CN104891481B - A kind of large-scale preparation method of high-quality graphene - Google Patents
A kind of large-scale preparation method of high-quality graphene Download PDFInfo
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Abstract
The present invention relates to a kind of large-scale preparation method of high-quality graphene, comprise the following steps：Aromatic hydrocarbons reagent is added into expanded graphite and obtains expanded graphite solution, oxidant is dissolved in organic solvent oxidizing agent solution is made, oxidizing agent solution is added in expanded graphite solution again, ultrasound makes it well mixed, after mixed solution reacts completely in the water bath of certain temperature, product is separated, that is, obtains graphene.Compared with prior art, the method that the present invention disassembles graphite using chemical oxidising polymerisation grafting, it is disassembled under the water bath condition no more than 100 DEG C to obtain graphene.This method economical and effective, simple to operate, the potentiality prepared with scale batch.Products therefrom quality better, defect is considerably less, there is good application prospect, is expected to be applied to the fields such as ultracapacitor, lithium ion battery, electronic device and ion-selective electrode.
Description
Technical field
The present invention relates to a kind of preparation method of graphene, more particularly, to a kind of prepare with scale of high-quality graphene
Method.
Background technology
Graphene is with sp by single layer of carbon atom2The mode of hydridization forms the planar structure of bi-dimensional cellular shape, is current institute
Know material most thin in the world.Graphene has the intensity of superelevation, and its Young's modulus reaches 1100GPa, modulus of elasticity reaches
130GPa, it is more than 100 times of hardness of steel；Thermal conductivity coefficient is up to 5000Wm-1·K-1, higher than the heat of diamond and CNT
Conductance；Electron mobility at room temperature reaches 15000cm2·V-1·S-1, it is more than 10 times of commercial silicon chip；Electrical conductivity is up to
106S/cm, it is current electrical conductivity highest material.In addition, graphene also has perfect quantum tunneling effect, the amount of half-integer
Sub- Hall effect, (theoretical value reaches 2630m to the specific surface area of superelevation2g-1), excellent translucency (light transmittance 97.7%)
(Novoselov K.S.,Geim A.K.,Morozov S.V.,et al.Electric Field Effect in
Atomically Thin Carbon Films.Science,2004,306(5696):666-669.) two dimension so unique
Structure and excellent electricity, optics and mechanical property determine grapheme material by with extremely wide application prospect, for example,
Graphene can be used in big sun can battery, light emitting diode, liquid crystal display device, flexible touch screen, electrode of lithium cell, super electricity
The various fields such as container electrode, field-effect transistor, various composites.Therefore, in recent years, graphene is by numerous researchers
Favor.
The preparation method of graphene has two approach, one be " from bottom to top " (Bottom-Up) chemical synthesis approach,
Another kind of is " from top to bottom " the micro-processing technology approach of (Top-Down).The former is to utilize methane, aromatic hydrocarbons and polycyclic fragrance
The non-graphite carbon source such as hydrocarbon, is grown to serve as graphene under certain condition, mainly includes machine synthetic method, chemical vapor deposition
(CVD), epitaxial growth method.Wherein organic synthesis method is a kind of to obtain continuous polycyclic aromatic hydrocarbon structure by dehydrocyclization process
Method, mainly using aromatic hydrocarbon ring or other aroma systems as presoma, 6 hydrogen in aromatic hydrocarbon ring are made to be taken by coupling reaction
In generation, then dehydrogenation forms new aromatic rings between adjacent substituents, and so carrying out multistep reaction makes aroma system become big, so as to make
Obtain the graphene of certain area.(Cai,J.；Ruffieux,P.；Jaafar,R.；Bieri,M.；Braun,T.；
Blankenburg,S.；Muoth,M.；Seitsonen,A.P.；Saleh,M.；Feng,X.；Müllen,K.；Fasel,
