CN103466612A - Method for preparing native grapheme by means of frequency mixing ultrasound - Google Patents
Method for preparing native grapheme by means of frequency mixing ultrasound Download PDFInfo
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Abstract
The invention discloses a method for preparing native grapheme by means of frequency mixing ultrasound. The frequency mixing ultrasound which contains more than two ultrasonic frequency components is used, graphite is used as preparation raw materials, and micro-bubbles with various sizes and bursting force are generated through an ultrasonic cavitation effect of the ultrasound of different frequencies to conduct mechanical stripping on the graphite raw materials to obtain native grapheme nanometer materials. According to the method for preparing the native grapheme by means of the frequency mixing ultrasound, firstly, the ultrasound is used in the preparation of the grapheme, the large enough stripping force is obtained, meanwhile, the destructive effect on the sheet-type structure and the surface crystal defects of the graphite raw materials can be greatly reduced, and the efficient preparation of the native grapheme which is high in quality, larger in sheet and small in number of layers is achieved.
Description
Technical field
The present invention relates to a kind of method for preparing primary Graphene by the frequency mixing ultrasonic effect.
Background technology
Graphene (Graphene), claim again mono-layer graphite, is a kind of by the monolayer carbon atomic building, is cellular planar crystal.For a long time, Graphene is considered to imaginary structure always, not necessary being.The physicist Konstantin Novoselov of Univ Manchester UK in 2004 and Andre Geim be take graphite as raw material, obtained the Graphene [Science of individual layer by the method for mechanically peel, 306(2004) 666], two people also serve as reasons because of " in the initiative experiment of two-dimentional grapheme material ", common acquisition Nobel Prize in physics in 2010, started the upsurge that Graphene is studied instantly immediately.
The reason that Graphene becomes study hotspot is machinery, optics, the electrical properties of its excellence.Except the common high-specific surface area (2630m of nano material
2/ g) outside, Graphene is current known the thinnest (about 0.34nm) [Science, 306(2004) 666], is also the highest nano material of Young's modulus (about 1.0Tpa) [Science, 321(2008) 385].Under normal temperature, its carrier mobility surpasses 200000cm
2/ Vs, far above ratio nano carbon pipe or silicon crystal [Solid State Comm., 146(2008) 351].The visible light transmissivity of single-layer graphene is 97.7%, and the hertzian wave of different wave length is all had to sorption [Science, 320(2008) 1308].Thermal conductivity is up to 5000W/mK, higher than carbon nanotube and diamond [Nano Lett., 8(2008) 902].But the motivation that Graphene is applied to gene sequencing of new generation not only is that Graphene has good electroconductibility, it is natural good electrode materials, and single-layer graphene only has 0.34nm thick, with the fine coupling of bulk (0.36nm) of single base [Nature, 467(2010) 190].
The preparation method of Graphene is divided into chemical method and the large class of Physical two at present.Chemical preparation is generally, by oxygenant, Graphene is oxidized into to graphene oxide (graphene oxide, be called for short GO) and disperseed, prepare redox graphene (reduced graphene oxide by the strong reductant effect again, be called for short RGO) [Acs Nano, 5(2011) 191].As the people such as Schniepp use sulfuric acid, salpeter solution, graphite is carried out to oxidation, then obtain the graphene film [J.Phys.Chem.B, 110(2006) 8535] of nearly individual layer (0.44nm) by high temperature reduction.Can prepare larger-size graphene film (can reach grade) with oxide-reduction method, preparation flow is easy to be controlled, and cost is lower.But due to residual chemical group on residual reagent and interface, as hydroxyl, the acting in conjunction of carboxyl etc. causes the RGO surface imperfection, and the character of the each side such as its power, electricity is poor, can't meet the demand of high-quality graphene Application Areas.
Physical method mainly adopts the mechanically peel method, as tape stripping method [Science, 306(2004) 666], ultrasonic stripping method [J.Phys.Chem.C, 115(2011) 5422] etc.The Graphene of first in the world that Geim etc. prepare obtains by the tape stripping method.The standby Graphene of adhesive tape legal system has the advantages such as stable chemical nature, electroconductibility be good; Shortcoming is to prepare fully uncontrollablely, yields poorly, the graphene film size is little, shift difficulty etc.And at present the ultrasonic stripping means of report all adopts the graphite flake effect to various forms of single-frequency, low-frequency ultrasonic waves.Although the ultrasonic method of single-frequency can improve the productive rate of high-quality graphene, it can't guarantee stably to obtain large stretch of individual layer or the Graphene of the less number of plies.This is mainly because the cavitation bubble size that the single-frequency ultrasonic wave produces is comparatively single, the power that the low frequency ultrasound cavitation bubble produces is larger, destruction to thin layer graphite alkene is excessive, makes a large amount of carbon granule of generation in preparation and is attached on Graphene, has a strong impact on lamella size and the quality of Graphene; Otherwise single high frequency ultrasound cavitation bubble can't produce enough mechanical forces and graphite be peeled off to the Graphene that becomes individual layer or few layer.
