CN103964426B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN103964426B CN103964426B CN201410205625.1A CN201410205625A CN103964426B CN 103964426 B CN103964426 B CN 103964426B CN 201410205625 A CN201410205625 A CN 201410205625A CN 103964426 B CN103964426 B CN 103964426B
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Abstract
The invention discloses the preparation method of a kind of Graphene, through the following steps that prepare: 1) prepare expansible graphite: natural flake graphite is scattered in the ethanol and concentrated nitric acid mixed solution that volume ratio is 50: 1～50: 10, 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, suspension is cooled down, filter, precipitate, wash, be dried, obtain expansible graphite；2) by 1) gained expansible graphite joins in organic foaming agent solution, places 30min～3h, stirring at normal temperature；3) by step 2) product heats, simultaneously stirring 1h～5h；4) ultrasonic vibration 3) product 13min～60min；5) by 4) products therefrom cools down, vacuum drying prepares Graphene monomer.The preparation method productivity of the Graphene that the present invention provides is high, and is not required to add stabilizer simultaneously, effectively keeps the superperformance of Graphene.
Description
Technical field
The present invention relates to technical field of graphene, particularly to the preparation method of a kind of Graphene.
Background technology
Graphene (Graphene) is that a kind of to be formed hexangle type by carbon atom with SP2 hybrid orbital be Nidus Vespae
The electric conductivity flat film only with monolayer atomic thickness of lattice.It is the thinnest also that Graphene is currently world
Being the hardest nano material, it is almost fully transparent, for the material that resistivity in the world is minimum.
Graphene is considered as the basic structural unit of fullerene, CNT and graphite, its special calorifics,
Mechanics and conduction property, making Graphene be expected in preparing composite becomes raising polymer calorifics, power
Learn and the ideal filler of electric property.To this end, people explore many methods preparing Graphene, respectively
For: mechanical stripping method, liquid phase or meteorological directly stripping method (dilatometry), chemical vapour deposition technique, crystalline substance
External epitaxial growth and oxidation-reduction method, wherein liquid phase or meteorological directly stripping method (dilatometry) are to adopt
Carrying out intercalation with acid and obtain the graphite flakes that expansion rate is relatively low, graphite flakes average thickness is about 30 μ
M, lateral dimension is about 400 μm, and this graphite flakes is exactly expansible graphite.By this inflatable
Graphite is put in microwave or high temperature furnace and is heated, it is possible to obtain the nanometer that thickness is several nanometers to several tens of nanometers
Graphite flake.This method is because with cheap graphite or expanded graphite as raw material, preparation process is not related to chemistry
Change, liquid phase or the direct stripping method of gas phase are prepared Graphene and are had low cost, simple to operate, product quality
Advantages of higher, but it is serious to there is also that single-layer graphene productivity is the highest, lamella is reunited, and need to slough steady further
Determine the defects such as agent.
Based on the above, the exploitation of the preparation method of the Graphene of a kind of improvement is by necessary property.
Summary of the invention
For the problems referred to above, the present invention provides the preparation method of the Graphene of a kind of improvement, by aoxidizing
Graphite is suspended in azodicarbonamide class foaming agent, and the peeling force produced by foaming is more than graphite flake layer
Interstructural Van der Waals force so that graphite flake layer is peeled off, thus prepare Graphene.The graphite of this improvement
The Graphene productivity that the preparation method of alkene prepares is high, and is not required to add stabilizer simultaneously.
The preparation method of Graphene disclosed by the invention, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in the second that volume ratio is 50: 1～50: 10
In alcohol and concentrated nitric acid mixed solution, forming finely dispersed concentration is the outstanding of 0.005g/mL～0.05g/mL
Supernatant liquid, by this suspension hydro-thermal reaction 6h～48h at 80 DEG C～160 DEG C, suspension cooled down, filter,
Precipitate, wash, be dried, obtain expansible graphite.Use concentrated nitric acid that natural flake graphite carries out acid
Intercalation, prepares expansible graphite, it is achieved the pretreatment of graphite；
2) by 1) gained expansible graphite joins in organic foaming agent solution, places 30min～3h,
Stirring at normal temperature.By step 2) make expansible graphite and organic foaming agent solution be sufficiently mixed；
3) by step 2) product heats, simultaneously stirring 1h～5h.Step 3) effect be to make foaming agent
Reducing foaming, being foamed between graphite flake layer by foaming agent forms peeling force to graphite flake layer, thus promotes
The further stripping of expansible graphite；
4) ultrasonic vibration 3) product 13min～60min；By further ultrasonic vibration effect, improve
The productivity of Graphene.
