CN103466608A - Ball milling preparation method of graphene - Google Patents
Ball milling preparation method of graphene Download PDFInfo
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Abstract
The invention provides a ball milling preparation method of graphene. The ball milling preparation method comprises the following steps of: putting a mixture of graphite carbon and an alkyl six-membered aromatic ring or condensed ring polyether nonionic surfactant in the mass-volume ratio of 1: 2 to 1: 15, and deionized water in a ball milling jar, and fixing the ball milling jar on a ball mill for ball milling at a rotating speed ranging from 200 to 500 rpm for 5-30 hours; next, transferring the ball milled mixture to deionized water for centrifuging at a rotating speed ranging from 3000 to 8000 rpm for 10-30 minutes, and then obtaining a black upper-layer colloidal suspension for preparing graphene aqueous solutions with different concentrations. The graphene produced by the ball milling preparation method provided by the invention is dispersed in aqueous solutions and is high in concentration; the surfactant can be easily removed by using ethanol, which is friendly to environment and advantageous for wide application of graphene. The adopted ball milling equipment is simple, convenient to operate and safe to run; no new surface oxygen-containing functional group defect is introduced by ball milling; furthermore, the ball milling preparation method is mild and simple in preparation process, and high in yield.
Description
Technical field
What the present invention relates to is a kind of method of preparing grapheme material relevant with technical field of nano material, is specifically related to a kind of method that obtains grapheme material with new processing mode.
Background technology
Graphene, the two-dimentional atomic crystal material that a kind of carbon atom close-packed arrays of individual layer forms.Within 2004, by people such as scientist Geim A K, pass through the adhesive tape plumbago single slice that exfoliated graphite obtains repeatedly.Before Graphene is found, theoretical and experimentally all think perfect two-dirnentional structure all can't be under non-zero absolute temperature stable existence, so the discovery of Graphene caused global concern, its discoverer has obtained the Nobel Prize in physics of 2010 simultaneously.
In fact, Graphene is the composition unit of other dimension carbon-based materials.The soccerballene of zero dimension can be regarded as the reunion of particular graphite alkene shape and forms; The carbon nanotube of one dimension can be regarded as the curling structure formed of Graphene; Three-dimensional graphite can be regarded as by Graphene and forms through piling up.Although Graphene only has the thickness of a carbon atom, and be the thinnest a kind of in known materials, its hardness ratio is taller 100 times of best iron and steel in the world.Electroconductibility is also best in current known materials, and the movement velocity of electronics has reached 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.The performance that these are superior and special two-dirnentional structure make Graphene have fine development prospect.
Due to the quantum effect of Graphene uniqueness and excellent chemical property, when the electronics in Graphene moves in track, can or not introduce foreign atom because of lattice imperfection scattering occurs.Because reactive force between its atom is very strong, though at normal temperatures on every side carbon atom telescope, the interference that the electronics in Graphene is subject to is also very little.At aspects such as electron device and transistor, photon sensor, matrix material, solar cell, ultracapacitor, hydrogen storage materials, be with a wide range of applications.As storing the New Type of Carbon sill of electric charge in ultracapacitor, the theoretical specific surface area of Graphene can reach 2630m
2/ g, this means that positive and negative charge ions a large amount of in electrolytic solution can be stored in a thin layer of formation in the Graphene monolithic, thereby reach high Charge Storage level, increased electrical capacity.This is significantly in the improvement shop and efficiency and the performance of hybrid vehicles.
The preparation method of Graphene, mainly contain numerous preparation methods such as mechanically peel method, crystal epitaxy method, chemistry redox method, chemical Vapor deposition process, electrochemical stripping method and organic synthesis at present.
