CN103663429A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103663429A CN103663429A CN201210358354.4A CN201210358354A CN103663429A CN 103663429 A CN103663429 A CN 103663429A CN 201210358354 A CN201210358354 A CN 201210358354A CN 103663429 A CN103663429 A CN 103663429A
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Abstract
The invention relates to a preparation method of graphene, which comprises the following steps: inserting a positive pole graphite and a negative pole platinum into an electrolyte mixed from water and an ionic liquid, and applying a 0.8-1.5V voltage between the positive pole and the negative pole to electrolyze for 4-10 minutes; applying a 10-15V voltage between the positive pole and the negative pole to electrolyze for 0.5-1 minute; filtering the electrolyte, and carrying out vacuum drying on the filtered solid at 60-100 DEG C; and under the condition of introducing protective gas, heating the solid to 700-800 DEG C, and keeping for 1-2 hours to obtain the graphene. The preparation method is environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of two-dimentional unimolecular layer material, has excellent physical properties, as high theoretical specific surface area, excellent physical strength, good snappiness and high specific conductivity etc., is subject to investigator's extensive concern.
The method of preparing at present Graphene mainly contains mechanically peel method, epitaxial growth method, oxidation reduction process and chemical Vapor deposition process.Chemical preparation Graphene often adopts the chemical reagent such as hydrazine hydrate, and these reagent have certain toxicity, and human body and environment are brought to harm, and the feature of environmental protection is poor.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method of Graphene of comparatively environmental protection.
A preparation method for Graphene, comprises the steps:
Take graphite as anodal, platinum is that negative pole inserts in the electrolytic solution being mixed by water and ionic liquid, between described positive pole and described negative pole, apply the voltage electrolysis 4 minutes ~ 10 minutes of 0.8V ~ 1.5V, described ionic liquid is selected from the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, N-methyl, at least one in the two fluoroform sulfimide salt of butyl pyrrolidine a tetrafluoro borate, 1-ethyl-3-methylimidazole a tetrafluoro borate and 1-ethyl-3-methylimidazole;
Between described positive pole and described negative pole, apply the voltage electrolysis 0.5 minute ~ 1 minute of 10V ~ 15V;
Filter described electrolytic solution, and the solids that filtration is obtained vacuum-drying under 60 ℃ ~ 100 ° C; And
Passing under the condition of protective gas, described solids is being heated to 700 ℃ ~ 800 ℃, and keeping obtaining for 1 hour ~ 2 hours Graphene.
In an embodiment, the mass ratio of described ionic liquid and water is 2:1 ~ 1:2 therein.
In an embodiment, the spacing between described positive pole and described negative pole is 0.1 meter ~ 1 meter therein.
In an embodiment, the described vacuum drying time is 12 hours ~ 24 hours therein.
In an embodiment, described protective gas is selected from least one in nitrogen and argon gas therein.
In an embodiment, the flow velocity of described protective gas is 200mL/min ~ 400mL/min therein.
Therein in an embodiment, the temperature of described solids is increased to 700 ℃ ~ 800 ℃ with the speed of 15 ℃/min ~ 25 ℃/min.
The preparation method of above-mentioned Graphene, consuming time shorter, equipment and technique are simple, convenient operation, the ionic liquid toxicity of use is less, comparatively environmental protection.
Accompanying drawing explanation
Fig. 1 is preparation method's the schema of the Graphene of an embodiment;
Fig. 2 is the adsorption-desorption isothermal curve of the Graphene of embodiment 1 preparation.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the Graphene of an embodiment, comprises the steps:
Step S110, take graphite as anodal, platinum is that negative pole inserts in the electrolytic solution being mixed by water and ionic liquid, between positive pole and negative pole, apply the voltage electrolysis 4 minutes ~ 10 minutes of 0.8V ~ 1.5V, ionic liquid is selected from the two fluoroform sulfimide salt ([BMIM] [TFSI]) of 1-butyl-3-Methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] [BF
4]), N-methyl, butyl pyrrolidine a tetrafluoro borate (PP
isosorbide-5-NitraebF
4), 1-ethyl-3-methylimidazole a tetrafluoro borate ([EMIM] [BF
4]) and the two fluoroform sulfimide salt ([EMIM] [TFSI]) of 1-ethyl-3-methylimidazole at least one.
