CN103964426A - Method for preparing graphene - Google Patents
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- CN103964426A CN103964426A CN201410205625.1A CN201410205625A CN103964426A CN 103964426 A CN103964426 A CN 103964426A CN 201410205625 A CN201410205625 A CN 201410205625A CN 103964426 A CN103964426 A CN 103964426A
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Abstract
The invention discloses a method for preparing graphene. The graphene is prepared by virtue of the following steps: 1) preparing expansible graphite, namely dispersing natural crystalline flake graphite into a mixed solution of ethanol and a concentrated nitric acid with the volume ratio of (50:1)-(50:10), forming evenly a 0.005-0.05g/mL dispersed suspension liquid, carrying out hydrothermal reaction on the suspension liquid at 80-160 DEG C for 6-48 hours, and cooling, filtering, participating, washing and drying the suspension liquid to obtain the expansible graphite; 2) adding the expansible graphite obtained in the step 1) into an organic foamer solution, placing for 30 minutes to 3 hours, and stirring at room temperature; 3) heating the product in the step 2), and simultaneously stirring for 1-5 hours; 4) carrying out ultrasonic vibration on the product in the step 3) for 13-60 minutes; 5) cooling and drying the product obtained in the step 4) in vacuum, so as to prepare a graphene monomer. The method for preparing the graphene provided by the invention is high in yield, meanwhile, a stabilizer does not need to be added, and good performance of the graphene is effectively kept.
Description
Technical field
The present invention relates to Graphene technical field, particularly a kind of preparation method of Graphene.
Background technology
Graphene (Graphene) is a kind ofly to form with SP2 hybridized orbital the electroconductibility flat film only with individual layer atomic thickness that hexangle type is honeycomb lattice by carbon atom.Graphene be at present the thinnest be in the world the hardest nano material also, it is almost completely transparent, is the material of resistivity minimum in the world at present.Graphene is considered to the basic structural unit of soccerballene, carbon nanotube and graphite, and its special calorifics, mechanics and conduction property make Graphene be expected to the ideal filler that becomes raising polymkeric substance calorifics, mechanics and electric property in matrix material preparing.For this reason, people have explored many methods of preparing Graphene, be respectively: mechanically peel method, liquid phase or meteorological directly stripping method (dilatometry), chemical Vapor deposition process, crystal epitaxy method and oxidation reduction process, wherein liquid phase or meteorological directly stripping method (dilatometry) are to adopt acid to carry out intercalation to obtain the graphite scale that rate of expansion is lower, graphite scale mean thickness is about 30 μ m, lateral dimension is in 400 μ m left and right, and this graphite scale is exactly expansible black lead.This expansible black lead is put into microwave or High Temperature Furnaces Heating Apparatus heats, just can obtain thickness is the nano graphite flakes of several nanometers to tens nanometers.This method because of the graphite taking cheap or expanded graphite be raw material, preparation process does not relate to chemical transformation, the direct stripping method of liquid phase or gas phase is prepared Graphene and is had that cost is low, simple to operate, high quality, but exist, single-layer graphene productive rate is not high, lamella is reunited seriously yet, need further slough the defects such as stablizer.
Based on the above, a kind of preparation method's of improved Graphene exploitation is by necessary property.
Summary of the invention
For the problems referred to above, the invention provides a kind of preparation method of improved Graphene, by graphite oxide being suspended in Cellmic C 121 class whipping agent, the peeling force producing by foaming is greater than the interstructural Van der Waals force of graphite flake layer, graphite flake layer is peeled off, thereby made Graphene.The Graphene productive rate that the preparation method of this improved Graphene makes is high, and does not need to add stablizer simultaneously.
The preparation method of Graphene disclosed by the invention is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 1～50: 10 that natural flake graphite is scattered in to volume ratio, form the suspension that finely dispersed concentration is 0.005g/mL～0.05g/mL, by this suspension hydro-thermal reaction 6h～48h at 80 DEG C～160 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead.Adopt concentrated nitric acid to carry out sour intercalation to natural flake graphite, make expansible black lead, realize the pre-treatment of graphite;
2) by 1) gained expansible black lead joins in organic blowing agent solution, places 30min～3h, stirring at normal temperature.By step 2) expansible black lead and organic blowing agent solution are fully mixed;
3) by step 2) product heating, stir 1h～5h simultaneously.Step 3) effect be that whipping agent is reduced foaming, foam between graphite flake layer by whipping agent graphite flake layer formed to peeling force, thereby promote further the peeling off of expansible black lead;
4) ultrasonic concussion 3) product 13min～60min; By further ultrasonic concussion effect, improve the productive rate of Graphene.