Patent US7824651B2 has described a kind of method that obtains being dispersed in the Graphene in tensio-active agent based on the supersound process graphite flake.The method is by adding dispersion agent sodium lauryl sulphate (SDS), and ultrasonic 2h obtains the graphite suspension of stable dispersion; In patent US2798878, use chemical oxidization method, by adding potassium permanganate, the vitriol oil, SODIUMNITRATE etc., pyrolytic graphite is carried out to the strong oxide treatment of low temperature, obtain graphite oxide, supersound process obtains the method for graphene oxide; In patent CN102275908A, disclose a kind of Hummers method traditional by improvement, through the ultrasonic sufficient graphene oxide colloidal solution of oxidation for preparing, added reductive agent, reacting by heating, process and obtain being dispersed in the Graphene colloidal solution in organic solvent.
At present, the method for using chemistry redox to obtain Graphene is the most general with widely, prolongs and has held the Hummers oxidation style, then obtained graphene oxide through ultrasonic dispersion, and last reductive agent reduction, obtain Graphene.But this method is used strong oxidizer and severe corrosive acid, introduced exhibiting high surface oxygen-containing functional group defect in the Graphene product, and experimentation is complicated, tediously long consuming time.
The present invention, use simple industrial ball milling method commonly used to make the high concentration graphene aqueous solution by cheap nonionogenic tenside naphthols Soxylat A 25-7 (NPE).
Summary of the invention
The Graphene surface oxygen functional group defect that the objective of the invention is to prepare for prior art is many, and condition harshness or cost are high, and the deficiency that can not produce in enormous quantities provides a kind of cost low, and output is high, the preparation method of the grapheme material that process is simple to operation.
The present invention is achieved by the following technical solutions:
A kind of ball-milling preparation method of grapheme material comprises the following steps:
1) be that 1:2～1:15 and deionized water mix and be loaded on ball grinder by the mass volume ratio of the hexa-atomic aromatic ring of graphite carbon and alkyl or condensed ring polyether nonionic surfactant, be fixed in the rotating speed ball milling 5-30 hour of ball mill with 200-500rpm.
2) by step 1) product proceed in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, make the different concns graphene aqueous solution.
Step 1) in, graphite carbon is one or more in Graphite Powder 99, crystalline flake graphite, pyrolytic graphite.
Step 1) the hexa-atomic aromatic ring of the alkyl in or condensed ring polyether nonionic surfactant are one or more in naphthols Soxylat A 25-7, nonyl naphthols Soxylat A 25-7, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
Graphene prepared by the present invention is scattered in the aqueous solution, and concentration is high, and tensio-active agent can easily be removed with ethanol, environmental protection and be conducive to the widespread use of Graphene.The employing ball-grinding machine is simple, easy to operate, operating safety, and ball milling is not introduced new surface oxygen functional group defect.Tensio-active agent of the present invention is with low cost, mild condition, can be mass-produced.
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The accompanying drawing explanation
Fig. 1 is the infrared figure of the Graphene for preparing of the present invention.
Embodiment
Below with embodiment, the present invention is described in more detail.
Example 1:
The 1g Graphite Powder 99,5ml naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 400rmp, ball milling 12h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, is aterrimus.
The graphene aqueous solution vacuum filtration, make graphene film, its resistivity of the graphene film of not washing with ethanol is up to 7 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.3 kilo-ohm of every side, illustrates that Graphene surface oxygen functional group defect prepared by the present invention is few.
As Fig. 1, figure a is for the centrifugal Graphene of washing of ethanol, schemes b for not with the centrifugal Graphene of washing of ethanol.Can not see the infrared peak of NPE after washing, illustrated that ethanol can be by the tensio-active agent wash clean on Graphene surface.And figure a has no any oxygen-containing functional group peak, illustrate that ball milling is for introducing any new surface oxygen functional group defect.
Example 2
The 1g crystalline flake graphite, 2ml naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 500rmp, ball milling 10h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 5000rmp, gets upper solution, is black.By prepared its resistivity of the graphene film of not washing with ethanol of embodiment 1 method, up to 5 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.4 kilo-ohm of every side
Example 3
The 1g pyrolytic graphite, 5ml naphthols Soxylat A 25-7 and 5ml nonyl naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 500rmp, ball milling 5h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 8000rmp, gets upper solution, is slightly black.By prepared its resistivity of the graphene film of not washing with ethanol of embodiment 1 method, up to 10 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.2 kilo-ohm of every side.
