CN108529607A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN108529607A CN108529607A CN201810054862.0A CN201810054862A CN108529607A CN 108529607 A CN108529607 A CN 108529607A CN 201810054862 A CN201810054862 A CN 201810054862A CN 108529607 A CN108529607 A CN 108529607A
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- graphene
- graphite
- stripping
- aromatic amine
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 353
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 239000010439 graphite Substances 0.000 claims abstract description 115
- 238000002604 ultrasonography Methods 0.000 claims abstract description 39
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention relates to a kind of preparation methods of graphene, and graphite is placed in aromatic amine, then to its continuous ultrasound or replace fresh aromatic amine and carry out more wheel ultrasounds, and product is centrifuged to get to graphene.Compared with prior art, the liquid phase that the present invention only leans on ultrasonication that graphene can be completed at room temperature is removed, it is not related to other energy consumption processes, preparation process simplicity, relative inexpensiveness, in 100% stripping that graphite may be implemented by limited stripping wheel number no more than the release system of the content of graphite of 1.5mg/mL, and the pure quality of gained graphene is high.The pure graphene of this perfect electronic structure, particularly no solvent residue can keep graphene inherent characteristic, so that it is played irreplaceable role in various fields such as nanocomposite, big sun energy battery, electrode of lithium cell, ultracapacitor, light emitting diode, field-effect transistor, liquid crystal display device, flexible touch screens, is expected to be widely used in all trades and professions.
Description
Technical field
The present invention relates to a kind of graphene preparation methods, belong to technical field of graphene preparation.
Background technology
Atom has been made by micromechanics stripping method from Britain Manchester universities Geim and Novoselov in 2004
Since the horizontal single-layer graphene film of grade (Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y,
Dubonos S V,Grigorieva I V,Firsov A.A.Electric field effect in atomically
thin carbon films.Science,2004,306(5696):666-669), due to its cheap cost of material and excellent electricity
It learns performance and becomes the hot spot that people competitively study overnight.Graphene is just used as a kind of star grade material, numerous new
Come out top in material, become in material and physics field and study new highlight, it is great to cause whole world scholars at different levels
Concern and research, unprecedented research boom are following.Single layer two-dimensional graphene is the universal toy bricks of carbon-based material, is
The parent of all other dimension graphite form.It, which is crimped, can construct zero dimension bucky-ball (buckyball) and other are many non-
Tubelike fullerene, one-dimensional nano carbon pipe, and be stacked and be returned to three-dimensional graphite block materials.The electronics of two-dimensional graphene
It is very different with common three-dimensional graphite with the motion mode in hole, it is but identical as relativistic paritcle.Its excellent crystal product
Matter and electronic property make it show the unapproachable performance level of common material (Peng H S, Chen D Y, Huang J
Y,Chikkannanavar S B,Hanisch J,Jain M,Peterson D E,Doorn S K,Lu Y F,Zhu Y T,
Jia Q X.Strong and ductile colossal carbon tubes with walls of rectangular
macropores.Phys.Rev.Lett.,2008,101: 145501).As the theoretical specific surface area of graphene may be up to about
2630m2/ g, thermal conductivity may be up to 5300 W/ (m.K), be higher than the thermal conductivity of carbon nanotube and diamond, and mechanical property may be up to
1060GPa, electron mobility may be up to 15000~60000cm under room temperature2/ (V.s), light transmittance 97.7%, conductivity is up to
106S/cm, the quantum hall effect with perfect quantum tunneling effect, half-integer.The graphene film of micro-meter scale has foot
Enough rigidity are also not folded without being crimped as flexible fabric, on the contrary, it has prodigious load capacity, Neng Goucheng
Carry more than own wt millions of times of objects (Booth T J, Blake P, Nair R R, Jiang D, Hill E W,
Bangert U,Bleloch A,Gass M,Novoselov K S,Katsnelson M I,Geim A K. Macroscopic
graphene membranes and their extraordinary stiffness.Nano Lett.,2008, 8(8):
2442-2446).And it is possible to open more new functions with the Graphene derivative of various molecules or modified with functional group.This
A little peculiar properties make it in solar cell, light emitting diode, the transparent electrode for substituting ITO and FTO, liquid crystal display device, big
Scale patterns retractable electrode, the electrode material of lithium ion battery, electrochemical capacitor, field-effect transistor, memory, biography
Sensor and electrochemica biological sensor, anticorrosive paint, hydrogen storage material, high activity bionic oxidation catalyst, methanol fuel cell are urged
The fields such as agent and various composite materials have broad application prospects, almost omnipotent.Especially in high-frequency circuit
In the field-effect transistor made of graphene be expected to substitute the silicon transistor of existing mainstream so that supercomputer etc. is various
The high boost of electronic equipment instrument becomes unlimited wide.Rarely has the tera-hertz spectra of developmental research in entire electromagnetic spectrum
Area's graphene is also had place to show one's prowess.This is related with the adjustable characteristic of its energy gap, becomes micron by cutting grapheme or receives
Rice bandwidth, can be designed into energy gap (Brey L, the Fertig H A.Electronic states of of 0~3eV
graphene nanoribbons studied with the dirac equation.Phys.Rev.B 2006,73(23):
235411) 1~10THz Terahertz frequency ranges (Ju L, Geng B, Horng J, Girit C, Martin M, Hao, are just covered
Z,Bechtel H A,Liang X,Zettl A,Shen Y R,Wang F.Graphene plasmonics for tunable
terahertz metamaterials.Nat.Nanotechnol.2011,6:630-634).This adjustable band gap makes
It is expected to be applied to terahertz transmitter and detector.This multiduty graphene of a many-side people is expected to develop into be received after carbon
Novel and multifunctional material after the high heat-resisting organic material of the contour fragrance of mitron, conducting polymer, conjugated polymer.
