CN105600781B - A kind of ball milling aids in CO2The method that intercalation prepares form the few-layer graphene alkene - Google Patents
A kind of ball milling aids in CO2The method that intercalation prepares form the few-layer graphene alkene Download PDFInfo
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- CN105600781B CN105600781B CN201610117654.1A CN201610117654A CN105600781B CN 105600781 B CN105600781 B CN 105600781B CN 201610117654 A CN201610117654 A CN 201610117654A CN 105600781 B CN105600781 B CN 105600781B
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Abstract
The invention discloses a kind of ball milling to aid in CO2The method that intercalation prepares form the few-layer graphene alkene, it includes：Ball milling ball and graphite are added in ball grinder；Ball grinder is fixed to ball milling on planetary ball mill and obtains milled sample；Milled sample is transferred to high temperature resistant loads in vessel and be sent into the CVD tube furnaces of atmosphere protection and seal and vacuumize, be then continuously passed through CO2Gas；Heat to obtain intercalation sample；Intercalation sample is dissolved in deionized water and carries out ultrasound 0.5 2h of stripping, form the few-layer graphene alkene solution is obtained, it is dried in vacuo and ground, obtain form the few-layer graphene alkene powder.The present invention is modified to improve intercalation effect, then from CO the microstructure and stacked state of graphite by mechanical ball mill2For intercalator energy-conserving and environment-protective, the CO in stripping process2Gas is not left in graphene solution, is avoided the introducing of impurity and is improved the quality of graphene and save cumbersome cleaning process and shorten manufacturing cycle.
Description
Technical field
The present invention relates to the preparation method of graphene, more particularly to a kind of ball milling auxiliary CO2Intercalation prepares form the few-layer graphene alkene
Method.
Background technology
Graphene makes it in conductive material, super capacitor by performances such as its special electricity, optics, mechanics and calorifics
The field such as device, conductive display, electrically conductive ink additive, sensor, biomedicine, extraction shows good application potential.From
Prepare graphene so far for the first time, researchers make great progress in its preparation field.The preparation side of graphene at present
Method mainly has mechanical stripping method, CVD, oxidation-reduction method, liquid phase or gas phase intercalation stripping method, dilatometry, crystalline epitaxial life
Regular way, arc discharge method etc..Wherein cost is relatively low, technique is simple and easy to control, yield is higher etc. because it is prepared for oxidation-reduction method
Advantage and as one of method of current prepare with scale graphene, but in the method oxidation and reduction process all along with complexity
Chemical reaction and some performances of graphene are caused damage, and introduce a large amount of impurity.And liquid phase or gas phase intercalation are peeled off
Method is a kind of mechanical means, and yield is of a relatively high, cost is low, simple to operate, and the chemistry that whole process is not related to complexity substantially is anti-
And a large amount of impurity should will not be introduced, be a kind of main method for preparing high-quality graphene.
The A of Chinese patent CN 103482610 disclose a kind of preparation method of graphene, and this method is first by graphite and halogen
Intermetallic compound is blended in 48~60h of reaction under 100~160 DEG C of sealing states and obtains graphite intercalation compound, then in protective atmosphere
0.5~1h of lower 700~900 DEG C of reactions just obtains graphene.Although the method cost is low, technique is simple, yield is higher, its is anti-
Should the cycle is longer and severe reaction conditions, the intercalator interhalogen compounds used（Such as lodine chloride）With corrosivity, high poison
Property, strong and stimulating, it forms iodic anhydride in ingress of air, meets water or vapor exothermic heat of reaction and produces poisonous corrosion
Property gas, meet high thermal decomposition and disengage high poison flue gas, therefore it is unfriendly to environment and serious security hidden trouble be present.
The content of the invention
It is an object of the invention to propose a kind of ball milling auxiliary CO2The method that intercalation prepares form the few-layer graphene alkene, to solve to carry on the back
The problem of being proposed in scape technology.
To solve the above problems, the present invention provides following technical scheme：
A kind of ball milling aids in CO2The method that intercalation prepares form the few-layer graphene alkene, it comprises the following steps：
（1）Ball milling ball is added in ball grinder, ball milling ball is accounted for 1/3rd of ball milling tank volume；
（2）Graphite is added into ball grinder so that the mass ratio of graphite and ball milling ball is 1：10~50；
（3）Ball grinder is fixed to ball milling on planetary ball mill and obtains milled sample, and milled sample is transferred to resistance to height
Temperature is loaded in vessel；
（4）High temperature resistant is loaded to the middle part of the CVD tube furnaces of vessel feeding atmosphere protection, CVD tube furnaces are sealed
And vacuumize, then continuously it is passed through CO2Gas；
（5）400-800 DEG C of holding 1-3h is heated to, is then cooled to not higher than 70 DEG C, obtains intercalation sample；
（6）Intercalation sample is dissolved in deionized water and carries out ultrasound stripping 0.5-2h, obtains form the few-layer graphene alkene solution, it is right
It is dried in vacuo and ground, and obtains form the few-layer graphene alkene powder.