Example 4
0.5g Graphite Powder 99 and 0.5g pyrolytic graphite, 15ml nonyl naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 200rmp, ball milling 20h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, is aterrimus.By prepared its resistivity of the graphene film of not washing with ethanol of embodiment 1 method, up to 13 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.2 kilo-ohm of every side.
Example 5
The 1g Graphite Powder 99, the 5ml polyoxyethylene nonylphenol ether, 10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 300rmp, ball milling 30h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, is furvous.By prepared its resistivity of the graphene film of not washing with ethanol of embodiment 1 method, up to 7 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.4 kilo-ohm of every side.
Example 6
The 1g Graphite Powder 99, the 5ml polyoxyethylene octylphenol ether, 10ml deionized water mixing and ball milling, the ball grinder diameter is 15cm, the ball milling pearl is diameter 6mm and two kinds of mixing of 11mm.Be fixed in planetary ball mill, rotating speed 400rmp, ball milling 25h.Products obtained therefrom proceeds in the 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, is black.By prepared its resistivity of the graphene film of not washing with ethanol of embodiment 1 method, up to 8 kilo-ohms of every sides, and the graphene film resistivity of washing with ethanol is low to moderate 0.3 kilo-ohm of every side.
Claims (3)
1. the ball-milling preparation method of a grapheme material is characterized in that comprising the following steps:
Be that 1:2～1:15 and deionized water mix and be loaded on ball grinder by the mass volume ratio of the hexa-atomic aromatic ring of graphite carbon and alkyl or condensed ring polyether nonionic surfactant, be fixed in the rotating speed ball milling 5-30 hour of ball mill with 200-500rpm;
By step 1) product proceed in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, make the different concns graphene aqueous solution.
2. the ball-milling preparation method of grapheme material as claimed in claim 1, its feature: the graphite carbon step 1) is one or more in Graphite Powder 99, crystalline flake graphite, pyrolytic graphite.
3. the ball-milling preparation method of grapheme material as claimed in claim 1, its feature: step 1) the hexa-atomic aromatic ring of described alkyl or condensed ring polyether nonionic surfactant are one or more in naphthols Soxylat A 25-7, nonyl naphthols Soxylat A 25-7, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
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Cited By (15)
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| CN104448074A (en) * | 2014-12-09 | 2015-03-25 | 厦门凯纳石墨烯技术有限公司 | Special modified graphene for polymerization of vinyl chloride |
| CN105084346A (en) * | 2014-05-08 | 2015-11-25 | 国能科技创新有限公司 | Method for preparing multi-layer graphene |
| CN105129776A (en) * | 2015-07-14 | 2015-12-09 | 合肥工业大学 | Few-layer graphene and preparation method thereof |
| CN105776196A (en) * | 2016-03-22 | 2016-07-20 | 中国石油大学(北京) | Quick peeling device and method for producing graphene |
| CN106587034A (en) * | 2017-02-24 | 2017-04-26 | 安徽桑瑞斯环保新材料有限公司 | Lamina graphene production method |
| CN104576078B (en) * | 2014-12-22 | 2017-04-26 | 西北师范大学 | Preparation for 1-naphthol and reductive oxidation graphene composite as well as application of composite as supercapacitor electrode material |
| WO2018107795A1 (en) * | 2016-12-12 | 2018-06-21 | 广东纳路纳米科技有限公司 | Method for exfoliating hexagonal boron nitride (h-bn) by means of ball milling |