5) by 4) products therefrom cools down, vacuum drying prepares Graphene monomer.
Preferably, the preparation method of described Graphene, wherein, described organic foaming agent is azo two
Benzamide type foaming agent.
Preferably, the preparation method of described Graphene, wherein, step 2) described in organic foaming
Agent is dissolved in dimethyl sulfoxide and prepares organic foaming agent solution.
Preferably, the preparation method of described Graphene, wherein, and step 3) it is heated to 160～260
℃
Preferably, the preparation method of described Graphene, wherein, step 3) mixing speed be 200～
600 turns/min.
Preferably, the preparation method of described Graphene, wherein, step 4) ultrasonic vibration is at room temperature
Under carry out.
Preferably, the preparation method of described Graphene, wherein, and step 5) vacuum drying condition
For room temperature, the vacuum drying time is 12h～48h.
The beneficial effect of the preparation method of the Graphene that the present invention provides: foamed by azodicarbonamide class
Graphene is prepared in agent foaming, and heating-up temperature only needs about 200 DEG C, reduces equipment requirements, makes stripping simultaneously
Promote from the Graphene productivity obtained；It is not required to add stabilizer during the preparation of this method, decreases at the later stage
Science and engineering sequence；Azodicarbonamide generates nitrogenous gas after decomposing, on product property impact minimum, and can be effective
Keep the superperformance of Graphene.
Detailed description of the invention
The present invention is described in further detail below, to make those skilled in the art with reference to description literary composition
Word can be implemented according to this.
Embodiment 1
The present embodiment provides the preparation method of Graphene, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in ethanol that volume ratio is 50: 1 and dense
In nitric acid mixed solution, form the suspension that finely dispersed concentration is 0.005g/mL, by this suspension
Hydro-thermal reaction 6h at 80 DEG C, cools down suspension, filters, precipitates, washs, is dried, and obtaining can be swollen
Swollen graphite；
2) by 1) gained expansible graphite joins in azodicarbonamide class foaming agent solution, and room temperature stirs
Mixing 30min, described azodicarbonamide class foaming agent solution solvent for use is dimethyl sulfoxide.
3) 2 being held) device of product puts in 160 DEG C of oil baths and heats, and stirs 1h, and mixing speed is
600 turns/min；
4) ultrasonic vibration 3 at normal temperatures) product 13min,
5) by 4) products therefrom cools down, vacuum drying 12h prepares Graphene monomer.
The lamellar spacing of the Graphene monomer prepared is 1.45nm；The specific surface area of described Graphene is
980m2/ g, productivity is 48%.
Embodiment 2
The present embodiment provides the preparation method of Graphene, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in ethanol that volume ratio is 50: 10 and dense
In nitric acid mixed solution, form the suspension that finely dispersed concentration is 0.05g/mL, this suspension is existed
Hydro-thermal reaction 48h at 160 DEG C, cools down suspension, filters, precipitates, washs, is dried, and obtaining can be swollen
Swollen graphite；
2) by 1) gained expansible graphite joins in azodicarbonamide class foaming agent solution, and room temperature stirs
Mixing 3h, described azodicarbonamide class foaming agent solution solvent for use is dimethyl sulfoxide.
3) 2 being held) device of product puts in 260 DEG C of oil baths, and constant temperature stirring 3h, mixing speed is
200 turns/min；
4) ultrasonic vibration 3 at normal temperatures) product 60min；
5) by 4) products therefrom cools down, vacuum drying 48h prepares Graphene monomer.
The lamellar spacing of the Graphene monomer prepared is 10nm；The specific surface of described Graphene is 450m2/ g,
Productivity is 78%.
Embodiment 3
The present embodiment provides the preparation method of Graphene, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in ethanol that volume ratio is 50: 5 and dense
In nitric acid mixed solution, form finely dispersed suspension, by this suspension hydro-thermal reaction at 100 DEG C
15h, cools down suspension, filters, precipitates, washs, is dried, obtain expansible graphite；
2) by 1) gained expansible graphite joins in azodicarbonamide class foaming agent solution, and constant temperature stirs
Mixing 40min, mixing speed is 300 turns/min, molten used by described azodicarbonamide class foaming agent solution
Agent is dimethyl sulfoxide.