In the two major classes preparation method of graphene ----" from bottom to top " (Bottom-Up) and " from top to bottom " (Top-
Down in), the former is related to micro-processing technology approach, easily prepared, and the single layer of better quality and few layer graphite can also be made
Alkene, but condition is harsh (high temperature, high vacuum), it is difficult to volume production.And the latter is shelled by intercalation, liquid phase using graphite as raw material
Graphene is made from approach such as, redox, there are volume production potentiality.Liquid phase stripping method among these have manufacturing cost it is cheap,
The advantages that operation is simple, gained graphene defect is few and paid high attention to.Liquid phase stripping method is that graphite is in liquid phase Jie
The method for realizing stripping by means of means such as ultrasonic wave, microwave, shearing force, thermal stress and electrochemistry in matter.Liquid phase stripping method
It is main to consider thinking is how to overcome the Van der Waals force of graphite between layers, achieve the purpose that remove graphene wafer.With
Liquid phase stripping research is goed deep into, and liquid phase stripping method has derived direct liquid phase stripping method and auxiliary agent auxiliary liquid phase stripping method two
Major class.The latter is the aqueous release system of green paid close attention in recent years, but since the surface energy of water is very big, needs to add adjuvant
The polycyclic chemical combination such as the high polymers such as such as SDS surfactants, sodium carboxymethylcellulose, chitosan, epoxy resin, porphyrin, pyrene
Object and sodium metasilicate, sodium aluminate, sodium hydroxide etc., charge stripping efficiency is not high, and water phase release system is generally required in autoclave
The water-heat process (Chinese patent 201110456632.5) of middle 200 DEG C of experience.
And directly liquid phase stripping method is using pure organic solvent, Diversity organic solvent (Chinese patent
Or even (Zhang Tongping spectroscopy and the spectrum analysis 2016,36 (10) such as ionic liquid 201110428499.2):It is 231-232) straight
The method for connecing stripping makes graphene nanometer sheet be dispersed stably in by the interaction between solvent and graphene wafer
In solvent.The research of Coleman is the representative of this research field.He summarizes surface of organic solvent can be to removing graphite
The influence of efficiency, it is indicated that the surface tension for being effectively peeled off solvent should be close to 40mJ/m2, the surface energy phase of this value and graphene
Closely, therefore energy needed for stripping graphite is easily peeled off out graphene close to zero.Further, direct liquid phase stripping method is wanted to obtain
The graphene of higher concentration is obtained, the total parameter δ t of Hildebrand solubility should be 23MPa1/2, wherein Hansen solubility
Three components of parameter are respectively：Dispersion force component 18MPa1/2, polar component 9.3MPa1/2, hydrogen bond force component 7.7MPa1/2
(Hernandez Y, NicoloSsiv,Lotya M,et al.High-yield production of graphene by
liquid-phase exfoliation of graphite.Nature Nanotechnology 2008,3:563-568；
Coleman J N.Liquid exfoliation of defect-Free graphene.Account Chemical
Research 2013,46(1):14–22).These researchs provide quantitative guideline to seek the stripping solvent of graphite.
But up to now, classical organic solvent is still confined to N-Methyl pyrrolidone (NMP) this single solvent
On, and the defect of NMP is also apparent.Its boiling point is high and steam is forced down and can not be completely removed in release system, remains
NMP in graphene makes the conductivity of the graphene film of its room temperature in vacuo drying be only 0.05 S/cm, through 300 DEG C of air gas
2h is dried in atmosphere, conductivity can be increased to 50S/cm, then add baking 2h in 250 DEG C of Ar/H2 that can also be increased to 65S/cm.Even if
It is such severe drying condition, the NMP for being strapped in graphene nano on piece can not be completely removed, still be had about
10% NMP residuals, corresponding every 75 graphene carbons have 1 NMP molecule, they are captured the inner surface for being strapped in graphene
(Hernandez Y, NicoloSsiv,Lotya M,et al.High-yield production of graphene by
liquid-phase exfoliation of graphite.Nature Nanotechnology 2008,3:563-568).Nothing
It doubts, this graphene for remaining NMP will produce significant limitation when further using.Some are that stripping is molten using NMP
The method of agent will also increase solvent thermal process to reinforce ultrasonic peeling effect, but prepared graphene is thicker, and stripping is not
Thoroughly in place, high-quality graphene (Chinese patent, 201310169706.6) can not be obtained；For being dissolved with the Hansen of NMP
Spend the organic solvent N,N-dimethylformamide (DMF) and diformazan that dispersive component is close and the Riders Xi Erbu aggregate parameter value is bigger
Base sulfoxide (DMSO), stripping yield also about only has 1wt%, extremely inefficient；And removed in acetonitrile solvent, it needs in advance
It can just be smoothly completed after the solvent-thermal method in autoclave pre-processes 12h at 180 DEG C, stripping yield is only
10wt%~12wt% (Qian W.Hao R, Hou Y L.et al.Solvothermal-assisted exfoliation
process to produce graphene with high yield and high quality.Nano Res 2009,2:
706-712)；The stripping of aliphatic organic amine solvent method is similarly needed by the solvent-thermal method in autoclave 170 DEG C~250
It could be completed after DEG C pretreatment 72h, and charge stripping efficiency is very low, the only tens of μ of μ g/mL~150 g/mL of graphene concentration of acquisition
(Chinese patent, 200910093581.7)；Perfluorinated aromatic organic solvent such as phenyl-pentafluoride nitrile, phenyl-hexafluoride and trifluoromethyl six
Fluorobenzene etc. only can obtain graphene by the ultrasound of 1h, but it is only 1wt%~2wt% that it, which removes yield, and perfluorinated
Aromatic organic solvent is expensive, corrosivity extremely strong (Bourlinos A B, Georgakilas V, Zboril R, et
al.Liquid-phase exfoliation of graphite towards solubilized graphenes.Small
2009,5(16):1841–1845).That delivers recently also has the alcohols solvent using C3~C8, such as isoamyl alcohol, butanol and pungent
Alcohol etc., bright spot be can obtain single-layer graphene, it require that in advance carry out phosphoric acid molecules intercalation processing, and this
Intercalation need the several months grow time be maintained at 90 DEG C under the conditions of could complete (Kovtyukhova N I, Perea-Lopez N,
Terrones M,et al.Atomically thin layers of graphene and hexagonal boron
nitride made by solvent exfoliation of their phosphoric acid intercalation
Compounds.ACS Nano 2017,11,6746-6754), very consumption energy consumption when.
As it can be seen that although dicyandiamide solution used in liquid phase stripping graphene has very much.But All Media cannot be taken into account
It is easy to operate, yield is higher, of low cost, volume production and the features such as high-quality.Therefore, find it is a kind of it is simple and practicable, can high yield
The preparation method for the high-quality graphene that rate, scale obtain no solvent residue is of great significance.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of preparations of graphene
Method.Preparation method economical and effective provided by the invention, it is simple for process, and can scale carry out, while no solvent residue, institute
It prepares graphene and has high-quality.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of graphene, graphite is placed in aromatic amine, to its continuous ultrasound or replaces fresh aromatic amine
More wheel ultrasounds are carried out, product is centrifuged to get to graphene.