In addition, method can be for the preparation of large-area Graphene in chemical vapour deposition (being called for short CVD), can reach the wafer level size, but manufacturing cost is high, and still can't obtain the thin layer graphite alkene film of few defect, cause graphene film electrical properties undesirable [Nano Lett., 10(2010) 4702].
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the invention provides a kind of method for preparing primary Graphene by the frequency mixing ultrasonic effect, the directed superpower frequency mixing ultrasonic ripple that the present invention has the different frequency composition by employing carries out mechanically peel to graphite raw material, utilize the cavitation bubble of the ultrasonic wave generation different size of different frequency, control ultrasonic wave to graphite raw material peel off strength and to the structural damage effect, obtain enough large peel off strength in, greatly reduce and destruction defect of crystal on crystal surface laminar structured to graphite raw material, finally realize high quality, larger lamella, the efficient preparation of few primary Graphene of the number of plies.
For achieving the above object, the technical solution used in the present invention is:
A kind of frequency mixing ultrasonic prepares the method for primary Graphene, the frequency mixing ultrasonic that use contains two or more ultrasonic frequency compositions, using graphite as preparing starting material, the microbubble that produces different size and bursting force by the hyperacoustic ultrasonic cavitation effect of different frequency carries out mechanically peel to graphite raw material, obtains primary graphene nano material.
Preferably, all hyperacoustic frequency that described frequency mixing ultrasonic comprises is all in 20～1000kHz.
Described frequency mixing ultrasonic acts on graphite raw material in two ways: a kind of be to act on simultaneously, be that the ultrasonic wave that described frequency mixing ultrasonic is two or three above ultrasonic frequency composition is mixed the rear ultrasonic source formed with any power ratio, the ultrasonic source that described mixing forms afterwards acts on graphite raw material; Another kind is to be divided into successively effect, and described frequency mixing ultrasonic comprises the ultrasonic wave of two or three above ultrasonic frequency composition, and the ultrasonic wave of described each composition successively acts on graphite raw material with any power.
Described graphite raw material is that purity is one or more the mixing in high purity raw ore China ink more than 97%, refining graphite, highly oriented pyrolytic graphite (being called for short HOPG) and expanded graphite, the particle diameter of described graphite raw material at micron order to the centimetre-sized scope, form is one or both the mixing in particle and sheet.
First graphite raw material be placed in or be scattered in liquid solvent, then using frequency mixing ultrasonic, in liquid phase, graphite raw material is carried out to ultrasonication.
Described liquid solvent is one or more the mixture in the material be in a liquid state under the normal temperature such as water, inorganic acid alkali solution, alcohols, aldehydes, ketone, liquid alkane class and alkane ketone.
The present invention is final obtain be directly by the graphite raw material upper glass, got off, the number of plies be 1～10 layer, the lamella area be 1～100 μ m, without the primary graphene nano material after chemical treatment, i.e. intrinsic Graphene.
Beneficial effect: frequency mixing ultrasonic provided by the invention prepares the method for primary Graphene, used ultrasonic wave first in the Graphene preparation, obtain enough large peel off strength in, can greatly reduce and destruction defect of crystal on crystal surface laminar structured to graphite raw material, realize the efficient preparation of high quality, larger lamella, few primary Graphene of the number of plies.
Embodiment
Below in conjunction with example, the present invention is further described.