In this step, while applying the voltage of 0.8V ~ 1.5V between positive pole and negative pole, the position that graphite contacts with electrolytic solution starts positively charged, and the negative ion in electrolytic solution is the surface to graphite by electrostatic adhesion.
Preferably, the mass ratio of ionic liquid and water is 2:1 ~ 1:2.
Preferably, the spacing between positive pole and negative pole is 0.1 meter ~ 1 meter.
Step S120, between positive pole and negative pole, apply the voltage electrolysis 0.5 minute ~ 1 minute of 10V ~ 15V.
In this step, between positive pole and negative pole, apply the voltage of 10V ~ 15V, the cellular lattice plane of graphite gradually becomes positively charged plane macromole, now, have a large amount of electronegative ions and water molecules and insert graphite layers, in electrolytic solution, start to have floating matter.
Step S130, filtration electrolytic solution, and the solids that filtration is obtained vacuum-drying under 60 ℃ ~ 100 ° C.
Preferably, the time of oven dry is 12 hours ~ 24 hours.
In this step, in the solids after oven dry, contain ionic liquid and water.
Step S140, passing under the condition of protective gas, described solids is being heated to 700 ℃ ~ 800 ℃, and keeps obtaining for 1 hour ~ 2 hours Graphene.
Preferably, protective gas is selected from least one in nitrogen and argon gas.
Preferably, the flow velocity of protective gas is 200mL/min ~ 400mL/min.
Preferably, the temperature of solids is increased to 700 ℃ ~ 800 ℃ with the speed of 15 ℃/min ~ 25 ℃/min.
In this step; solids carries out pyroprocessing under the atmosphere of protective gas; the ionic liquid and the water that insert graphite layers can change water vapour into; carbon monoxide and carbon dioxide; these gases form very large pressure at interlayer; when the power of bringing when this pressure is greater than the Van der Waals force between graphite flake layer, graphite flake layer will be peeled off generation Graphene.
The preparation method of above-mentioned Graphene, consuming time shorter, equipment and technique are simple, convenient operation; The ionic liquid toxicity of using is less, comparatively environmental protection; By electrochemical method, making graphite Efficient Conversion is Graphene, and prepared Graphene has higher reference area.
Below in conjunction with specific embodiment, further illustrate.
Embodiment 1
It is as follows that the present embodiment is prepared the technical process of Graphene:
Graphite → Graphene
(1) graphite: purity 99.5%;
(2) Graphene: the graphite in (1) is made to graphite rod, be used as positive pole with graphite rod, use platinum rod in the presence of negative pole, external source; Again positive and negative electrode is inserted to (water: [BMIM] [TFSI]=1g:1g) in the electrolytic solution being formed by water and the two fluoroform sulfimide salt ([BMIM] [TFSI]) of 1-butyl-3-Methylimidazole, between positive and negative electrode, apply a 1.2V voltage, continue 5 minutes, between positive and negative electrode, apply again 10V voltage, continue after 1 minute, electrolyte solution is filtered, and the vacuum drying oven that solid product is placed in 60 ° of C is dried 12 hours; Last argon gas (the flow velocity: 400ml/ minute) under protection that again solid product after drying is placed in; with 15 ° of temperature rise rates of C/ minute, the temperature of solid product is risen to 700 ° of C; and keep 1 hour; continue afterwards at argon gas (flow velocity: 400ml/ minute) protection drops to room temperature, obtains Graphene.
Refer to Fig. 2, Figure 2 shows that the adsorption-desorption isothermal curve that the Graphene of embodiment 1 preparation utilizes BET PORE SIZE APPARATUS FOR to draw.Curve is wherein isothermal desorption curve, and curve is below isothermal adsorption curve.The specific surface area that can be drawn the Graphene of embodiment 1 preparation by Fig. 2 is 674m
2/ g.