In an embodiment of the invention, the aromatic amine be selected from aniline, ortho-aminotoluene, meta-aminotoluene, to toluene
Amine, adjacent ethylbenzene amine, ethylbenzene amine, to ethylbenzene amine, adjacent propyl aniline, propyl aniline, to propyl aniline, methylphenylamine, N-
One kind or their binary in ethyl aniline, N propyl aniline or poly-blended solvent.
In an embodiment of the invention, the graphite be natural flake graphite or expansible graphite, preferably can be swollen
Swollen graphite.
In an embodiment of the invention, the proportioning of the graphite, aromatic amine is no more than 10/1 (mg/mL), preferably
For 1/1 (mg/mL).
In an embodiment of the invention, to its continuous ultrasound or before replacing the more wheel ultrasounds of fresh aromatic amine progress,
After graphite is placed in aromatic amine, the step of being sealed immersion.
In an embodiment of the invention, graphite is placed in aromatic amine, and the sealed soak time is 1 day~60 days, excellent
It is selected as 7 days.
In an embodiment of the invention, graphite is placed in aromatic amine, and soaking temperature is room temperature~60 DEG C, preferably
For room temperature.
In an embodiment of the invention, the temperature of supersound process be room temperature~60 DEG C, preferably 40 DEG C.
In an embodiment of the invention, ultrasonic power is rod-type ultrasound or water bath sonicator, and preferably water-bath is super
Sound.
In an embodiment of the invention, ultrasonic frequency range is 20kHz to 70kHz, preferably 53kHz.
In an embodiment of the invention, the continuous ultrasound time is 1h~200h, depending on graphite initial concentration.
Initial concentration is higher, and ultrasonic time is longer.
In an embodiment of the invention, replace fresh aromatic amine carry out more wheel ultrasounds refer to will be after sealed soak
Graphene replaces fresh fragrant amine solvent, then ultrasonic again, and centrifugation taking-up graphite, is added new aromatic amine again after ultrasound
Solvent is again ultrasonic, repeats such operation and carries out more wheel ultrasounds, more ultrasonic numbers of wheel are 2 times~20 times, initially dense depending on graphite
Depending on degree.Initial concentration is higher, and ultrasound wheel number is more, repeats operation, and can all remove graphite.
In an embodiment of the invention, the mode for obtaining graphene dispersing solution is：System after ultrasound is existed
30min~120min is centrifuged under 200rpm~1000rpm, is drawn and is collected upper liquid i.e. acquisition graphene dispersing solution.
In an embodiment of the invention, by graphene dispersing solution centrifugal treating, the graphene being collected into is washed
Afterwards, it freezed, dried, remove remaining aromatic amine, obtain powder graphite alkene.
Preferably, the mode of acquisition powder graphite alkene is：By graphene dispersing solution at 7000rpm~10000rpm from
Heart 30min~120min is transferred to the cold-trap of freeze drier after washing the graphene being collected into deionized water, ethyl alcohol
Middle freezing 8h, re-dry 40h, finally 150 DEG C of baking 36h in vacuum drying oven, you can it is fragrant thoroughly to remove remaining stripping solvent
Amine.
In an embodiment of the invention, the ultraviolet spectroscopy of graphene dispersing solution：For the graphite obtained
After alkene dispersion liquid carries out the dilution of proper proportion using stripping solvent aromatic amine, to remove solvent aromatic amine as reference solution,
UV, visible light optical scanning is carried out in 200nm~1100nm wave-length coverages to obtain the final product；
The absorptivity ε of graphene is measured：Absorbance of the different graphene concentration under 660nm light waves is measured, is inhaled with this
Luminosity maps to its concentration, and carries out the linear fit of origin, according to bright nurse Beer law：
A=ε b C
A is the absorbance under 660nm light waves in formula, and b is light path, and C is graphene concentration, by the oblique of the straight line that is fitted
Rate can calculate the absorptivity ε of graphene.
The conductance measurement of graphene：For the powdered graphite alkene obtained, being first compressed into thickness using press is
The thin slice of some tens of pm~hundreds of microns tests its conductivity using four probe modes.
Compared with prior art, innovative point of the invention embodies in the following areas：
The present invention places it in stripping in fragrant amine solvent and prepares graphene, make full use of aromatic amine using graphite as raw material
Polar Amides on molecule open up inducing action to its intercalation in graphite layers, and being powered property amino increases pi-electron
The aromatic rings of density promotes the π in graphite between carbon atomic layer-pi-electron effect to be converted to carbon atomic layer and organic solvent aromatic rings
Effect between the pi-electron of both different conjugated degrees, it is final to realize to overcome the cohesive energy between graphene platelet
The stripping of graphite.Graphene obtained by this stripping means not only has perfect sp2Electronics hybrid structure, and because solvent has
Certain vapour pressure and boiling point appropriate are easy to remove and no solvent residue.Obviously, this composition is pure, it is heteroatomic to be free of
Graphene can obtain graphene intrinsic various performances originally, without as it is other fetter have residual solvent graphene that
Sample is suppressed or influences.The liquid phase stripping method of the present invention has not been reported.
Beneficial effects of the present invention embody in the following areas：
The present invention selects fragrant amine solvent to carry out the liquid phase stripping of graphite at room temperature, utilizes fragrant amine molecule and graphite
Between wetability and compatibility, intercalation simultaneously removes the graphene at single layer and few layer.It is 1.0mg/ for graphite initial concentration
The release system of mL is removed by more wheels of finite number of time, can be almost completely exfoliated.Reaching stripping during more wheel strippings
When peak period, gained release system graphene therein after 900rpm centrifugations 90min~150min throws away unstripped graphite is dense
Degree reaches as high as 219 μ g/mL.Different with stripping technology parameter according to graphite initial content difference, the graphene is to 660nm waves
Long absorptivity is 2840~5996L/ (g.m) range, and apparent dindar effect occurs in the graphene dispersing solution after dilution
It answers, it is all these all to show that graphite is stripped at few layer graphene.Electronic Speculum observation further demonstrates that gained graphene is few
Layer graphene, lateral dimension are micron order.The graphene dispersion stable system, the graphene dispersion body of a concentration of 17 μ g/mL
The sedimentation time constant of system is 65.4h, wherein the graphene concentration C of stable dispersion0It is that can settle graphene concentration C11.04
~1.19 times, also that is, graphene more than half will not settle.And the graphene settled during standing, reunion is temporary
When property it is soft-agglomerated, can pass through ultrasound completely open restore.The washed drying of solvent in this graphene dispersing solution
It is completely removed, the conductivity that gained powder graphite alkene is measured through tabletting four probe method is made to reach 38.5S/cm.