R.Atomically precise bottom-up fabrication of graphene nanoribbons.Nature
2010,466:470-473；Blankenburg,S.；Cai,J.；Ruffieux,P.；Jaafar,R.；Passerone,D.；
Feng,X.；Müllen,K.；Fasel,R.；Pignedoli,C.A.Intraribbon heterojunction formation
in ultranarrow graphene nanoribbons.ACS Nano 2012,6(3):2020-2025.).It is this from organic
The method that small molecule is set out can be made with the graphene nanobelt for determining structure, and reaction condition is more gentle, easily controllable,
But the shortcomings that also having clearly：Reactions steps are more, comparatively laborious, and when needing to prepare the graphene of large area, need
More catalyst is wanted, and the reaction time is grown, and dehydrogenation is inefficient, it is possible to partial only occurs.And CVD prepares stone
Black alkene is using carbon compounds such as methane, acetylene as carbon source, as carbon source finally grows in the pyrolytic of matrix surface
Go out graphene (Wassei, J.K.；Mecklenburg,M.；Torres,J.A.；Fowler,J.D.；Regan,B.C.；Kaner,
R.B.；Weiller,B.H.Chemical vapor deposition of graphene on copper from
methane,ethane and propane:evidence for bilayer selectivity.Small 2012,8:
1415-1422；Hao,Y.；Bharathi,M.S.；Wang,L.；Liu,Y.；Chen,H.；Nie,S.；Wang,X.；Chou,H.；
Tan,C.；Fallahazad,B.；Ramanarayan,H.；Magnuson,C.W.；Tutuc,E.；Yakobson,B.I.；
McCarty,K.F.；Zhang,Y.-W.；Kim,P.；Hone,J.；Colombo,L.；Ruoff,R.S.,The Role of
Surface Oxygen in the Growth of Large Single-Crystal Graphene on
Copper.Science2013,342(6159),720-723.).The usual quality of graphene made from this method is higher, also may be used
To realize the growth of larger area, but this method also has some shortcomings, for example, resulting graphene film uneven thickness
Even, metallic matrix typically has higher cost, and how easily and effectively to shift obtained graphene is also a hardly possible
Topic, is unfavorable for producing on a large scale.The crystal epitaxy method of SiC high vacuum annealing is one kind on a crystal structure
Go out the method for another crystal by lattice-matched growth, although the individual layer of better quality and few layer graphene can be made,
It is that the condition that it needs is very harsh (high temperature, high vacuum), and obtained graphene is not easy to separate from substrate,
Along with carborundum and metal substrate price itself also costly (Sutter, P.W.；Flege,J.I.；Sutter,
E.A.Epitaxial graphene on ruthenium.Nat.Mater.2008,7(5):406-411.)。
The micro-processing technology of another kind of " from top to bottom " (Top-Down) be then using graphite as raw material, by stripping, intercalation,
Graphene is made in the approach such as redox, mainly there is two kinds of realizing routes：One is graphite oxidation is first passed through into covalent bond or non-
The effects such as covalent bond modification graphene oxide (GO), then obtain graphene, hereinafter referred to as GO methods through reduction；The second is directly utilize
Graphite or expanded graphite, without graphite oxide, but graphene is directly obtained by approach such as physics, chemical actions, this bag
Include micromechanics stripping method, liquid phase or gas phase stripping method, arc discharge method, electrochemical stripping method and chemical stripping method.
The general principle of GO methods is first to handle graphite with strong protonic acid, forms compound between graphite layers, then adds strong oxygen
Agent aoxidizes to it.GO is reduced again afterwards, can by GO planar structures oxy radical remove, can make it is big its
Pi bond conjugated system is restored, you can graphene is made.GO paths, which prepare graphene, has cost more cheap, simple to operate
Easy, easy the advantages of realizing prepare with scale, and stable graphene dispersing solution can be prepared, largely solve
Graphene of having determined is not easy the problem of scattered.But after GO is reduced, gained graphene sheet layer easily can reunite one again again
Rise, and certain fault of construction from the graphene obtained by this approach generally be present, such as five-membered ring, heptatomic ring, hydroxyl, carboxylic
The oxy radicals such as base, epoxy radicals and more hetero atom etc..