Frequency mixing ultrasonic ripple provided by the invention carries out the method for mechanically peel to graphite, graphite is a kind of or its arbitrary proportion mixture in raw ore graphite, refining graphite, expanded graphite or highly oriented pyrolytic graphite, state is solid-state, and pattern is sheet or the particulate state of micron to centimetre-sized.The dispersion solvent of solid graphite is the organic solvents such as water, Organic Alcohol or ketone, aromatic liquid compounds of group, methyl-2-pyrrolidone.The frequency mixing ultrasonic wave frequency is 20～1000kHz.Use is carried out more than the ultrasonication of 1 time graphite dispersing solution more than the monofrequency of a kind is ultrasonic, or uses the mixing ultrasonic wave after superposeing more than a kind of frequency content, with any power ratio to carry out ultrasonication to graphite dispersing solution, or the combination of said two devices.The ultrasonic wave of different frequency can form the ultrasonic cavitation bubble with different mean sizess in liquid, the mean sizes of low frequency cavitation bubble is larger, the mechanical force that its spalling produces is larger, thereby bulk graphite is had to the effect of peeling off preferably, yet also larger to the destruction of graphite-structure; Otherwise high frequency cavitation bubble mean sizes is less; the mechanical force that spalling produces is little; be not enough to large stretch of graphite is peeled off and become lamelliform; but can carry out further meticulous peeling off for the graphite flake that becomes thin layer; make it to become to have and be less than 10 layers of graphene nano material that carbon atom is stacking, can protect Graphene sheet form and surface not to be subject to large destruction simultaneously.Therefore, graphite is subject to the hyperacoustic cavitation effect effect of different frequency in dispersion liquid, can be stripped from become individual layer or few layer, uniformly, high-quality graphene with larger lamella size.
A kind of example based on above-mentioned explanation is: select grade high purity graphite chip solid, be dispersed in dehydrated alcohol, use the ultrasonic wave of 40kHz and 400kHz, form the frequency mixing ultrasonic ripple after the equipower stack, to graphite dispersing solution effect 1～3 hour, through the centrifuging and taking upper strata, obtain the dispersion liquid of few layer graphene.
Another kind of example based on above-mentioned explanation is: select centimetre-sized highly oriented pyrolytic graphite chip solid, immerse in the crassitude ketone solvent, successively use the single-frequency ultrasonic wave of 100kHz and 600kHz, Graphene is acted on respectively to 1～3 hour, through the centrifugal upper strata of going, can obtain the graphene dispersing solution of nearly individual layer, sheet.
Below in conjunction with example, the present invention is further illustrated.
Embodiment 1:
(1) take 30mg grade high purity graphite sheet (purity > 99.9%), be placed in the centrifuge tube that fills the 10mL dehydrated alcohol standing 1 hour;
(2) produce 100kHz and 400kHz ultrasonic wave, all power is adjusted to 100W, output probe hybrid junction is placed on centrifuge tube outer wall bottom, adds ultrasonic water medium used until its ethanol liquid level with centrifuge tube inside is equal in tank;
(3) use above-mentioned two kinds of frequencies to graphite dispersing solution effect 2 hours simultaneously; Notice that the water temperature in the controlled circulation tank can not surpass 40 degrees centigrade therebetween, as excess Temperature, should change in time water or the cooling of ON cycle water device;
(4) after ultrasonic end, that dispersion liquid is centrifugal with 20000rpm, after taking out centrifuge tube reposefully, with pipettor, slowly draw upper strata 6mL liquid, be primary graphene dispersing solution.
Implementation result:
(1) Graphene content in the gained dispersion liquid is measured.The demonstration of wavelength 670nm Graphene characteristic absorption spectrum, in dispersion liquid, Graphene content reaches 0.1mg/mL;
(2) the gained Graphene is carried out to transmission electron microscope observation.With after the sample preparation of ultra-thin micro-grid copper mesh, utilize high resolution transmission electron microscopy to carry out the observation at Graphene size and edge.Result shows, primary graphene film prepared by the method, and mean sizes is at 1～10 μ m
2, 3～5 layers of its edge average out to, and defect is less.Image spot after Fast Fourier Transform (FFT) is sharp-pointed, and boundary is clearly demarcated.Graphene prepared by above analytical results explanation the method has very high quality.
(3) the gained Graphene is carried out on silicon dioxide substrates to AFM surface topography sign.Graphene thickness is about 1～1.5nm, and its surface has the special pleated structure of Graphene.The characterization result explanation, the method can the very high few layer graphene of preparation quality.