The present invention only leans on ultrasonication that the liquid phase stripping of graphene can be completed at room temperature, is not related to other consumed energy
Journey, preparation process simplicity, relative inexpensiveness are limited passing through no more than the release system of the content of graphite of 1.5mg/mL
The stripping of most graphite may be implemented in stripping wheel number, and the pure quality of gained graphene is high.This perfect electronics knot
The pure graphene of structure, particularly no solvent residue can keep graphene inherent characteristic, such as the electron transfer of superelevation
Rate, the electronic conduction of superelevation and ion conduction, the heat conductivility of superelevation, excellent translucency etc., make it nano combined
Material, big sun can battery, electrode of lithium cell, ultracapacitor, light emitting diode, field-effect transistor, liquid crystal display device,
The various fields such as flexible touch screen play irreplaceable role, are expected to be widely used in all trades and professions.
Description of the drawings
Fig. 1 is the ultraviolet spectra (a) of 1 gained graphene dispersing solution of embodiment and corresponding digital photograph (b)；
Fig. 2 is the ultraviolet spectra (a) of 2 gained graphene dispersing solution of embodiment and corresponding digital photograph (b)；
Fig. 3, which is the Tyndall phenomenon (a) of 7 gained graphene dispersing solution of embodiment and the graphene of overrich, to be observed
To Tyndall phenomenon (b)；
Fig. 4 (a) is ultraviolet-visible spectrum of the gained graphene dispersing solution after 6 times of dilutions in embodiment 9；
Fig. 4 (b) is ultraviolet-visible spectrum of the gained graphene dispersing solution after 6 times of dilutions in embodiment 10；
Fig. 4 (c) is ultraviolet-visible spectrum of the gained graphene dispersing solution after 6 times of dilutions in embodiment 11；
Fig. 4 (d) is ultraviolet-visible spectrum of the gained graphene dispersing solution after 6 times of dilutions in embodiment 12；
Fig. 4 (e) is ultraviolet-visible spectrum of the gained graphene dispersing solution after 6 times of dilutions in embodiment 13；
Fig. 5 is between A660 of the gained graphene dispersing solution in embodiment 9~13 after 6 times of dilutions and ultrasound wheel number
Relationship；
In Fig. 6 embodiments 6 and embodiment 9~12 soaking time respectively be completely exfoliated needed for graphite take turns number, theoretical calculation
Total graphene dispersing solution concentration, each round actual measurement A660 addition and values relationship；
Fig. 7 is the UV absorption light collection of illustrative plates that 14 gained upper liquid of embodiment dilutes 6 times；
Fig. 8 is the subsidence curve of 18 gained graphene of embodiment 17 and embodiment；
Fig. 9 is the Raman spectrum of 3 gained graphene of embodiment；
Figure 10 (a) is that the stereoscan photograph of 12 gained graphene of embodiment shows corrugated lamella；
Figure 10 (b) is that the stereoscan photograph of 12 gained graphene of embodiment shows gauffer porous structure；
Figure 10 (c) is the stereoscan photograph of 12 gained micron order graphene of embodiment；
Figure 11 (a) is the transmission electron microscope photo of few layer graphene without stacking in 16 gained graphene of embodiment；
Figure 11 (b) is the electron diffraction pattern in graphene constituency in Figure 11 (a)；
Figure 12 left figures are the transmission electron microscope photo that 16 gained single layer of embodiment and few layer graphene are stacked, right figure
For the selective electron diffraction style of graphene in Figure 12 left figures；
Figure 13 left figures are the transmission electron microscope photo of the few layer graphene of 16 gained of embodiment, and right figure is 16 gained stone of embodiment
The crimping pattern that the sample preparation in ethanol medium of black alkene occurs.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Rod-type ultrasound effect experiment
20mg graphite and 20mL ortho-aminotoluenes are added in small test tube, at this point, the initial concentration of graphite is 1.0mg/mL.
Using JY92-IIN ultrasonic cell disruptors (650W, 20~25kHz), rod-type ultrasound is carried out in 40% power, between ultrasound is
It has a rest progress, often super 3s stops 1s, amounts to ultrasound 1h and 4h, after 20 times of gained graphene dispersing solution dilutes after different ultrasonic times
Uv-spectrogram see that Fig. 1 (a), appearance photo and dindar photo are shown in Fig. 1 (b).As it can be seen that super by the 1h especially rod-types of 4h
Sound obtains the graphene dispersing solution shaped like prepared Chinese ink, and ultraviolet spectra generates apparent absorption to the light wave of 660nm, but passes through
After the standing in one evening again it is done it is ultraviolet declined, and observe a small amount of particle sedimentation.
Embodiment 2
Water bath sonicator effect experiment
20mg graphite and 20mL ortho-aminotoluenes are added in small test tube, at this point, the initial concentration of graphite is 1.0mg/mL.
It places it in SK3300HP supersonic cleaning machines (180W, 53kHz), 100% power carries out water bath sonicator, amounts to ultrasound 33h.
Uv-spectrogram under several ultrasonic time nodes after the 11 times of dilutions of gained graphene dispersing solution is shown in Fig. 2 (a), appearance photo and fourth
Da Er photos are shown in Fig. 2 (b).As it can be seen that with the extension of ultrasonic time, ultraviolet spectra obviously increases the absorption of the light wave of 660nm
Add, illustrate that obtained graphene concentration extends and increases at any time, graphene dispersing solution is in Gao Bo after the standing in an evening
Long absorption spectrum is declined, but fall is significantly less than the ultrasound of the rod-type in embodiment 1.Illustrate in such cases, institute
It is less to obtain graphene number of plies, therefore water bath sonicator is better than rod-type ultrasound.