3) 2 being held) device of product puts in 200 DEG C of oil baths and heats, constant temperature stirring 3h, stirring speed
Degree is 300 turns/min；
4) ultrasonic vibration 3 at normal temperatures) product 30min；
5) by 4) products therefrom cools down, vacuum drying 16h prepares Graphene monomer.
The lamellar spacing of the Graphene monomer prepared is 7nm, and the specific surface of described Graphene is 800m2/ g,
Productivity is 62%.
Embodiment 4
The present embodiment provides the preparation method of Graphene, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in ethanol that volume ratio is 50: 3 and dense
In nitric acid mixed solution, form finely dispersed suspension, by this suspension hydro-thermal reaction at 120 DEG C
24h, cools down suspension, filters, precipitates, washs, is dried, obtain expansible graphite；
2) by 1) gained expansible graphite joins in azodicarbonamide class foaming agent solution, and constant temperature stirs
Mixing 45min, described azodicarbonamide class foaming agent solution solvent for use is dimethyl sulfoxide.
3) by 2) product heats in 200 DEG C of oil baths, constant temperature stirring 1h, and mixing speed is 450 turns/min,；
4) ultrasonic vibration 3 at normal temperatures) product 40min,
5) by 3) products therefrom cools down, vacuum drying prepares Graphene monomer.
The lamellar spacing of the Graphene prepared is 6nm, and the specific surface of described Graphene is 600m2/ g, produces
Rate is 58%.
Embodiment 5
The present embodiment provides the preparation method of Graphene, through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in ethanol that volume ratio is 50: 8 and dense
In nitric acid mixed solution, form finely dispersed suspension, by this suspension hydro-thermal reaction at 150 DEG C
36h, cools down suspension, filters, precipitates, washs, is dried, obtain expansible graphite；
2) by 1) gained expansible graphite joins in azodicarbonamide class foaming agent solution, and constant temperature stirs
Mixing 50min, described azodicarbonamide class foaming agent solution solvent for use is dimethyl sulfoxide.
3) 2 being held) device of product puts in 220 DEG C of oil baths, constant temperature stirring 2.5h, mixing speed
It is 500 turns/min；
4) ultrasonic vibration 3 at normal temperatures) product 50min
5) by 4) products therefrom cools down, vacuum drying 20h prepares Graphene monomer.
The lamellar spacing of the Graphene prepared is 9nm；The specific surface of described Graphene is 750m2/ g, produces
Rate is 60%.
Although embodiment of the present invention are disclosed as above, but it is not restricted to description and embodiment party
Listed utilization in formula, it can be applied to various applicable the field of the invention completely, for being familiar with ability
For the personnel in territory, be easily achieved other amendment, therefore without departing substantially from claim and etc. homotype
Enclosing under limited general concept, the present invention is not limited to specific details.
Claims (3)
1. the preparation method of a Graphene, it is characterised in that through the following steps that prepare:
1) expansible graphite is prepared: natural flake graphite is scattered in the second that volume ratio is 50:1～50:10
In alcohol and concentrated nitric acid mixed solution, forming finely dispersed concentration is the outstanding of 0.005g/mL～0.05g/mL
Supernatant liquid, by this suspension hydro-thermal reaction 6h～48h at 80 DEG C～160 DEG C, suspension cooled down, filter,
Precipitate, wash, be dried, obtain expansible graphite；
2) by 1) gained expansible graphite joins in organic foaming agent solution, places 30min～3h,
Stirring at normal temperature, described organic foaming agent is azodicarbonamide class foaming agent, and described organic foaming agent dissolves
Organic foaming agent solution is prepared in dimethyl sulfoxide；
3) by step 2) product heats, stirring 1h～5h, is heated to 160～260 DEG C simultaneously, stirring
Speed is 200～600 turns/min；
4) ultrasonic vibration 3) product 13min～60min；
5) by 4) products therefrom cools down, vacuum drying prepares Graphene monomer.
The preparation method of Graphene the most according to claim 1, it is characterised in that step 4) super
Acoustic shock is swung and is carried out at normal temperatures.
The preparation method of Graphene the most according to claim 1, it is characterised in that step 5) true
The empty condition being dried is room temperature, and the vacuum drying time is 12h～48h.
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| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
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| 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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| 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 |
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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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