5) by 4) products therefrom is cooling, vacuum-drying makes Graphene monomer.
Preferably, the preparation method of described Graphene, wherein, described organic blowing agent is Cellmic C 121 class whipping agent.
Preferably, the preparation method of described Graphene, wherein, step 2) described in organic blowing agent be dissolved in and in dimethyl sulfoxide (DMSO), make organic blowing agent solution.
Preferably, the preparation method of described Graphene, wherein, and step 3) be heated to 160～260 DEG C
Preferably, the preparation method of described Graphene, wherein, step 3) stirring velocity is 200～600 turn/min.
Preferably, the preparation method of described Graphene, wherein, step 4) ultrasonic concussion carries out at normal temperatures.
Preferably, the preparation method of described Graphene, wherein, step 5) vacuum drying condition is normal temperature, the vacuum-drying time is 12h～48h.
The preparation method's of Graphene provided by the invention beneficial effect: prepare Graphene by the foaming of Cellmic C 121 class whipping agent, Heating temperature only needs 200 DEG C of left and right, has reduced equipment requirements, makes to peel off the Graphene productive rate obtaining simultaneously and promotes; In this method preparation process, do not need to add stablizer, reduced post-processed operation; After Cellmic C 121 decomposes, generate nitrogenous gas, on product property impact minimum, can effectively keep the superperformance of Graphene.
Embodiment
The present invention is described in further detail below, to make those skilled in the art can implement according to this with reference to specification sheets word.
Embodiment 1
The present embodiment provides the preparation method of Graphene, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 1 that natural flake graphite is scattered in to volume ratio, form the suspension that finely dispersed concentration is 0.005g/mL, by this suspension hydro-thermal reaction 6h at 80 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in Cellmic C 121 class foaming agent solution, stirring at normal temperature 30min, described Cellmic C 121 class foaming agent solution solvent for use is dimethyl sulfoxide (DMSO).
3) will holding 2) device of product puts into 160 DEG C of oil baths and heats, and stirs 1h, and stirring velocity is 600 turn/min;
4) ultrasonic concussion 3 at normal temperatures) product 13min,
5) by 4) products therefrom is cooling, vacuum-drying 12h makes Graphene monomer.
The lamellar spacing of the Graphene monomer making is 1.45nm; The specific surface area of described Graphene is 980m
2/ g, productive rate is 48%.
Embodiment 2
The present embodiment provides the preparation method of Graphene, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 10 that natural flake graphite is scattered in to volume ratio, form the suspension that finely dispersed concentration is 0.05g/mL, by this suspension hydro-thermal reaction 48h at 160 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in Cellmic C 121 class foaming agent solution, stirring at normal temperature 3h, described Cellmic C 121 class foaming agent solution solvent for use is dimethyl sulfoxide (DMSO).
3) will holding 2) device of product puts into 260 DEG C of oil baths, and constant temperature stirs 3h, and stirring velocity is 200 turn/min;
4) ultrasonic concussion 3 at normal temperatures) product 60min;
5) by 4) products therefrom is cooling, vacuum-drying 48h makes Graphene monomer.
The lamellar spacing of the Graphene monomer making is 10nm; The specific surface of described Graphene is 450m
2/ g, productive rate is 78%.
Embodiment 3
The present embodiment provides the preparation method of Graphene, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 5 that natural flake graphite is scattered in to volume ratio, form finely dispersed suspension, by this suspension hydro-thermal reaction 15h at 100 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in Cellmic C 121 class foaming agent solution, and constant temperature stirs 40min, and stirring velocity is 300 turn/min, and described Cellmic C 121 class foaming agent solution solvent for use is dimethyl sulfoxide (DMSO).
3) will holding 2) device of product puts into 200 DEG C of oil baths and heats, and constant temperature stirs 3h, and stirring velocity is 300 turn/min;
4) ultrasonic concussion 3 at normal temperatures) product 30min;
5) by 4) products therefrom is cooling, vacuum-drying 16h makes Graphene monomer.
The lamellar spacing of the Graphene monomer making is 7nm, and the specific surface of described Graphene is 800m
2/ g, productive rate is 62%.
Embodiment 4
The present embodiment provides the preparation method of Graphene, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 3 that natural flake graphite is scattered in to volume ratio, form finely dispersed suspension, by this suspension hydro-thermal reaction 24h at 120 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in Cellmic C 121 class foaming agent solution, and constant temperature stirs 45min, and described Cellmic C 121 class foaming agent solution solvent for use is dimethyl sulfoxide (DMSO).