Embodiment 3~4：The experiment of drying mode
Embodiment 3
Ethylbenzene amine between 10mg expanded graphites and 20mL is added in small test tube, at this point, the initial concentration of graphite is 0.5mg/
mL.It places it in SK3300HP supersonic cleaning machines (180W, 53kHz), 100% power carries out intermittent mode water bath sonicator
During which 48h controls temperature and is no more than 40 DEG C.The release system removes unstripped graphite by 900rpm centrifugations 45min,
It is 1.87mg to remain in the unstripped graphite for centrifuging tube wall weight after alcohol wash water washes freeze-drying, then 36h is dried in vacuo at 150 DEG C
Weight saving is 1.35 mg after thoroughly removing residual solvent.
The collected upper liquid of centrifugation is dense black graphene dispersing solution, is shaken up and according to volume ratio 1:5 use solvent
Uv-spectrogram is scanned after 6 times of dilution, indicates its absorbance A 660 up to 1.53 to 660nm wavelength.The supernatant is passed through
10000rpm centrifugations 90min makes graphene settle, and concussion 2~3 times is washed with absolute ethyl alcohol ultrasound 5min, so that second
Alcohol washes away the organic solvent that graphene surface adheres to, and 90 min of 10000rpm collect clean graphene later, are transferred to glass
In glass surface plate, 40h is lyophilized after carrying out freezing 8h, obtains black graphene powder 11.09mg, then transfers them to 150 DEG C of vacuum
Dry 36h, obtains black graphene powder 6.91mg in baking oven, and a concentration of of its former graphene dispersing solution is calculated with this
0.3455mg/mL, stripping yield are 69.1%.
Embodiment 4
Difference from Example 3 is that stripping solvent uses isometric aniline, methylphenylamine and meta-aminotoluene instead
Tertiary blending solvent removed, room temperature immersion treatment 60 days before ultrasound.It is equally collected in 10000 rpm 90min after ultrasound
Clean graphene is transferred in glass surface ware, and 40h is lyophilized after carrying out freezing 8h, obtains black graphene powder 9.27mg,
Dry 36h in 150 DEG C of vacuum drying ovens is transferred them to again, obtains black graphene powder 5.67mg, its former graphite is calculated with this
A concentration of 0.2835mg/mL of alkene dispersion liquid, stripping yield are 56.7%.
By embodiment 3,4 as it can be seen that residual solvent can farthest be removed by increasing vacuum drying.
Embodiment 5~6：More wheels stripping when 1.0mg/mL
Embodiment 5
Isometric mixed solvent of 20mg graphite and 20mL aniline and N-ethylaniline is added in small test tube, at this point, stone
The initial concentration of ink is 1.0mg/mL.Place it in SK3300HP supersonic cleaning machines (180W, 53 kHz), 100% power into
Row water bath sonicator 20h, exfoliation temperature are no more than 50 DEG C, and after completing the 1st wheel stripping, 800rpm centrifuges 60min, draws on 70%
It is shaken up in layer liquid to test tube, observes Tyndall effect, and be taken out a little according to 1:Ultraviolet-visible light is carried out after 10 dilutions
Scanning.Again 90min is centrifuged in 10000rpm to collect all graphenes, it is freeze-dried and true with ethyl alcohol centrifuge washing 2 times
It is weighed after sky is dry, calculates the stripping rate and graphene concentration of the 1st wheel.The unstripped graphite of the sedimentation in former bottom of bottle portion is mended
Fresh mixed solvent is added to carry out the stripping of the 2nd wheel 20h；In this way, carry out more wheel strippings, until centrifugation cannot throw away it is unstripped
Until graphite.The result shows that 4 wheel strippings just complete whole strippings of graphite.The weight of graphene, stripping obtained by each round
The conductivity that the four probe method of rate, graphene concentration and pressed powder graphene measures is shown in Table 1.Gained release system passes through
Graphene concentration therein reaches as high as 474 μ g/mL after 800rpm centrifugations 60min throws away unstripped graphite.It is diluted according to 11 times
The absorbance and respective concentration of each round graphene dispersing solution afterwards carry out stone obtained by linear fit according to bright nurse Beer law
The absorptivity of black alkene is 2841L/ (g.m), and wherein linearly dependent coefficient is 0.998, and the range of linearity is 10~15 μ g/mL.From
Absorptivity numerical values recited can reflect that the graphene is few layer graphene.
Graphite obtained by 800rpm centrifugations 60min mostly after wheel stripping graphite when a concentration of 1.0mg/mL of 1. starting graphite alkene of table
The stripping yield of alkene, the conductivity of concentration and graphene
Embodiment 6
More wheel strippings are similarly carried out, but use aniline, to ethyl aniline and N propyl aniline (volume ratio 5:3:2)
Mixed solvent is as stripping mixed solvent.Exfoliation temperature be no more than 40 DEG C, and using 900rpm centrifugation 45min throw away it is unstripped
Graphite.Gained graphene dispersing solution is according to 1:UV-Vis scan is carried out after 6 dilutions.In the washing and drying stage, in order to
Working efficiency is improved, washing and drying processing is carried out after merging for graphene dispersing solution similar in absorbance.The result shows that 10
Wheel stripping can complete the stripping of graphite.Weight, stripping rate and the graphene concentration of graphene obtained by each round are shown in Table 2.Institute
It obtains release system graphene concentration therein after 900rpm centrifugations 90min throws away unstripped graphite and reaches as high as 298.5 μ g/
mL.Since sample size has less, the conductivity that the four probe method of pressed powder graphene measures only has the conjunction of the 8th wheel and the 9th wheel
And the sample of sample and the 10th wheel, their conductivity is respectively 16S/cm and 19S/cm.According to each after 6 times of dilutions
The absorbance and respective concentration of wheel graphene dispersing solution, the suction that graphene obtained by linear fit is carried out according to bright nurse Beer law
Backscatter extinction logarithmic ratio is 4388L/ (g.m), and wherein linearly dependent coefficient is 0.931, and the range of linearity is 0.76~49.8 μ g/mL.From suction
Backscatter extinction logarithmic ratio numerical values recited can reflect that the graphene is few layer graphene.