Micromechanics stripping method is prepared by one kind that the Geim and Novoselov by graceful Chester university of Britain in 2004 develops
Graphene method (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.), the graphite flake of high orientation is bonded on adhesive tape, then will
Graphite flake another side is clung in adhesive tape doubling, then tears adhesive tape, and so, graphite just completes to be separated for the first time.Then constantly
This process is repeated, until being stained with transparent mottled thin slice on adhesive tape, a series of graphite of different numbers of plies may finally be obtained
Alkene nanometer sheet.This micromechanics stripping means has obtained the stable graphene of two-dimension plane structure for the first time, in its principle very
Simply, obtained graphene crystal structure is very complete, and does not almost have defect.But this method can not be carried out on a large scale
It is prepared by production.
Arc discharge method is to maintain high voltage, high current, under hydrogen atmosphere, when two graphite electrodes are close to certain journey
Arc discharge can be produced when spending, CNT and the carbonizable substance of other forms are collected near negative electrode, and in reative cell
Inner wall area can obtain graphene (Subrahmanyam, K.S.；Panchakarla,L.S.；Govindaraj,A.；Rao,
C.N.R.Simple Method of Preparing Graphene Flakes by an Arc-Discharge
Method.J.Phys.Chem.C2009,113(11):4257-4259.).The graphene arranging rule that arc discharge method obtains,
Crystal formation is preferable, can obtain higher electric conductivity and preferable chemical property, but is arc discharge process the shortcomings that this method
Middle temperature is high, and reaction is violent, with certain danger.
Liquid phase or gas phase stripping method are that directly graphite or expanded graphite are added in certain organic solvent or water, by ultrasound
Ripple, heating or the effect of air-flow, graphite flake layer is peeled off, so as to prepare certain density single or multiple lift graphene dispersing solution
(Fan,C.W.；Zhang,X.；Chen,S.；Wang,H.F.；Cao,A.N.Solution-processable,highly
conductive,permanently rippled graphene sheets.Acta Phys.-Chim.Sin.2012,28
(10):2465-2470.).This method is simple, directly, and obtained graphene there's almost no compared with other method it is scarce
Fall into and it is not oxidized, preparation process is not related to chemical change, and cost is cheap, but simultaneously there is also graphene yield very
Low, lamella the defects of agglomeration is very serious again, and liquid phase stripping method is usually required by prolonged ultrasonic mistake
Journey, easily graphite flake is crushed, it is difficult to large-sized graphene is made.
Electrochemical stripping method is the LiClO using graphite as electrode4Electrolysis is used as with using the mixed liquor of propene carbonate (PC)
Matter, being charged under high voltage condition, lithium ion and PC enter graphite layers in the form of compound, after graphite expansion,
It is dispersed in the mixed solution of LiCl, DMF and PC composition, with the help of ultrasound, obtains the dispersion liquid of few layer graphene, wherein
5 layers of (Wang J., Manga K.K., Bao Q., et al.High-Yield Synthesis of are all less than more than 70%
Few-Layer Graphene Flakes through Electrochemical Expansion of Graphite in
Propylene Carbonate Electrolyte.J.Am.Chem.Soc.,2011,133(23):8888-8891.).But electricity
Chemical method is generally limited by electrode volume and surface area, and preparative-scale is very limited.
Compared to the above, can be compared by way of the chemical modification method of non-covalent bond, covalent bond peels off graphite
Complete graphene film, and easy scale, but most chemical modification methods can introduce a part of hetero atom.