3) by 2) product heats in 200 DEG C of oil baths, and constant temperature stirs 1h, and stirring velocity is 450 turn/min;
4) ultrasonic concussion 3 at normal temperatures) product 40min,
5) by 3) products therefrom is cooling, vacuum-drying makes Graphene monomer.
The lamellar spacing of the Graphene making is 6nm, and the specific surface of described Graphene is 600m
2/ g, productive rate is 58%.
Embodiment 5
The present embodiment provides the preparation method of Graphene, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 8 that natural flake graphite is scattered in to volume ratio, form finely dispersed suspension, by this suspension hydro-thermal reaction 36h at 150 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in Cellmic C 121 class foaming agent solution, and constant temperature stirs 50min, and described Cellmic C 121 class foaming agent solution solvent for use is dimethyl sulfoxide (DMSO).
3) will holding 2) device of product puts into 220 DEG C of oil baths, and constant temperature stirs 2.5h, and stirring velocity is 500 turn/min;
4) ultrasonic concussion 3 at normal temperatures) product 50min
5) by 4) products therefrom is cooling, vacuum-drying 20h makes Graphene monomer.
The lamellar spacing of the Graphene making is 9nm; The specific surface of described Graphene is 750m
2/ g, productive rate is 60%.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification sheets and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (7)
1. a preparation method for Graphene, is characterized in that, is to make by following steps:
1) prepare expansible black lead: it is in the ethanol and concentrated nitric acid mixing solutions of 50: 1～50: 10 that natural flake graphite is scattered in to volume ratio, form the suspension that finely dispersed concentration is 0.005g/mL～0.05g/mL, by this suspension hydro-thermal reaction 6h～48h at 80 DEG C～160 DEG C, by cooling suspension, filtration, precipitation, washing, dry, obtain expansible black lead;
2) by 1) gained expansible black lead joins in organic blowing agent solution, places 30min～3h, stirring at normal temperature;
3) by step 2) product heating, stir 1h～5h simultaneously;
4) ultrasonic concussion 3) product 13min～60min;
5) by 4) products therefrom is cooling, vacuum-drying makes Graphene monomer.
2. the preparation method of Graphene according to claim 1, is characterized in that, described organic blowing agent is Cellmic C 121 class whipping agent.
3. the preparation method of Graphene according to claim 2, is characterized in that step 2) described in organic blowing agent be dissolved in and in dimethyl sulfoxide (DMSO), make organic blowing agent solution.
4. the preparation method of Graphene according to claim 3, is characterized in that step 3) be heated to 160～260 DEG C.
5. the preparation method of Graphene according to claim 1, is characterized in that step 3) stirring velocity is 200～600 turn/min.
6. the preparation method of Graphene according to claim 1, is characterized in that step 4) ultrasonic concussion carries out at normal temperatures.
7. the preparation method of Graphene according to claim 1, is characterized in that step 5) vacuum drying condition is normal temperature, the vacuum-drying time is 12h～48h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106825591A (en) * | 2017-03-23 | 2017-06-13 | 厦门圣之岛金属科技有限公司 | A kind of tin alkene raw powder's production technology |
| CN110775966A (en) * | 2019-11-21 | 2020-02-11 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
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| CN102476797A (en) * | 2010-11-29 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method for expansible graphite |
| CN102874797A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for massively preparing high-quality graphene |
| CN102874798A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene |
| CN103771396A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof, and electrochemical capacitor |
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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476797A (en) * | 2010-11-29 | 2012-05-30 | 海洋王照明科技股份有限公司 | Preparation method for expansible graphite |
| CN102874797A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for massively preparing high-quality graphene |
| CN102874798A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene |
| CN103771396A (en) * | 2012-10-23 | 2014-05-07 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof, and electrochemical capacitor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106825591A (en) * | 2017-03-23 | 2017-06-13 | 厦门圣之岛金属科技有限公司 | A kind of tin alkene raw powder's production technology |
| CN110775966A (en) * | 2019-11-21 | 2020-02-11 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
| CN110775966B (en) * | 2019-11-21 | 2021-07-27 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
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Address after: 223900 Sihong Province Economic Development Zone, West Ocean Road, No. 6, No. Patentee after: Jiangsu Stick new materials Polytron Technologies Inc Address before: 215400 Taicang Economic Development Zone, Jiangsu, Qingdao West Road, No. 11, No. Patentee before: Suzhou Sidike New Material Science & Technology Co., Ltd. |
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