite and 1,2-dimethyl-3-ethyl imidazol(e) a tetrafluoro borate.
6. the preparation method of grapheme material as claimed in claim 1, is characterized in that, melt temperature during described ionic liquid melting is 150 ~ 300 ℃.
7. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described supersound process, and ultrasonic power is 5～8kW, the supersound process time is 20～50 minutes.
8. the preparation method of grapheme material as claimed in claim 1, is characterized in that, described organic solvent N, N-dimethyl pyrrolidone or DMF.
9. the preparation method of grapheme material as claimed in claim 1, is characterized in that, being operating as of described dry screening: the filter residue after cleaning up is put in vacuum drying oven, with 60～100 ℃ dry 10～20 hours.
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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| CN107416809A (en) * | 2017-06-01 | 2017-12-01 | 黄凯 | A kind of method for preparing graphene |
| CN107469855A (en) * | 2017-09-29 | 2017-12-15 | 清华大学 | A kind of preparation method of the monatomic catalyst of nitrogen-doped graphene carried metal |
| CN107840326A (en) * | 2016-09-21 | 2018-03-27 | 比亚迪股份有限公司 | A kind of method for preparing graphene |
| WO2019196144A1 (en) * | 2018-04-09 | 2019-10-17 | 北京航空航天大学 | Method for preparing graphene by intercalation of alkali metal |
| CN110357082A (en) * | 2018-04-09 | 2019-10-22 | 北京航空航天大学 | A kind of graphene of alkali metal containing |
| CN111170314A (en) * | 2020-01-16 | 2020-05-19 | 王庆丰 | Method for efficiently preparing graphene through alkali metal intercalation and graphene |
| CN111331144A (en) * | 2020-04-02 | 2020-06-26 | 河北铷铯科技有限公司 | Preparation method of metal rubidium nano sol |
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