CN105600781A - Method for preparing single-layer graphene through CO2 intercalation assisted by ball milling - Google Patents
Method for preparing single-layer graphene through CO2 intercalation assisted by ball milling Download PDFInfo
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a method for preparing single-layer graphene through CO2 intercalation assisted by ball milling. The method includes the steps that ball milling balls and graphite are added into a ball milling tank; the ball milling tank is fixed to a planetary ball mill for ball milling, and a ball milling sample is obtained; the ball milling sample is transferred into a high-temperature-resistant loading vessel and conveyed into a CVD tubular furnace protected by atmosphere to be sealed and vacuumized, and then CO2 gas is continuously introduced; heating is conducted to obtain an intercalation sample; the intercalation sample is dissolved in deionized water to be subjected to ultrasonic stripping for 0.5-2 h, a single-layer graphene solution is obtained, the single-layer graphene solution is vacuumized, dried and ground, and single-layer graphene powder is obtained. The microstructure and the stacking state of graphite are modified through mechanical ball milling so that the intercalation effect can be improved, CO2 is selected as an intercalation agent, energy conservation and environment friendliness are achieved, the CO2 gas will not be left in the graphene solution in the stripping process, introduction of impurities is avoided, the quality of graphene is improved, the complex cleaning process is omitted, and the preparation period is shortened.
Description
Technical field
The present invention relates to the preparation method of Graphene, particularly the auxiliary CO of a kind of ball milling2Intercalation is prepared few layer grapheneMethod.
Background technology
Graphene relies on the performances such as its special electricity, optics, mechanics and calorifics to make it at conductive material, super capacitorThe fields such as device, conduction demonstration, electrically conductive ink additive, sensor, biomedicine, extraction show good application potential. FromPrepare for the first time Graphene so far, researchers make great progress in its preparation field. The preparation side of Graphene at presentMethod mainly contains mechanical stripping method, CVD method, oxidation-reduction method, liquid phase or gas phase intercalation stripping method, dilatometry, the life of crystal extensionRegular way, arc discharge method etc. Wherein oxidation-reduction method is because its preparation cost is lower, technique is simple and easy to control, output is more highAdvantage and become current scale and prepare one of method of Graphene, but in the method, oxidation and reduction process are all accompanied by complexityChemical reaction and some performance of Graphene is caused damage, and introduce a large amount of impurity. And liquid phase or gas phase intercalation are peeled offMethod is a kind of mechanical means, and output is relatively high, cost is low, simple to operate, and it is anti-that whole process does not relate to complicated chemistry substantiallyShould and can not introduce a large amount of impurity, be a kind of main method of preparing high-quality graphene.
Chinese patent CN103482610A discloses a kind of preparation method of Graphene, and the method is first by graphite and halogenMutually compound is blended in and under 100～160 DEG C of sealing states, reacts 48～60h and obtain graphite intercalation compound, then at protective atmosphereLower 700～900 DEG C of reaction 0.5～1h just obtain Graphene. Although the method cost is low, technique simple, productive rate is higher, it is anti-The cycle of answering is length and severe reaction conditions, and the intercalator interhalogen compounds using (for example lodine chloride) has corrosivity, high poisonProperty, strong and stimulating, it forms iodic anhydride in the time of ingress of air, meets water or steam exothermic heat of reaction and also produces poisonous corrosionProperty gas, meet high thermal decomposition and disengage high toxic smoke gas, therefore it is unfriendly and have a serious security hidden trouble to environment.
Summary of the invention
The object of the invention is to propose the auxiliary CO of a kind of ball milling2Intercalation is prepared the method for few layer graphene, to solve the back of the bodyThe problem proposing in scape technology.
For addressing the above problem, the invention provides following technical scheme:
The auxiliary CO of a kind of ball milling2Intercalation is prepared the method for few layer graphene, and it comprises the following steps:
(1) ball milling ball is joined in ball grinder, make ball milling ball account for 1/3rd of ball grinder volume;
(2) in ball grinder, add graphite, the mass ratio that makes 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 dressCarry in vessel;
(4) high temperature resistant loading vessel are sent into the middle part of the CVD tube furnace of atmosphere protection, CVD tube furnace is sealed and taken outVacuum, then passes into CO continuously2Gas;
(5) heat to 400-800 DEG C and keep 1-3h, be then cooled to not higher than 70 DEG C, obtain intercalation sample;
(6) intercalation sample dissolution is carried out in deionized water to the ultrasonic 0.5-2h that peels off, obtain few layer graphene solution, it is enteredRow vacuum drying is also ground, and obtains few layer graphene powder.