Graphite obtained by 900rpm centrifugations 45min mostly after wheel stripping graphite when a concentration of 1.0mg/mL of 2. starting graphite alkene of table
The stripping yield and dispersion liquid concentration of alkene
Embodiment 7~8：More wheels stripping when 1.5mg/mL and 2.5mg/mL
30mg and 50mg graphite and 20mL aniline and N propyl aniline 1 are separately added into 2 test tubes:1 blend solvent,
At this point, the initial concentration of graphite is respectively 1.5mg/mL and 2.5mg/mL, subsequent ultrasonic is washed with embodiment 6.With 1.5mg/mL
For, since the graphene of the 1st wheel stripping, gained graphene dispersing solution is black ink sap-shape, it is observed that significantly
Tyndall phenomenon is shown in Fig. 3, and with the increase of stripping wheel number, the concentration of graphene gradually increases, and the graphene of overrich makes nothing
Method observes Tyndall phenomenon.When reaching the peak of stripping phase, gained release system centrifuges 90min through 900rpm for more wheel strippings
Graphene concentration therein reaches as high as 219 μ g/mL after throwing away unstripped graphite.The stripping of preceding 14 wheel and preceding 11 wheel is tied in detail
Fruit is shown in Table 3.As it can be seen that after increasing starting graphite concentration, stripping wheel number will greatly increase, although 10 wheels can not also complete whole stones
The stripping of black alkene, but more wheels of a concentration of 1.5mg/mL of starting graphite are removed, the stripping of 14 wheels can complete big portion
The stripping of the graphite divided, stripping gross production rate is up to 78.7%.The conductivity highest that powder graphite alkene is measured through tabletting four probe method
Up to 38.5S/cm.
In addition, for the graphene removed from 1.5mg/mL and 2.5mg/mL, according to each round graphite after 6 times of dilutions
The absorbance and respective concentration of alkene dispersion liquid, the absorptivity that graphene obtained by linear fit is carried out according to bright nurse Beer law
For 5996L/ (g.m), wherein linearly dependent coefficient is 0.995, and the range of linearity is 1.6~17 μ g/mL.From absorptivity numerical value
Size can reflect that the graphene is few layer graphene.
900 rpm are centrifuged after mostly wheel removes graphite when 3. starting graphite alkene concentration of table is respectively 1.5mg/mL and 2.5mg/mL
The stripping yield and dispersion liquid concentration of graphene obtained by 90min
Embodiment 9~13：Dipping pretreatment assists liquid phase stripping
It takes 5 parts of 20mg graphite to pour into 5 test tubes, 20mL aniline is added, seal infiltration 2 days, 5 up for safekeeping at room temperature respectively
It, 7 days and 21 days and at 60 DEG C stirring impregnate 7 days, then carried out after taking turns stripping and graphene according to embodiment 6 more
Processing etc..The ultraviolet-visible collection of illustrative plates of each wheel stripping graphene dispersing solution of gained is shown in Fig. 4 (a), Fig. 4 under this 5 kinds of soaking conditions
(b), Fig. 4 (c), Fig. 4 (d), Fig. 4 (e), it is seen that the A of 6 times of dilution660Reach as high as 2.With at room temperature impregnate number of days increase,
It all removes required wheel number and is reduced to 9 wheels, 8 wheels, 7 wheels and 6 wheels successively.Not only the time is obviously shortened, but also used
Stripping solvent dosage also gradually declines, and drops to 110mL from 165mL, has dropped 33.3%.Refer to table 4.This shows to impregnate pre-
Processing is conducive to remove intercalation and the stripping of solvent, improves charge stripping efficiency.
Influence of the 4. preparation immersion treatment of table to graphite peeling effect
On the other hand, from the point of view of the concentration for the graphene dispersing solution being stripped out, there is highest stripping graphene concentration
Number is taken turns in advance, for 7 days graphite of immersion treatment, stripping outbreak period, the A of 6 times of dilution have been put into since taking turns the 4th660
1.2 or more, the block diagram (Fig. 5) of absorbance and ultrasound wheel number is referred to.Infiltrating time is longer, the more early arrival of peak.And
The effect that stirring impregnates 7 days at 60 DEG C illustrated that immersion treatment has time temperature equivalence close to 21 days soaking at room temperature.
For seeing Fig. 6 with the graphite impregnated at room temperature, soaking time and the relationship that wheel number needed for graphite is completely exfoliated,
Wherein, the data impregnated 0 day are derived from embodiment 6.Meanwhile the starting graphite weight by putting into and stripping process solvent for use
Total volume can theoretically calculate total graphene dispersing solution concentration in the case where being completely exfoliated.When the concentration is with impregnating
Between relation curve also see Fig. 6.As it can be seen that removing is not impregnated outside sample, (its charge stripping efficiency is limited, and stripping every time is only capable of taking out
14mL dispersion liquids), as soaking time extends, wheel number needed for graphite is completely exfoliated and is decreased obviously, while total graphene dispersing solution
Concentration but obviously increases.If again by soaking time and the actual measurement A for often taking turns graphene dispersing solution660Addition and value is associated, can be with
It was found that its each round surveys A660Addition and value does not increase, basic maintenance level (Fig. 6), according to its fewer suction of the number of plies of graphene
The smaller rule of backscatter extinction logarithmic ratio can speculate that the graphene number of plies that the extension with soaking time is stripped out gradually is tailing off.
As it can be seen that no matter from charge stripping efficiency or from peeling effect, immersion is all conducive to solvent to graphite worm shape pore passage structure
Wetting, or even graphite microcrystal is fully wet by the capillary phenomenon in vermiform duct, to promote the stripping of graphite.
Embodiment 14：Bull wheel is removed
It takes 20mg graphite and 20mL toluidines to pour into test tube, seals infiltration 2 months up for safekeeping at room temperature, then used 480W
Supersonic cleaning machine carries out bull wheel ultrasound for several times at 40kHz with long period when 40h, and the stripping of most of graphite is completed after 4 wheels
From remaining graphite can be ignored, and stripping gross production rate is up to 83.3% after the completion of 4 wheel strippings, especially in 40h and 80h
Between after point completes the 1st wheel and the 2nd wheel ultrasound stripping, 900rpm centrifuges 90min centrifuged supernatants and dilutes 6 times of UV absorption light
Collection of illustrative plates is shown in that Fig. 7, A660 are respectively 2.8556 and 2.4308, and corresponding graphite stripping rate respectively reaches 42.6% and 40.7%,
Illustrate that the bull wheel stripping for increasing duration equally can prepare graphene with high yield.