Embodiment 2:
(1) use laser scriber, draw and get 5 * 10mm highly oriented pyrolytic graphite a slice, be weighed as 30mg, be fixed on fixture in the centrifuge tube that fills the 10mL methyl-2-pyrrolidone, the surrounding of graphite flake does not contact with centrifuge tube, and the graphite flake direction is consistent with centrifugal tubular axis;
(2) by the frequency adjustment of high-frequency ultrasonic generator, be 40kHz, output rating 100W, its ultrasonic generation probe is placed in circulating water channel, at the bottom of centrifuge tube under;
(3) add water to equally with reagent liquid level in centrifuge tube in circulating water channel, open ultrasonic wave, to graphite flake effect 1 hour.The close attention water temperature changes, and changes in time water cooling.Now can be observed the solvent color and graduate into light grey by water white transparency;
(4) by the frequency adjustment of high-frequency ultrasonic generator, be 600kHz, all the other conditions are constant, repeating step (2)～(3);
(5) ultrasonic end, after taking out reposefully in centrifuge tube the fixture that accompanies graphite flake, that dispersion liquid is centrifugal with 20000rpm, slowly draw upper strata 6mL liquid with pipettor, be primary graphene dispersing solution.
Implementation result:
(1) the Graphene content of above-mentioned gained dispersion liquid is measured.The Graphene characteristic absorption spectrum demonstration of wavelength 670nm, the Graphene content in dispersion liquid is 30～100 μ g/mL.
(2) the gained Graphene is carried out to transmission electron microscope observation.After the sample preparation of the micro-grid copper mesh of ultrathin carbon films, utilize transmission electron microscope to carry out the observation at Graphene size and edge.Result shows, primary graphene film prepared by the method, and mean sizes is at 10～100 μ m
2, 1～4 layer of its edge average out to, have no defect substantially in the visual field.Image spot after Fast Fourier Transform (FFT) is sharp-pointed, and border is clearly demarcated.Above analytical results explanation the method can be used for the Graphene that preparation is as thin as individual layer, and the Graphene of preparation has high quality.
(3) the gained Graphene is carried out on silicon dioxide substrates to AFM surface topography sign.Graphene thickness is 0.4～1.5nm, and its surface has the special pleated structure of Graphene.Characterization result explanation, can the preparation quality high individual layer of the method preparation is layer graphene at least.
(4) the gained Graphene is carried out on copper substrate to the Raman spectrum characteristic peak analysis.The feature Raman peaks intensity ratio D/2G of Graphene is 0.4～0.8.Characterization result illustrates that the Graphene that this preparation method obtains has high quality.
Embodiment 3:
(1) take the 30mg expanded graphite particles, be well dispersed in the centrifuge tube that fills 10mL methyl-2-pyrrolidone reagent.Use the 40kHz ultrasonic wave, power 15W processes 10 minutes dispersion liquid;
(2) by the frequency setting of high frequency ultrasound generator, be 100kHz, power 100W, its ultrasonic generation probe is placed in circulating water channel, at the bottom of centrifuge tube under;
(3) add water to equally with reagent liquid level in centrifuge tube in circulating water channel, open ultrasonic wave, to graphite flake effect 30 minutes.The close attention water temperature changes, and changes in time water cooling.Now can be observed upper strata solvent color and graduate into grey black by water white transparency;
(4) by the frequency adjustment of high-frequency ultrasonic generator, be 800kHz, all the other conditions are constant, repeating step (2)～(3);
(5) ultrasonic end, take out centrifuge tube reposefully, centrifugal with 20000rpm, with pipettor, slowly draws upper strata 6mL liquid, obtains graphene dispersing solution.
Implementation result:
(1) the Graphene content of above-mentioned gained dispersion liquid is measured.The Graphene characteristic absorption spectrum demonstration of wavelength 670nm, the Graphene content in dispersion liquid is 0.4～0.7mg/mL, output is higher.
(2) the gained Graphene is carried out to transmission electron microscope observation.With after the sample preparation of ultra-thin micro-grid copper mesh, utilize high resolution transmission electron microscopy to carry out the observation at Graphene size and edge.Result shows, primary graphene film prepared by the method, and mean sizes is at 5～10 μ m
2, 3～10 layers of its edge average out to, have a small amount of lattice defect.Image spot after Fast Fourier Transform (FFT) is still sharp keen.Graphene prepared by above analytical results explanation the method has better quality.
(3) the gained Graphene is carried out on silicon dioxide substrates to AFM surface topography sign.Graphene thickness is about 2.4～10.2nm, and its surface has the special pleated structure of Graphene.The characterization result explanation, the method can the higher Graphene of preparation quality.