Further scheme, the ball grinder in described step (1) be agate jar, nylon ball grinder, zirconia ball grinding jar,Polytetrafluoroethylene (PTFE) ball grinder, corundum ball grinder, PU ball grinder, carbide alloy ball grinder or stainless steel jar mill;
Ball milling ball is polytetrafluoroethylene (PTFE) ball, zirconia ball, wear-resisting high aluminium ball, PU ball, agate ball, wear-resistant chromium steel ball, stainless steelAt least one in ball and high rigidity sintered carbide ball; The diameter of ball milling ball is 2-10mm.
Preferably, the graphite in described step (2) is crystalline flake graphite, expansible graphite, highly oriented pyrolytic graphite or sphericalGraphite; The particle diameter of graphite is 200～625 orders.
Preferably, the mass ratio of the graphite in described step (2) and ball milling ball is 1:20.
Preferably, the high temperature resistant loading vessel in described step (3) are quartzy kiln furnitures or aluminium oxide ceramics kiln furnitures.
Preferably, the middle ball grinder of described step (3) is with rotating speed ball milling 6～48h of 300～600r/min.
Preferably, in described step (4), pass into continuously CO2The flow of gas is 0.3～0.8L/min.
Preferably, the heating rate of 400-800 DEG C of heating in described step (5) is 5 DEG C/min; Be cooled to notBe 5 DEG C/min higher than the rate of temperature fall of 70 DEG C.
Preferably, in described step (6), intercalation sample dissolution is formed to the dense of intercalation sample aqueous solution in deionized waterDegree is not higher than 10mg/mL; The ultrasonic ultrasonic power of peeling off is 300～1200W; Vacuum drying temperature is 60～120 DEG C.
Beneficial effect of the present invention:
1, the present invention by mechanical ball milling the microstructure to graphite and stacked state modify, thereby improve CO2With graphiteContact angle, increase CO2With the contact-making surface of graphite, and then improve intercalation effect to make the less Graphene of the number of plies.
2, the present invention selects CO2For intercalator, can not introduce complicated chemical reaction; And in stripping process CO2GasCan not stay in graphene solution, avoided the introducing of impurity and improved the quality of Graphene, and having saved loaded down with trivial details cleaning processAnd shortening manufacturing cycle.
3, the present invention avoids adopting the raw material of high risk, the unfriendly property of environment, safety, energy-saving and environmental protection, and easily realExisting large-scale production.
Brief description of the drawings
Fig. 1 is the SEM figure of original crystalline flake graphite;
Fig. 2 is the SEM figure of the Graphite that makes of the present invention;
Fig. 3 is the FT-IR spectrogram of the intercalation sample that makes of the present invention;
Fig. 4 is the XRD figure of the few layer graphene that makes of the present invention;
Fig. 5 is the TEM figure of the few layer graphene that makes of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the present invention can be defined by the claimsImplement with the multitude of different ways covering.
Embodiment 1:
The auxiliary CO2 intercalation of ball milling is prepared a method for few layer graphene, comprises the following steps:
(1) zirconia ball that is 3mm by diameter joins in the zirconia ball grinding jar of 100mL, makes zirconia ball account for zirconia ball/ 3rd of a grinding jar volume;
(2) be 625 object crystalline flake graphites to adding 3g particle diameter in zirconia ball grinding jar, make the matter of crystalline flake graphite and ball milling ballAmount is than being 1:10;
(3) zirconia ball grinding jar is fixed to the rotating speed ball milling 8h with 400r/min on planetary ball mill, obtains milled sample, andMilled sample is transferred in quartzy kiln furnitures;
(4) quartzy kiln furnitures are sent into the middle part of the CVD tube furnace of atmosphere protection, CVD tube furnace are sealed and vacuumized,Then pass into continuously CO with the flow of 0.5L/min2Gas;
(5) taking speed as 5 DEG C/min heats, be warmed up to 650 DEG C and keep 1.5h, then enter taking rate of temperature fall as 5 DEG C/minRow is cooled to not higher than 70 DEG C, obtains intercalation sample;
(6) intercalation sample dissolution is formed in deionized water to the solution of concentration 5mg/mL, then taking power as 600W, it is enteredThe ultrasonic 1h that peels off of row, obtains few layer graphene solution, finally it is carried out vacuum drying and grind obtaining few layer graphene powder.