| CN109294283A (en) * | 2018-09-29 | 2019-02-01 | 青岛黑猫炭黑科技有限责任公司 | A kind of preparation method of multiphase nanoscale complex carbon material |
| CN109956499A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院深圳先进技术研究院 | The stripping means of two-dimensional material |
| CN113201301A (en) * | 2021-04-09 | 2021-08-03 | 北京科技大学 | Modification method of carbon nano tube for copper-clad plate |
| CN113307257A (en) * | 2021-07-06 | 2021-08-27 | 长春工业大学 | Preparation method of high-concentration water-based graphene dispersion liquid |
| CN113380556A (en) * | 2021-06-08 | 2021-09-10 | 福建师范大学泉港石化研究院 | Nano flaky conductive agent |
| CN113479866A (en) * | 2021-07-12 | 2021-10-08 | 丁民修 | Method for preparing graphene by stripping high-efficiency grinding body |
| CN114426271A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| WO2022161091A1 (en) * | 2021-01-27 | 2022-08-04 | 广东邦普循环科技有限公司 | Method for preparing graphene by mechanical exfoliation and application thereof |
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Cited By (18)
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| CN105084346A (en) * | 2014-05-08 | 2015-11-25 | 国能科技创新有限公司 | Method for preparing multi-layer graphene |
| CN104448074B (en) * | 2014-12-09 | 2017-02-22 | 厦门凯纳石墨烯技术股份有限公司 | Special modified graphene for polymerization of vinyl chloride |
| CN104448074A (en) * | 2014-12-09 | 2015-03-25 | 厦门凯纳石墨烯技术有限公司 | Special modified graphene for polymerization of vinyl chloride |
| CN104576078B (en) * | 2014-12-22 | 2017-04-26 | 西北师范大学 | Preparation for 1-naphthol and reductive oxidation graphene composite as well as application of composite as supercapacitor electrode material |
| CN105129776A (en) * | 2015-07-14 | 2015-12-09 | 合肥工业大学 | Few-layer graphene and preparation method thereof |
| CN105776196A (en) * | 2016-03-22 | 2016-07-20 | 中国石油大学(北京) | Quick peeling device and method for producing graphene |
| WO2018107795A1 (en) * | 2016-12-12 | 2018-06-21 | 广东纳路纳米科技有限公司 | Method for exfoliating hexagonal boron nitride (h-bn) by means of ball milling |
| CN106587034A (en) * | 2017-02-24 | 2017-04-26 | 安徽桑瑞斯环保新材料有限公司 | Lamina graphene production method |
| CN109956499A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院深圳先进技术研究院 | The stripping means of two-dimensional material |
| CN109294283A (en) * | 2018-09-29 | 2019-02-01 | 青岛黑猫炭黑科技有限责任公司 | A kind of preparation method of multiphase nanoscale complex carbon material |
| CN109294283B (en) * | 2018-09-29 | 2020-11-17 | 青岛黑猫炭黑科技有限责任公司 | Preparation method of multiphase nanoscale composite carbon material |
| CN114426271A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Graphene and preparation method thereof |
| WO2022161091A1 (en) * | 2021-01-27 | 2022-08-04 | 广东邦普循环科技有限公司 | Method for preparing graphene by mechanical exfoliation and application thereof |
| GB2617023A (en) * | 2021-01-27 | 2023-09-27 | Guangdong Brunp Recycling Technology Co Ltd | Method for preparing graphene by mechanical exfoliation and application thereof |
| CN113201301A (en) * | 2021-04-09 | 2021-08-03 | 北京科技大学 | Modification method of carbon nano tube for copper-clad plate |
| CN113380556A (en) * | 2021-06-08 | 2021-09-10 | 福建师范大学泉港石化研究院 | Nano flaky conductive agent |
| CN113307257A (en) * | 2021-07-06 | 2021-08-27 | 长春工业大学 | Preparation method of high-concentration water-based graphene dispersion liquid |
| CN113479866A (en) * | 2021-07-12 | 2021-10-08 | 丁民修 | Method for preparing graphene by stripping high-efficiency grinding body |
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