The above is only the preferred embodiment of the present invention; be noted that for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a frequency mixing ultrasonic prepares the method for primary Graphene, it is characterized in that: use the frequency mixing ultrasonic that contains two or more ultrasonic frequency compositions, using graphite as preparing starting material, the microbubble that produces different size and bursting force by the hyperacoustic ultrasonic cavitation effect of different frequency carries out mechanically peel to graphite raw material, obtains primary graphene nano material.
2. frequency mixing ultrasonic according to claim 1 prepares the method for primary Graphene, it is characterized in that: all hyperacoustic frequency that described frequency mixing ultrasonic comprises is all in 20～1000kHz.
3. frequency mixing ultrasonic according to claim 1 and 2 prepares the method for primary Graphene, it is characterized in that: the ultrasonic source that the ultrasonic wave that described frequency mixing ultrasonic is two or three above ultrasonic frequency composition forms after mixing with any power ratio, the ultrasonic source that described mixing forms afterwards acts on graphite raw material.
4. frequency mixing ultrasonic according to claim 1 and 2 prepares the method for primary Graphene, it is characterized in that: described frequency mixing ultrasonic comprises the ultrasonic wave of two or three above ultrasonic frequency composition, and the ultrasonic wave of described each composition successively acts on graphite raw material with any power.
5. frequency mixing ultrasonic according to claim 1 and 2 prepares the method for primary Graphene, it is characterized in that: described graphite raw material is one or more the mixing in raw ore graphite, refining graphite, highly oriented pyrolytic graphite and the expanded graphite of purity more than 97%, the particle diameter of described graphite raw material at micron order to the centimetre-sized scope, form is one or both the mixing in particle and sheet.
6. frequency mixing ultrasonic according to claim 1 and 2 prepares the method for primary Graphene, it is characterized in that: first graphite raw material be placed in or be scattered in liquid solvent, then using frequency mixing ultrasonic, in liquid phase, graphite raw material is carried out to ultrasonication.
7. frequency mixing ultrasonic according to claim 6 prepares the method for primary Graphene, it is characterized in that: described liquid solvent is one or more the mixture in water, inorganic acid alkali solution, alcohols, aldehydes, ketone, liquid alkane class and alkane ketone.
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| CN105506742A (en) * | 2015-12-11 | 2016-04-20 | 山东大学 | Orthorhombic-phase two-dimension-layered SiP2 single-crystal thin film, and preparation method and application thereof |
| CN106744883A (en) * | 2017-01-05 | 2017-05-31 | 中山科普斯特电源技术有限公司 | The preparation method of Graphene |
| CN106744884A (en) * | 2017-01-16 | 2017-05-31 | 王奉瑾 | A kind of Graphene and preparation method thereof |
| CN107117603A (en) * | 2017-06-16 | 2017-09-01 | 成都新柯力化工科技有限公司 | A kind of utilization pulse ultrasonic wave peels off grading system for the method for graphene |
| CN108314333A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of Electrostatic Absorption preparation method of Graphene glass |
| CN110072808A (en) * | 2016-07-27 | 2019-07-30 | 凯诺斯创新有限公司 | Improvement relevant to graphene nano material |
| CN112689611A (en) * | 2018-07-24 | 2021-04-20 | Npl管理有限公司 | Method and apparatus for producing material |
| CN112919457A (en) * | 2021-02-26 | 2021-06-08 | 中科雷舜智能科技(宁波)有限公司 | Nano material and preparation method thereof |
| DE202023101511U1 (en) | 2023-03-27 | 2023-04-18 | 2D Innovation Gmbh | Apparatus for producing low-layer graphene |
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| CN105506742A (en) * | 2015-12-11 | 2016-04-20 | 山东大学 | Orthorhombic-phase two-dimension-layered SiP2 single-crystal thin film, and preparation method and application thereof |
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| CN108314333A (en) * | 2018-04-24 | 2018-07-24 | 盐城师范学院 | A kind of Electrostatic Absorption preparation method of Graphene glass |
| CN112689611A (en) * | 2018-07-24 | 2021-04-20 | Npl管理有限公司 | Method and apparatus for producing material |
| CN112919457A (en) * | 2021-02-26 | 2021-06-08 | 中科雷舜智能科技(宁波)有限公司 | Nano material and preparation method thereof |
| DE202023101511U1 (en) | 2023-03-27 | 2023-04-18 | 2D Innovation Gmbh | Apparatus for producing low-layer graphene |
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Application publication date: 20131225 |