Test analysis:
Get respectively the few layer graphene of the present embodiment Raw crystalline flake graphite and intermediate milled sample, intercalation sample and end productPowder, carries out respectively vacuum drying 3h in 60 DEG C.
Above-mentioned dry crystalline flake graphite, milled sample, intercalation sample and few layer graphene are tested respectively to its testResult is as follows:
Wherein, SEM that Fig. 1 is original crystalline flake graphite figure, Fig. 2 is the SEM figure of the milled sample that makes of the embodiment of the present invention 1. RightCan find out than Fig. 1,2, in Fig. 1, original crystalline flake graphite is larger-size laminated structure; And milled sample size obviously subtracts in Fig. 2Little, change into graininess by sheet, marginalisation degree obviously improves and occurs in a large number empty (as shown in circles in Fig. 2), therebyBe conducive to intercalation.
Fig. 3 is the FT-IR spectrogram of the intercalation sample that makes of embodiment 1, as can be seen from Figure 3, and at 2330cm-1And 627cm-1Near the stronger absworption peak of appearance, this is due to the CO inserting in graphite2In the asymmetric stretching vibration of molecule and face (outward)Flexural vibrations cause; 1737cm in addition-1Near peak belongs to sample lamella edge carboxyl-C=O stretching vibration;1168cm-1Near peak belongs to the C-O-C stretching vibration between sample layer.
Fig. 4 is the XRD figure of the few layer graphene that makes of the embodiment of the present invention 1, can find out, near 2 θ are 23 °, occursDiffraction maximum, close with (002) crystal face diffraction maximum position of graphite, but diffraction maximum broadens, remitted its fury, and this is due to ball milling, insertsThe rear graphite flake layer size of layer dwindled, the integrality of crystal structure declines, degree of disorder increase causes; Near 2 θ are 43 ° a little less thanDiffraction maximum, be (100) crystal face diffraction maximum of Graphene.
Fig. 5 is the TEM figure of the few layer graphene that makes of the embodiment of the present invention 1, can find out, prepared few layer graphene isLamellar structure and transparency are higher, show that its number of plies is less.
Embodiment 2:
The auxiliary CO2 intercalation of ball milling is prepared a method for few layer graphene, comprises the following steps:
(1) the polytetrafluoroethylene (PTFE) ball that is 3.5mm by diameter joins in the polytetrafluoroethylene (PTFE) ball grinder of 100mL, makes polytetrafluoroethyl-neAlkene ball accounts for 1/3rd of polytetrafluoroethylene (PTFE) ball grinder volume;
(2) be 400 object spherical graphites, make spherical graphite and polytetrafluoro to adding 3g particle diameter in polytetrafluoroethylene (PTFE) ball grinderThe mass ratio of ethene ball is 1:20;
(3) polytetrafluoroethylene (PTFE) ball grinder is fixed to the rotating speed ball milling 6h with 600r/min on planetary ball mill, obtains ball milling sampleProduct, 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 furnace of atmosphere protection, CVD tube furnace is sealed and taken outVacuum, then passes into CO continuously taking flow as 0.8L/min2Gas;
(5) heat to 800 DEG C taking speed as 5 DEG C/min and keep 1h, then fall taking rate of temperature fall as 5 DEG C/minTemperature, to 60 DEG C, obtains intercalation sample;
(6) intercalation sample dissolution is formed in deionized water to the solution of concentration 8mg/mL, then taking power as 300W, it is enteredThe ultrasonic 2h that peels off of row, obtains few layer graphene solution, finally it is carried out vacuum drying and grind obtaining few layer graphene powder.
Embodiment 3:
The auxiliary CO2 intercalation of ball milling is prepared a method for few layer graphene, comprises the following steps:
(1) agate ball that is 4mm by diameter joins in the agate jar of 100mL, makes agate ball account for agate jar volume1/3rd;
(2) be 325 object expansible graphites to adding 3g particle diameter in agate jar, make the matter of expansible graphite and agate ballAmount is than being 1:50;
(3) agate jar is fixed to the rotating speed ball milling 48h with 300r/min on planetary ball mill, obtains milled sample, andMilled sample is transferred in quartzy kiln furnitures;
(4) quartzy kiln furnitures are sent into the middle part of the CVD tube furnace of atmosphere protection, CVD tube furnace are sealed and vacuumized,Then pass into continuously CO taking flow as 0.3L/min2Gas;
(5) heat to 400 DEG C taking speed as 5 DEG C/min and keep 3h, then fall taking rate of temperature fall as 5 DEG C/minTemperature, to 50 DEG C, obtains intercalation sample;
(6) intercalation sample dissolution is formed in deionized water to the solution of concentration 1mg/mL, then taking power as 1200W, it is enteredThe ultrasonic 0.5h that peels off of row, obtains few layer graphene solution, finally it is carried out vacuum drying and grind obtaining few layer graphene powderBody.
