CN103466608B - A kind of ball milling preparation method of Graphene - Google Patents
A kind of ball milling preparation method of Graphene Download PDFInfo
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Abstract
A kind of ball-milling preparation method of grapheme material, the mass volume ratio of hexa-atomic to graphite carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant is that 1:2 ~ 1:15 and deionized water mix and be loaded on ball grinder by the present invention, is fixed on ball mill with the rotating speed ball milling 5-30 hour of 200-500rpm; Proceed to again in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, obtained different concns graphene aqueous solution.The graphene dispersion that the present invention produces is in the aqueous solution, and concentration is high, and tensio-active agent easily can be removed with ethanol, environmental protection and be conducive to the widespread use of Graphene.Employing ball-grinding machine is simple, easy to operate, operating safety, and ball milling does not introduce new surface oxygen functional group defect.Preparation process gentleness is simple and easy, and output is large.
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 obtaining grapheme material with new processing mode.
Background technology
Graphene, a kind of two-dimensional atomic crystal material of carbon atom close-packed arrays formation of individual layer.2004 by the people such as scientist Geim A K by adhesive tape repeatedly exfoliated graphite obtain plumbago single slice.Before Graphene is found, theoretical and experimentally all think perfect two-dirnentional structure all cannot under non-zero absolute temperature stable existence, therefore the discovery of Graphene causes global concern, and its discoverer obtains 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 of Graphene; Three-dimensional graphite can be regarded as and formed through piling up by Graphene.Although Graphene only has the thickness of a carbon atom, and be one the thinnest in known materials, taller 100 times of the iron and steel that its hardness ratio is best in the world.Electroconductibility is also best in current known materials, and the movement velocity of electronics reaches 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.These superior performances and special two-dirnentional structure make Graphene have fine development prospect.
Due to quantum effect and the excellent chemical property of Graphene uniqueness, when the electronics in Graphene moves in track, or foreign atom can not be introduced and scattering occurs because of lattice imperfection.Because its interatomic force is very strong, even if carbon atom telescopes at normal temperatures, the interference that the electronics in Graphene is subject to is also very little.Be with a wide range of applications in electron device and transistor, photon sensor, matrix material, solar cell, ultracapacitor, hydrogen storage material etc.As the New Type of Carbon sill storing 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 Graphene monolithic and forms a thin layer, thus reach high Charge Storage level, add electrical capacity.This can significantly in improvement shop and the efficiency of hybrid vehicles and performance.
The preparation method of Graphene, mainly contains 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 describes a kind of method obtaining the Graphene be dispersed in tensio-active agent based on supersound process graphite flake.The method, by adding dispersion agent sodium lauryl sulphate (SDS), ultrasonic 2h, obtains the graphite suspension of stable dispersion; In patent US2798878, use chemical oxidization method, carry out the process of low temperature Strong oxdiative by adding potassium permanganate, the vitriol oil, SODIUMNITRATE etc. to pyrolytic graphite, obtain graphite oxide, supersound process obtains the method for graphene oxide; In patent CN102275908A, disclose a kind of Hummers method traditional by improvement, obtain being oxidized sufficient graphene oxide colloidal solution, add reductive agent, reacting by heating through ultrasonic preparation, process obtains the Graphene colloidal solution disperseed in organic solvent.
At present, the method using chemistry redox to obtain Graphene is the most general with widely, namely prolongs and has held Hummers oxidation style, then obtain graphene oxide through ultrasonic disperse, and last reductive agent reduction, obtains Graphene.But this method uses strong oxidizer and severe corrosive acid, introduce exhibiting high surface oxygen-containing functional group defect, and experimentation is complicated, tediously long consuming time in graphene product.
The present invention, uses simple industrial conventional ball milling method by the obtained high concentration graphene aqueous solution of cheap nonionogenic tenside naphthols Soxylat A 25-7 (NPE).
Summary of the invention
The graphenic surface oxygen-containing functional group defect that the object of the invention is to prepare for prior art is many, and condition is harsh or cost is high, and the deficiency that can not produce in enormous quantities, provide a kind of cost low, 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 ball-milling preparation method for 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 hexa-atomic to graphite carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant, be fixed on ball mill with the rotating speed ball milling 5-30 hour of 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, obtained different concns graphene aqueous solution.
Step 1) in graphite carbon be one or more in Graphite Powder 99, crystalline flake graphite, pyrolytic graphite.
Step 1) in the hexa-atomic aromatic ring of alkyl or condensed ring polyether nonionic surfactant be one or more in naphthols Soxylat A 25-7, nonyl naphthols Soxylat A 25-7, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether.