Further scheme, the step（1）In ball grinder for agate jar, nylon ball grinder, zirconia ball grinding jar,
Polytetrafluoroethylene (PTFE) ball grinder, corundum ball grinder, PU ball grinders, hard alloy ball grinder or stainless steel jar mill；
Ball milling ball is polytetrafluoroethylene (PTFE) ball, zirconia ball, wear-resisting high aluminium ball, PU balls, agate ball, wear-resistant chromium steel ball, no
Become rusty at least one of steel ball and high rigidity sintered carbide ball；A diameter of 2-10mm of ball milling ball.
Preferably, the step（2）In graphite for crystalline flake graphite, expansible graphite, highly oriented pyrolytic graphite or spherical
Graphite；The particle diameter of graphite is 200~625 mesh.
Preferably, the step（2）In the mass ratio of graphite and ball milling ball be 1:20.
Preferably, the step（3）In high temperature resistant load vessel be quartzy kiln furnitures or aluminium oxide ceramics kiln furnitures.
Preferably, the step（3）Middle ball grinder is with 300~600r/min 6~48h of rotating speed ball milling.
Preferably, the step（4）In continuous be passed through CO2The flow of gas is 0.3~0.8L/min.
Preferably, the step（5）In the heating rate for heating to 400-800 DEG C be 5 DEG C/min；It is cooled to not
Rate of temperature fall higher than 70 DEG C is 5 DEG C/min.
Preferably, the step（6）Middle intercalation sample is dissolved in deionized water forms the dense of intercalation sample aqueous solution
Degree is not higher than 10mg/mL；The ultrasonic power that ultrasound is peeled off is 300~1200W；Vacuum drying temperature is 60~120 DEG C.
Beneficial effects of the present invention：
1st, the present invention is modified the microstructure and stacked state of graphite by mechanical ball mill, so as to improve CO2With
Contact angle, the increase CO of graphite2With the contact surface of graphite, and then intercalation effect is improved so that the less graphene of the number of plies is made.
2nd, the present invention selects CO2For intercalator, complicated chemical reaction will not be introduced；And the CO in stripping process2Gas
It is not left in graphene solution, avoids the introducing of impurity and improve the quality of graphene, and saves cumbersome cleaning process
And shorten manufacturing cycle.
3rd, the present invention is avoided using high risk, the raw material of the unfriendly property of environment, safety, energy-saving and environmental protection, and easily real
Existing large-scale production.
Brief description of the drawings
Fig. 1 is that the SEM of original crystalline flake graphite schemes；
Fig. 2 is that the SEM of Graphite produced by the present invention schemes；
Fig. 3 is the FT-IR spectrograms of intercalation sample produced by the present invention；
Fig. 4 is the XRD of form the few-layer graphene alkene produced by the present invention；
Fig. 5 is that the TEM of form the few-layer graphene alkene produced by the present invention schemes.
Embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be defined by the claims
Implement with the multitude of different ways of covering.
Embodiment 1：
A kind of method that ball milling auxiliary CO2 intercalations prepare form the few-layer graphene alkene, comprises the following steps：
（1）A diameter of 3mm zirconia ball is added in 100mL zirconia ball grinding jar, zirconia ball is accounted for oxidation
/ 3rd of zirconium ball milling tank volume；
（2）The crystalline flake graphite that 3g particle diameters are 625 mesh is added into zirconia ball grinding jar so that crystalline flake graphite and ball milling ball
Mass ratio be 1：10；
（3）Zirconia ball grinding jar is fixed on planetary ball mill with 400r/min rotating speed ball milling 8h, obtains ball milling sample
Product, and milled sample is transferred in quartzy kiln furnitures；
（4）Quartzy kiln furnitures are sent into the middle part of the CVD tube furnaces of atmosphere protection, CVD tube furnaces are sealed and taken out true
Sky, CO is continuously then passed through with 0.5L/min flow2Gas；
（5）Heated by 5 DEG C/min of speed, be warming up to 650 DEG C holding 1.5h, then using rate of temperature fall as 5 DEG C/
Min is cooled to not higher than 70 DEG C, obtains intercalation sample；
（6）Intercalation sample is dissolved in the solution that concentration 5mg/mL is formed in deionized water, then using power as 600W pairs
It carries out ultrasound and peels off 1h, obtains form the few-layer graphene alkene solution, finally it is dried in vacuo and grinds to obtain form the few-layer graphene alkene
Powder.