Embodiment 2
It is as follows that the present embodiment is prepared the technical process of Graphene:
Graphite → Graphene
(1) graphite: purity 99.5%;
(2) Graphene: the graphite in (1) is made to graphite rod, be used as positive pole with graphite rod, use platinum rod in the presence of negative pole, external source; Again positive and negative electrode is inserted by water and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM] [BF
4] (water: [BMIM] [BF in the electrolytic solution that forms
4]=2g:1g), between positive and negative electrode, apply a 1V voltage, continue 4 minutes, then between positive and negative electrode, apply 12V voltage, continue, after 0.5 minute, electrolyte solution to be filtered, and the vacuum drying oven that solid product is placed in 60 ° of C is dried 24 hours; Last argon gas (the flow velocity: 400ml/ minute) under protection that again solid product after drying is placed in; with 30 ° of temperature rise rates of C/ minute, the temperature of solid product is risen to 900 ° of C; and keep 1 hour; continue afterwards at argon gas (flow velocity: 400ml/ minute) protection drops to room temperature, obtains Graphene.
The Graphene of embodiment 2 preparations is through the test of BET PORE SIZE APPARATUS FOR, and its specific surface area is 619m
2/ g.
Embodiment 3
It is as follows that the present embodiment is prepared the technical process of Graphene:
Graphite → Graphene
(1) graphite: purity 99.5%;
(2) Graphene: the graphite in (1) is made to graphite rod, be used as positive pole with graphite rod, use platinum rod in the presence of negative pole, external source; Again positive and negative electrode is inserted to (water: [BMIM] [TFSI]=1g:1g) in the electrolytic solution being formed by water and the two fluoroform sulfimide salt [BMIM] [TFSI] of 1-butyl-3-Methylimidazole, between positive and negative electrode, apply a 1.5V voltage, continue 5 minutes, between positive and negative electrode, apply again 15V voltage, continue after 0.5 minute, electrolyte solution is filtered, and the vacuum drying oven that solid product is placed in 60 ° of C is dried 12 hours; Last argon gas (the flow velocity: 200ml/ minute) under protection that again solid product after drying is placed in; with 20 ° of temperature rise rates of C/ minute, the temperature of solid product is risen to 800 ° of C; and keep 1 hour; continue afterwards at argon gas (flow velocity: 200ml/ minute) protection drops to room temperature, obtains Graphene.
The Graphene of embodiment 3 preparations is through the test of BET PORE SIZE APPARATUS FOR, and its specific surface area is 723m
2/ g.
Embodiment 4
It is as follows that the present embodiment is prepared the technical process of Graphene:
Graphite → Graphene
(1) graphite: purity 99.5%;
(2) Graphene: the graphite in (1) is made to graphite rod, be used as positive pole with graphite rod, use platinum rod in the presence of negative pole, external source; Again positive and negative electrode is inserted to (water: [EMIM] [TFSI]=1g:2g) in the electrolytic solution being formed by water and the two fluoroform sulfimide salt ([EMIM] [TFSI]) of 1-ethyl-3-methylimidazole, between positive and negative electrode, apply a 1.5V voltage, continue 10 minutes, between positive and negative electrode, apply again 15V voltage, continue after 1 minute, electrolyte solution is filtered, and the vacuum drying oven that solid product is placed in 60 ° of C is dried 12 hours; Last argon gas (the flow velocity: 400ml/ minute) under protection that again solid product after drying is placed in; with 25 ° of temperature rise rates of C/ minute, the temperature of solid product is risen to 800 ° of C; and keep 2 hours; continue afterwards at argon gas (flow velocity: 400ml/ minute) protection drops to room temperature, obtains Graphene.
The Graphene of embodiment 4 preparations is through the test of BET PORE SIZE APPARATUS FOR, and its specific surface area is 786m
2/ g.