Embodiment 15：The stripping of graphite under 50mL amplification scales
2 parts of 50mg graphenes are separately added into two 100mL test tubes, it is each that aniline and toluidines 3 is added:2 volume ratios
They are placed in SK3300HP supersonic cleaning machines (180W, 60kHz) by mixed solvent 50mL, and it is super that 100% power carries out water-bath
Sound, to 60h after complete the first round ultrasound, 900rpm centrifuge 90min, acquisition supernatant merging shake up dilution 6 times after survey UV,
Unstripped continuously adds solvent stripping, and per 20h, centrifugation obtains supernatant later, and 6 times of survey UV of same dilution the results are shown in Table 5.
It can be seen that second takes turns the absorbance A of supernatant after stripping6602.4713 are can reach, and graphite unstripped after being taken turns to the 4th is residual altogether
26.7mg is stayed, while stripping gross production rate illustrates that amplification stripping scale equally can be higher up to 73.3% after the completion of 4 wheel strippings
Yield prepares graphene.
The peel results of graphite under 5 50mL scales of table
Above-mentioned removed graphene dispersing solution is all merged into mixing, takes 300mL points of 2 conical flask ultrasounds
30min makes it be restored to graphene dispersing solution completely；Graphene dispersing solution after recovery is dispensed into centrifuge tube, 900rpm
The a small amount of unstripped graphite thrown away after 90min abandons it.Upper liquid is centrifuged to the graphene grade thrown away after 90 points at 1000rpm
Part is G900~1000, after its constant volume with Dilution absorbance step by step, remaining dispersion liquid finally will be cleaned drying title
Weight, calculates the concentration C of graphene in mother liquor1, acquisition absorptivity is after carrying out linear fit with A~C relation curves
4591L/ (g.m), linear ranging from 2.0~31.9 μ g/mL, linearly dependent coefficient 0.992.
Similarly, then the upper liquid after 90 points of 1000rpm centrifugations centrifuges 90 points at 2000rpm, the graphene grade thrown away
Part is G2000~1000, after its constant volume with Dilution absorbance step by step, remaining dispersion liquid finally will be cleaned drying title
Weight, calculates the concentration C of graphene in mother liquor2, acquisition absorptivity is after carrying out linear fit with A~C relation curves
4180L/ (g.m), linear ranging from 3.1~50.4 μ g/mL, linearly dependent coefficient 0.994.
Similarly, then the upper liquid after 90 points of 2000rpm centrifugations centrifuges 90 points at 3,000 rpm, the graphene grade thrown away
Part is G3000~2000, after its constant volume with Dilution absorbance step by step, remaining dispersion liquid finally will be cleaned drying title
Weight, calculates the concentration C of graphene in mother liquor3, acquisition absorptivity is after carrying out linear fit with A~C relation curves
4126L/ (g.m), linear ranging from 2.7~43.5 μ g/mL, linearly dependent coefficient 0.995.
It is found that the absorptivity of these three graphene fractions of G900-1000, G1000-2000, G2000-3000 is 4100
It is few layer graphene in~4600L/ (g.m) range.
Embodiment 16
It takes 20mg graphite and 20mL aniline to pour into test tube, infiltrates 6 weeks, be then cleaned by ultrasonic it with 180W at room temperature
Machine carries out 4 wheel ultrasounds at 53kHz with the wheels of 40h 1, and centrifuging 120 min in 900rpm after often wheel stripping throws away unstripped stone
Ink, gross production rate is up to 57.6% after 4 wheel strippings.The upper liquid obtained merging is further continued for ultrasonic 33h, 900rpm centrifugations
Thicker graphene is thrown away after 120min, can be collected into the graphene fraction that 90min is centrifuged in 1000- 2000rpm.
Embodiment 17~18：The research of subsidence curve
7~8 gained graphene dispersing solution 30mL of Example is transferred in test tube, first carries out the supersound process of 30min,
Time after ultrasound is calculated as t=0, later keep stand it is motionless, to visually observe, Tyndall effect and UV scanning come
Its natural subsidence situation of follow-up study.Wherein UV scanning sample is derived under liquid level the dispersion liquid at half, and presses 1:5
Ratio with stripping solvent dilute 6 times after, using fresh solvent be reference scanning UV-Vis spectra.By extinction at 660nm
Spend A660Gained concentration C0Be plotted against time, subsidence curve see Fig. 8.By curve obtained according to C=C0+C1e-t/τIt is fitted,
It obtains each parameter of subsidence curve and is shown in Table 6.
The subsidence curve fitting parameter of 6. graphene dispersing solution of table
C0Stable dispersion concentration is represented, that is, settles the supernatant after infinite time；
C1The initial concentration of sedimentation substance is represented, that is, settles the deposit after infinite time in original initial time
Concentration；
τ represents sedimentation time constant.
As it can be seen that the graphene dispersion stable system, concentration is about the sedimentation time of the graphene dispersion system of 17 μ g/mL
Constant is 65.4h, wherein the graphene concentration C of stable dispersion0It is that can settle graphene concentration C11.04~1.19 times, also
That is, graphenes more than half will not settle.And the graphene settled during standing be can be complete by short time ultrasound
What full opening was restored, it was demonstrated that this is a kind of temporary soft-agglomerated, mainly originates from larger graphene lateral dimension, and
It is not that graphene is stacked into graphite again.
Embodiment 19：Elemental analysis
12 gained graphene powder of embodiment is used in right amount elemental analyser test the content (detection limit of its CHNS
0.3%) elemental analysis of graphite after expanding, as a comparison, has also been made.The result shows that the CHNS contents of graphite are distinguished after expansion
The CHNS contents point for the graphene for being not detected, 0.83wt% and 0.71wt%, and removing for 95.75wt%, less than 0.3wt%
It Wei 91.87wt%, 0.3wt%, 1.33wt% and 1.36wt%, it is seen that the content of the N and H of CHNS are increased slightly after stripping,
The aniline content being converted into is 3.32wt%.Illustrate that removing solvent residual amount can be ignored.In addition, unstripped expansion
The CHNS element weight percents of graphite and graphene add up to respectively 97.59wt% and 94.86wt%, if remaining member
Element is oxygen, then the molar ratio of the carbon of graphene and oxygen element is 24, although the value is less than the expanded graphite before stripping
(54), but it is far above general redox graphene rGO.Illustrate that gained graphene defect is seldom.