Graphene dispersion prepared by the present invention is in the aqueous solution, and concentration is high, and tensio-active agent easily can be removed with ethanol, environmental protection and be conducive to the widespread use of Graphene.Employing ball-grinding machine is simple, easy to operate, operating safety, and ball milling does not introduce new surface oxygen functional group defect.Tensio-active agent of the present invention is with low cost, mild condition, can be mass-produced.
Accompanying drawing explanation
Fig. 1 is the infrared figure of Graphene prepared by the present invention.
Embodiment
The present invention is described in more detail to use embodiment below.
Example 1:
1g Graphite Powder 99,5ml naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 400rmp, ball milling 12h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, in aterrimus.
Graphene aqueous solution vacuum filtration, obtained graphene film, its resistivity of the graphene film not using ethanol washed is every side up to 7 kilo-ohms, and is low to moderate 0.3 kilo-ohm of every side by the graphene film resistivity that ethanol is washed, illustrates that graphenic surface oxygen-containing functional group defect prepared by the present invention is few.
As Fig. 1, figure a is for using the centrifugal washed Graphene of ethanol, and figure b is not for use the centrifugal washed Graphene of ethanol.Can not see the infrared peak of NPE after washing, illustrated that ethanol can by the tensio-active agent wash clean of graphenic surface.And figure a has no any oxygen-containing functional group peak, illustrate that ball milling is introduce any new surface oxygen functional group defect.
Example 2
1g crystalline flake graphite, 2ml naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 500rmp, ball milling 10h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 5000rmp, gets upper solution, in black.Every square up to 5 kilo-ohms by its resistivity of the graphene film not using ethanol washed obtained by embodiment 1 method, and be low to moderate 0.4 kilo-ohm of every side by the graphene film resistivity that ethanol is washed
Example 3
1g pyrolytic graphite, 5ml naphthols Soxylat A 25-7 and 5ml nonyl naphthols Soxylat A 25-7,10ml deionized water mixing and ball milling, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 500rmp, ball milling 5h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 8000rmp, gets upper solution, in omiting black.Every square up to 10 kilo-ohms by its resistivity of the graphene film not using ethanol washed obtained by embodiment 1 method, and be low to moderate 0.2 kilo-ohm of every side by the graphene film resistivity that ethanol is washed.
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, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 200rmp, ball milling 20h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, in aterrimus.Every square up to 13 kilo-ohms by its resistivity of the graphene film not using ethanol washed obtained by embodiment 1 method, and be low to moderate 0.2 kilo-ohm of every side by the graphene film resistivity that ethanol is washed.
Example 5
1g Graphite Powder 99,5ml polyoxyethylene nonylphenol ether, 10ml deionized water mixing and ball milling, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 300rmp, ball milling 30h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, in furvous.Every square up to 7 kilo-ohms by its resistivity of the graphene film not using ethanol washed obtained by embodiment 1 method, and be low to moderate 0.4 kilo-ohm of every side by the graphene film resistivity that ethanol is washed.
Example 6
1g Graphite Powder 99,5ml polyoxyethylene octylphenol ether, 10ml deionized water mixing and ball milling, ball grinder diameter is 15cm, and ball milling pearl is diameter 6mm and 11mm two kinds mixing.Be fixed on planetary ball mill, rotating speed 400rmp, ball milling 25h.Products obtained therefrom proceeds in 200ml deionized water, with the centrifugal 20min of the rotating speed of 3000rmp, gets upper solution, in black.Every square up to 8 kilo-ohms by its resistivity of the graphene film not using ethanol washed obtained by embodiment 1 method, and be low to moderate 0.3 kilo-ohm of every side by the graphene film resistivity that ethanol is washed.
Claims (2)
1. a ball-milling preparation method for grapheme material, is characterized in that comprising 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 hexa-atomic to graphite carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant, be fixed on ball mill with the rotating speed ball milling 5-30 hour of 200-500rpm; 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;
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, obtained different concns graphene aqueous solution.
2. the ball-milling preparation method of grapheme material as claimed in claim 1, its feature: step 1) described in graphite carbon be one or more in Graphite Powder 99, crystalline flake graphite, pyrolytic graphite.
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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 |
| 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 |
| CN106744875A (en) * | 2016-12-12 | 2017-05-31 | 广东纳路纳米科技有限公司 | A kind of method that ball milling peels off white graphite alkene |
| 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 |
| 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 |
| CN112777588B (en) * | 2021-01-27 | 2022-10-18 | 广东邦普循环科技有限公司 | Method for preparing graphene through mechanical stripping and application thereof |
| CN113201301B (en) * | 2021-04-09 | 2022-04-08 | 北京科技大学 | Modification method of carbon nano tube for copper-clad plate |
| CN113380556B (en) * | 2021-06-08 | 2022-10-28 | 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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