Test analysis：
Raw material crystalline flake graphite and intermediate milled sample in the present embodiment, intercalation sample and final product widow's layer stone are taken respectively
Black alkene powder, vacuum drying 3h is carried out respectively in 60 DEG C.
The crystalline flake graphite of above-mentioned drying, milled sample, intercalation sample and form the few-layer graphene alkene are tested respectively, it is tested
As a result it is as follows：
Wherein, Fig. 1 is that the SEM of original crystalline flake graphite schemes, and Fig. 2 is the SEM of milled sample made from the embodiment of the present invention 1
Figure.Comparison diagram 1,2 can be seen that original crystalline flake graphite is in larger-size laminated structure in Fig. 1；And milled sample size in Fig. 2
It is obviously reduced, graininess is changed into by sheet, marginalisation degree significantly improves and a large amount of cavities occurs（Such as circle institute in Fig. 2
Show）, so as to be advantageous to intercalation.
Fig. 3 is the FT-IR spectrograms of intercalation sample made from embodiment 1, as can be seen from Figure 3, in 2330cm-1And 627cm-1Nearby there is stronger absworption peak, this is due to the CO inserted in graphite2In the asymmetric stretching vibration and face of molecule（Outside）
Caused by flexural vibrations；Other 1737cm-1Neighbouring peak belongs to-C=O stretching vibrations of sample lamella edge carboxyl；
1168cm-1Neighbouring peak belongs to the C-O-C stretching vibrations of sample interlayer.
Fig. 4 is the XRD of form the few-layer graphene alkene made from the embodiment of the present invention 1, it can be seen that is 23 ° in 2 θ and nearby spreads out
Peak is penetrated, with graphite（002）Crystallographic plane diffraction peak position is close, but diffraction maximum broadens, remitted its fury, and this is due to ball milling, intercalation
Graphite flake layer size reduction, the integrality of crystal structure decline, caused by degree of disorder increase afterwards；It it is 43 ° weaker nearby in 2 θ
Diffraction maximum, it is (100) crystallographic plane diffraction peak of graphene.
Fig. 5 is that the TEM of form the few-layer graphene alkene made from the embodiment of the present invention 1 schemes, it can be seen that prepared form the few-layer graphene alkene is in
Lamellar structure and transparency is higher, shows that its number of plies is less.
Embodiment 2：
A kind of method that ball milling auxiliary CO2 intercalations prepare form the few-layer graphene alkene, comprises the following steps：
（1）A diameter of 3.5 mm polytetrafluoroethylene (PTFE) ball is added in 100mL polytetrafluoroethylene (PTFE) ball grinder, makes poly- four
PVF ball accounts for 1/3rd of polytetrafluoroethylene (PTFE) ball milling tank volume；
（2）The spherical graphite for 400 mesh by 3g particle diameters is added into polytetrafluoroethylene (PTFE) ball grinder so that spherical graphite is with gathering
The mass ratio of tetrafluoroethene ball is 1：20；
（3）Polytetrafluoroethylene (PTFE) ball grinder is fixed on planetary ball mill with 600r/min rotating speed ball milling 6h, obtains ball
Grind away product, and milled sample is transferred in aluminium oxide ceramics kiln furnitures；
（4）Aluminium oxide ceramics kiln furnitures are sent into the middle part of the CVD tube furnaces of atmosphere protection, CVD tube furnaces are sealed
And vacuumize, then continuously it is passed through CO by 0.8L/min of flow2Gas；
（5）Carry out heating to 800 DEG C of holding 1h using speed as 5 DEG C/min, then enter by 5 DEG C/min of rate of temperature fall
Row is cooled to 60 DEG C, obtains intercalation sample；
（6）Intercalation sample is dissolved in the solution that concentration 8mg/mL is formed in deionized water, then using power as 300W pairs
It carries out ultrasound and peels off 2h, obtains form the few-layer graphene alkene solution, finally it is dried in vacuo and grinds to obtain form the few-layer graphene alkene
Powder.
Embodiment 3：
A kind of method that ball milling auxiliary CO2 intercalations prepare form the few-layer graphene alkene, comprises the following steps：
（1）A diameter of 4mm agate ball is added in 100mL agate jar, agate ball is accounted for agate jar
/ 3rd of volume；
（2）The expansible graphite that 3g particle diameters are 325 mesh is added into agate jar so that expansible graphite and agate ball
Mass ratio be 1：50；
（3）Agate jar is fixed on planetary ball mill with 300r/min rotating speed ball milling 48h, obtains ball milling sample
Product, and milled sample is transferred in quartzy kiln furnitures；
（4）Quartzy kiln furnitures are sent into the middle part of the CVD tube furnaces of atmosphere protection, CVD tube furnaces are sealed and taken out true
Sky, then continuously it is passed through CO by 0.3L/min of flow2Gas；
（5）Carry out heating to 400 DEG C of holding 3h using speed as 5 DEG C/min, then enter by 5 DEG C/min of rate of temperature fall
Row is cooled to 50 DEG C, obtains intercalation sample；
（6）Intercalation sample is dissolved in the solution that concentration 1mg/mL is formed in deionized water, then using power as 1200W pairs
It carries out ultrasound and peels off 0.5h, obtains form the few-layer graphene alkene solution, finally it is dried in vacuo and grinds to obtain form the few-layer graphene
Alkene powder.