Embodiment 20：Raman spectrum is observed
Graphene powder prepared by embodiment 3 is a little, is tested using Raman spectrometer, and gained Raman spectrum is shown in Fig. 9
(a), the Raman spectrum of the unstripped graphite compareed therewith is shown in Fig. 9 (b).Wherein, the peaks D can reflect the defect letter of graphene
Breath, and the peaks G reflect SP2The in plane vibration intensity of hydbridized carbon atoms.The ratio between D peak intensities and G peak intensities can reflect graphene
Defect level.Compare the Raman spectrum of the graphene and graphite in Fig. 8 it is found that under using G peak intensities as internal standard, audio-visual picture
Show and shows that the D peak intensities of graphene are only slightly higher than graphite, IG/IDRatio illustrates removed graphene down to 0.084
It is seldom with defect as initial feed graphite.Graphite is observed again in 2717.8cm-1The peaks 2D, stripping at graphene after, the peak position
Move on to 2701.0cm-1.The peaks 2D show that the graphene is few layer graphene to the displacement of lower wave number direction.
Embodiment 21：SEM is observed
Graphene powder prepared by embodiment 12 is dispersed on silicon chip, silicon chip is sticked on conducting resinl and is placed in the U.S.
It is observed under FEIQuanta200 scanning electron microscope (SEM), gained different amplification photo is shown in Figure 10.It can see visual field
Under be few layer graphene, edge tends to corrugated lamella [Figure 10 (a)], the lamella be graphite flakes from outside to inside not
It is disconnected to remove, refine, disintegrating, it ultimately forms intensive, abundant stripping lamellar structure and is thus built into crisscross gauffer
Multiple hole structural form [Figure 10 (b)].Graphene sheet layer is further amplified, it can be seen that its lateral dimension is up to a few micrometers of [figures
10 (c), 10 (d)], belong to the graphene of relatively larger transverse size.
Embodiment 22：Tem observation
Graphene fraction collected by Example 16 is a small amount of, disperses in ethanol and carry out the ultrasonic disperse of 30min
Processing, keeps sample dispersion uniform, and a small amount of drop is drawn on copper mesh, with JEM-2100F high-resolution Flied emission electricity after drying with dropper
Sub- microscope (TEM) carries out observation and takes pictures.Selective electron diffraction (SAED) collection of illustrative plates of gained TEM photos and red circle selected areas
See Figure 11, Figure 12, Figure 13.As can be seen that there is few layer graphene in gained graphene, this can be by it close to transparent contrast
It is confirmed and [sees Figure 11 (a) and Figure 12 left figures], and according to the selective electron diffraction in red circle region it is known that Selected area electron
The dotted diffraction spot of regular hexagon is presented in diffraction pattern, shows that gained graphene has complete lattice structure.In Figure 11
(a) multi-layer graphene in is single few layer graphene, and a set of regular hexagon [Figure 11 (b)] occurs in diffraction pattern；
And the multi-layer graphene in the figure of the left sides Figure 12 is stacked by 2 kinds of few layer graphenes, hexagon diffraction pattern occurs
Dislocation, there are 2 sets of hexagon diffraction spots [Figure 12 right figures] can determine whether that brightness is weaker according to the difference in brightness of point diffraction
Reflection is single-layer graphene, and the stronger reflection of brightness is few layer graphene.This is lacked layer graphene to be further amplified,
It can be seen that 3 layers of pattern [Figure 13 left figures] are presented in its edge, it is known that it is 3 layer graphenes.In addition the graphene sample is in second
It is prepared in alcohol, since the affinity of graphene and ethyl alcohol is less than the affinity with stripping media, gained graphene film is not
Enough fully to unfold, some edges crimp, and see Figure 11 (a) and Figure 12 left figures and Figure 13 right figures.
Hair can be understood and used the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-mentioned implementations
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene, which is characterized in that graphite is placed in aromatic amine, then to its continuous ultrasound or more
Renew fresh aromatic amine and carry out more wheel ultrasounds, product is centrifuged to get to graphene.
2. a kind of preparation method of graphene according to claim 1, which is characterized in that the aromatic amine be selected from aniline,
Ortho-aminotoluene, meta-aminotoluene, para-totuidine, adjacent ethylbenzene amine, ethylbenzene amine, to ethylbenzene amine, adjacent propyl aniline, propyl aniline,
To one kind or their binary or poly-blended molten in propyl aniline, methylphenylamine, N-ethylaniline, N propyl aniline
Agent.
3. a kind of preparation method of graphene according to claim 1, which is characterized in that the graphite, aromatic amine are matched
Than being no more than 10/1 (mg/mL), preferably 1/1 (mg/mL).
4. a kind of preparation method of graphene according to claim 1, which is characterized in that by graphite be placed in aromatic amine into
Row sealed soak, then to its continuous ultrasound or replace the more wheel ultrasounds of fresh aromatic amine progress.
5. a kind of preparation method of graphene according to claim 4, which is characterized in that graphite is placed in aromatic amine, close
It is 1 day~60 days, preferably 7 days to seal soaking time；
Graphite is placed in aromatic amine, and soaking temperature is room temperature~60 DEG C, preferably room temperature.
6. a kind of preparation method of graphene according to claim 1, which is characterized in that the temperature of supersound process is room temperature
~60 DEG C, preferably 40 DEG C.
7. a kind of preparation method of graphene according to claim 1, which is characterized in that ultrasonic frequency range 20kHz
To 70kHz, preferably 53kHz.
8. a kind of preparation method of graphene according to claim 1, which is characterized in that the mode of centrifugation is：It will
System after ultrasound is centrifuged, and is drawn and is collected upper liquid i.e. graphene dispersing solution of the acquisition containing graphene,
Centrifuging optimum condition is：30min~120min is centrifuged at 200rpm~1000rpm.
9. a kind of preparation method of graphene according to claim 8, which is characterized in that at graphene dispersing solution centrifugation
Reason is freezed, is dried, remove remaining aromatic amine, obtain powder graphite alkene after washing the graphene being collected into.
10. a kind of preparation method of graphene according to claim 9, which is characterized in that graphene dispersing solution exists
30min~120min is centrifuged under 7000rpm~10000rpm, is turned after the graphene being collected into deionized water, ethyl alcohol are washed
Move in the cold-trap of freeze drier and freeze 8h, re-dry 40h, finally in vacuum drying oven 150 DEG C baking 36h, you can thoroughly remove
Remaining aromatic amine is removed, powder graphite alkene is obtained.
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| CN110931261A (en) * | 2019-12-18 | 2020-03-27 | 中原工学院 | Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance |
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