Embodiment 5
It is as follows that the present embodiment is prepared the technical process of Graphene:
Graphite → Graphene
(1) graphite: purity 99.5%;
(2) Graphene: the graphite in (1) is made to graphite rod, be used as positive pole with graphite rod, use platinum rod in the presence of negative pole, external source; Again positive and negative electrode is inserted by water and N-methyl to butyl pyrrolidine a tetrafluoro borate (PP
isosorbide-5-NitraebF
4) (water: (PP in the electrolytic solution that forms
isosorbide-5-NitraebF
4)=1g:2g), between positive and negative electrode, apply a 1.2V voltage, continue 10 minutes, then between positive and negative electrode, apply 15V voltage, continue, after 3 minutes, electrolyte solution to be filtered, and the vacuum drying oven that solid product is placed in 60 ° of C is dried 12 hours; Last argon gas (the flow velocity: 400ml/ minute) under protection that again solid product after drying is placed in; with 25 ° of temperature rise rates of C/ minute, the temperature of solid product is risen to 900 ° of C; and keep 2 hours; continue afterwards at argon gas (flow velocity: 400ml/ minute) protection drops to room temperature, obtains Graphene.
The Graphene of embodiment 5 preparations is through the test of BET PORE SIZE APPARATUS FOR, and its specific surface area is 823m
2/ g.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. a preparation method for Graphene, is characterized in that, comprises the steps:
Take graphite as anodal, platinum is that negative pole inserts in the electrolytic solution being mixed by water and ionic liquid, between described positive pole and described negative pole, apply the voltage electrolysis 4 minutes ~ 10 minutes of 0.8V ~ 1.5V, described ionic liquid is selected from the two fluoroform sulfimide salt of 1-butyl-3-Methylimidazole, 1-butyl-3-methyl imidazolium tetrafluoroborate, N-methyl, at least one in the two fluoroform sulfimide salt of butyl pyrrolidine a tetrafluoro borate, 1-ethyl-3-methylimidazole a tetrafluoro borate and 1-ethyl-3-methylimidazole;
Between described positive pole and described negative pole, apply the voltage electrolysis 0.5 minute ~ 1 minute of 10V ~ 15V;
Filter described electrolytic solution, and the solids that filtration is obtained vacuum-drying under 60 ℃ ~ 100 ° C; And
Passing under the condition of protective gas, described solids is being heated to 700 ℃ ~ 800 ℃, and keeping obtaining for 1 hour ~ 2 hours Graphene.
2. the preparation method of Graphene according to claim 1, is characterized in that, the mass ratio of described ionic liquid and water is 2:1 ~ 1:2.
3. the preparation method of Graphene according to claim 1, is characterized in that, the spacing between described positive pole and described negative pole is 0.1 meter ~ 1 meter.
4. the preparation method of Graphene according to claim 1, is characterized in that, the described vacuum drying time is 12 hours ~ 24 hours.
5. the preparation method of Graphene according to claim 1, is characterized in that, described protective gas is selected from least one in nitrogen and argon gas.
6. the preparation method of Graphene according to claim 1, is characterized in that, the flow velocity of described protective gas is 200mL/min ~ 400mL/min.
7. the preparation method of Graphene according to claim 1, is characterized in that, the temperature of described solids is increased to 700 ℃ ~ 800 ℃ with the speed of 15 ℃/min ~ 25 ℃/min.
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| CN201210358354.4A CN103663429A (en) | 2012-09-24 | 2012-09-24 | Preparation method of graphene |
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|---|---|---|---|
| CN201210358354.4A CN103663429A (en) | 2012-09-24 | 2012-09-24 | Preparation method of graphene |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102534642A (en) * | 2011-12-23 | 2012-07-04 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing graphene powder by electrochemistry |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102465309A (en) * | 2010-11-10 | 2012-05-23 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN102534642A (en) * | 2011-12-23 | 2012-07-04 | 深圳市贝特瑞纳米科技有限公司 | Method for preparing graphene powder by electrochemistry |
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Application publication date: 20140326 |