Example discussed above is only that the preferred embodiment of the present invention is described, not to the scope of the present invention
It is defined, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art are to technical scheme
The various modifications made and improvement, it all should fall into the protection domain of claims of the present invention determination.
Claims (9)
1. a kind of ball milling aids in CO2The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Comprise the following steps：
（1）Ball milling ball is added in ball grinder, ball milling ball is accounted for 1/3rd of ball milling tank volume；
（2）Graphite is added into ball grinder so that the mass ratio of graphite and ball milling ball is 1：10~50；
（3）Ball grinder is fixed to ball milling on planetary ball mill and obtains milled sample, and milled sample is transferred to high temperature resistant dress
Carry in vessel；
（4）High temperature resistant is loaded to the middle part of the CVD tube furnaces of vessel feeding atmosphere protection, CVD tube furnaces are sealed and taken out
Vacuum, then continuously it is passed through CO2Gas；
（5）400-800 DEG C of holding 1-3h is heated to, is then cooled to not higher than 70 DEG C, obtains intercalation sample；
（6）Intercalation sample is dissolved in deionized water and carries out ultrasound stripping 0.5-2h, form the few-layer graphene alkene solution is obtained, it is entered
Row is dried in vacuo and ground, and obtains form the few-layer graphene alkene powder.
A kind of 2. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（1）In ball grinder for agate jar, nylon ball grinder, zirconia ball grinding jar, polytetrafluoroethylene (PTFE) ball grinder, corundum
Ball grinder, PU ball grinders, hard alloy ball grinder or stainless steel jar mill；
Ball milling ball is polytetrafluoroethylene (PTFE) ball, zirconia ball, wear-resisting high aluminium ball, PU balls, agate ball, wear-resistant chromium steel ball, stainless steel
At least one of ball；A diameter of 2-10mm of ball milling ball.
A kind of 3. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（2）In graphite be crystalline flake graphite, expansible graphite, highly oriented pyrolytic graphite or spherical graphite；The particle diameter of graphite is
200~625 mesh.
A kind of 4. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（2）In the mass ratio of graphite and ball milling ball be 1:20.
A kind of 5. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（3）In high temperature resistant load vessel be quartzy kiln furnitures or aluminium oxide ceramics kiln furnitures.
A kind of 6. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（3）Middle ball grinder is with 300~600r/min 6~48h of rotating speed ball milling.
A kind of 7. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（4）In continuous be passed through CO2The flow of gas is 0.3~0.8L/min.
A kind of 8. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（5）In the heating rate for heating to 400-800 DEG C be 5 DEG C/min；It is cooled to the cooling speed not higher than 70 DEG C
Rate is 5 DEG C/min.
A kind of 9. ball milling auxiliary CO according to claim 12The method that intercalation prepares form the few-layer graphene alkene, it is characterised in that：Institute
State step（6）The middle concentration that intercalation sample is dissolved in formation intercalation sample aqueous solution in deionized water is not higher than 10mg/mL；It is super
The ultrasonic power that sound is peeled off is 300~1200W；Vacuum drying temperature is 60~120 DEG C.
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| CN106430167B (en) * | 2016-09-20 | 2018-10-30 | 中国石油大学(北京) | A kind of lipophilic graphene and preparation method thereof |
| CN107021477A (en) * | 2017-05-26 | 2017-08-08 | 国家纳米科学中心 | A kind of method of macroscopic preparation of graphene and graphene oxide |
| CN109273702B (en) * | 2018-11-28 | 2020-10-27 | 西安交通大学 | All-solid-state preparation method for uniformly coating graphene on surface of irregular micro-nano particle |
| CN113683084A (en) * | 2021-08-24 | 2021-11-23 | 洛阳师范学院 | Preparation method of functionalized few-layer graphene |
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| US8287699B2 (en) * | 2009-07-27 | 2012-10-16 | Nanotek Instruments, Inc. | Production of chemically functionalized nano graphene materials |
| CN103482610A (en) * | 2012-06-14 | 2014-01-01 | 海洋王照明科技股份有限公司 | Graphene preparation method |
| CN103030138B (en) * | 2012-12-17 | 2015-08-19 | 鸿纳（东莞）新材料科技有限公司 | Prevent back component and the preparation of folded few layer graphene powder and matrix material thereof |
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