Above-described example is only that the preferred embodiment of the present invention is described, not to scope of the present inventionLimit, design under the prerequisite of spirit not departing from the present invention, those of ordinary skill in the art are to technical scheme of the present inventionVarious distortion and the improvement made, all should fall in the definite protection domain of the claims in the present invention book.
Claims (9)
1. the auxiliary CO of ball milling2Intercalation is prepared the method for few layer graphene, it is characterized in that: comprise the following steps:
(1) ball milling ball is joined in ball grinder, make ball milling ball account for 1/3rd of ball grinder volume;
(2) in ball grinder, add graphite, the mass ratio that makes 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 dressCarry in vessel;
(4) high temperature resistant loading vessel are sent into the middle part of the CVD tube furnace of atmosphere protection, CVD tube furnace is sealed and taken outVacuum, then passes into CO continuously2Gas;
(5) heat to 400-800 DEG C and keep 1-3h, be then cooled to not higher than 70 DEG C, obtain intercalation sample;
(6) intercalation sample dissolution is carried out in deionized water to the ultrasonic 0.5-2h that peels off, obtain few layer graphene solution, it is enteredRow vacuum drying is also ground, and obtains few layer graphene powder.
2. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteThe ball grinder of stating in step (1) is agate jar, nylon ball grinder, zirconia ball grinding jar, polytetrafluoroethylene (PTFE) ball grinder, corundumBall grinder, PU ball grinder, carbide alloy ball grinder or stainless steel jar mill;
Ball milling ball is polytetrafluoroethylene (PTFE) ball, zirconia ball, wear-resisting high aluminium ball, PU ball, agate ball, wear-resistant chromium steel ball, stainless steelAt least one in ball and high rigidity sintered carbide ball; The diameter of ball milling ball is 2-10mm.
3. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteThe graphite of stating in step (2) is crystalline flake graphite, expansible graphite, highly oriented pyrolytic graphite or spherical graphite; The particle diameter of graphite is200～625 orders.
4. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteStating graphite in step (2) and the mass ratio of ball milling ball is 1:20.
5. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteThe high temperature resistant loading vessel of stating in step (3) are quartzy kiln furnitures or aluminium oxide ceramics kiln furnitures.
6. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteState the rotating speed ball milling 6～48h of the middle ball grinder of step (3) with 300～600r/min.
7. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteState and pass into continuously CO in step (4)2The flow of gas is 0.3～0.8L/min.
8. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteThe heating rate of 400-800 DEG C of heating to of stating in step (5) is 5 DEG C/min; Be cooled to the not cooling speed higher than 70 DEG CRate is 5 DEG C/min.
9. the auxiliary CO of a kind of ball milling according to claim 12Intercalation is prepared the method for few layer graphene, it is characterized in that: instituteState the concentration that in step (6), intercalation sample dissolution is formed in deionized water to intercalation sample aqueous solution not higher than 10mg/mL; SuperThe ultrasonic power that sound is peeled off is 300～1200W; Vacuum drying temperature is 60～120 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430167A (en) * | 2016-09-20 | 2017-02-22 | 中国石油大学(北京) | 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 |
| CN109273702A (en) * | 2018-11-28 | 2019-01-25 | 西安交通大学 | The all solid state preparation method of irregular micro-nano particle coated with uniform graphene |
| 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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| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | Production of chemically functionalized nano graphene materials |
| CN103030138A (en) * | 2012-12-17 | 2013-04-10 | 鸿纳（东莞）新材料科技有限公司 | Folding preventing less-layer graphene powder, components of composite material thereof, and application |
| CN103482610A (en) * | 2012-06-14 | 2014-01-01 | 海洋王照明科技股份有限公司 | Graphene preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090026086A1 (en) * | 2007-07-27 | 2009-01-29 | Aruna Zhamu | Electrochemical method of producing nano-scaled graphene platelets |
| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430167A (en) * | 2016-09-20 | 2017-02-22 | 中国石油大学(北京) | 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 |
| CN109273702A (en) * | 2018-11-28 | 2019-01-25 | 西安交通大学 | The all solid state preparation method of irregular micro-nano particle coated with uniform graphene |
| 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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