Up to the present, although the method for preparing graphene is a lot.But all methods can not take into account it is easy to operate,
Yield is higher, cost is cheap, volume production and the features such as high-quality.Therefore, find it is a kind of it is simple and easy, can cheap prepare with scale height
The synthetic method of quality graphene will develop significant to it.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of economical and effective, technique
The large-scale preparation method of simple high-quality graphene.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of large-scale preparation method of high-quality graphene, comprises the following steps：Aromatic hydrocarbons examination is added into expanded graphite
Agent obtains expanded graphite solution, oxidant is dissolved in organic solvent oxidizing agent solution is made, then oxidizing agent solution is added to
In expanded graphite solution, ultrasound makes it well mixed, after mixed solution reacts completely in the water bath of certain temperature, will produce
Thing is separated, that is, obtains graphene.
Described oxidant, expanded graphite, aromatic hydrocarbons, the ratio range of organic solvent are (20~40) g：1.5g：(5~10)
mL：(20~75) mL, it is preferably (23.1~32.4) g：1.5g：5mL：75mL, more preferably 26.2g：1.5g：5mL：75mL.
Described oxidant is anhydrous ferric trichloride, anhydrous dichloride copper, aluminum trichloride (anhydrous), anhydrous molybdenum pentachloride or nothing
Water Antimony pentachloride, preferably anhydrous ferric trichloride.
Described aromatic hydrocarbons reagent is selected from least one of toluene, ethylbenzene, dimethylbenzene, benzene, isopropylbenzene or detergent alkylate
Or a variety of mixture.
Described organic solvent is selected from acetonitrile, dimethyl sulfoxide, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, N, N-
At least one of dimethyl acetamide, hexane, nitromethane or nitroethane or a variety of mixtures.
Reaction temperature is room temperature~99 DEG C, preferably 93~99 DEG C, more preferably 97 DEG C, and the reaction time is 20 small
When.
The separate mode of graphene is in the present invention：Weighed again after solution after reaction is washed with deionized water, 95% ethanol
Newly it is dispersed in absolute ethyl alcohol, 3h is stood after ultrasonic 40min, upper strata suspension is removed and collected, then adds into precipitation anhydrous
Ethanol, repeat to operate above, carry out 6 operations altogether.After suspension is collected, 24h is dried under 120 DEG C of normal pressures.
Compared with prior art, the method that the present invention disassembles graphite using chemical oxidising polymerisation grafting, no more than 100 DEG C
Water bath condition under it is disassembled obtain graphene, its principle is：Benzene monomer is copolymerized with graphite base plane in aromatic hydrocarbons, benzene
Increase benzene chain also by chemical oxidising polymerisation between monomer, so that graphite flake is peeled off, obtain graphene.This method economy
Effectively, it is simple to operate, there are potentiality prepared by scale batch.Products therefrom quality better, defect is considerably less, there is good answer
With prospect, it is expected to be applied to the fields such as ultracapacitor, lithium ion battery, electronic device and ion-selective electrode.
Brief description of the drawings
Fig. 1 is the XRD spectrum of original graphite and expanded graphite；
Fig. 2 is uv-spectrogram of the graphene in absolute ethyl alcohol and 98% sulfuric acid；
Fig. 3 is the XRD of the gained graphene of embodiment 14~17 and expanded graphite；
Fig. 4 is uv-spectrogram of the gained graphene of embodiment 18~20 in 98% sulfuric acid；
Fig. 5 is the XRD spectrum of the gained graphene of embodiment 18~20 and expanded graphite；
Fig. 6 is ultraviolet-visible of the gained graphene in three kinds of 98% sulfuric acid, absolute ethyl alcohol and water media in embodiment 29
Spectrum；
Fig. 7 is dispersiveness of the gained graphene in different solvents in embodiment 29；
The stereoscan photograph of Fig. 8 graphenes；
The transmission electron microscope photo of Fig. 9 graphenes.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Muffle furnace is heated to 1050 DEG C, 0.4g graphite is weighed in 50mL porcelain crucibles, crucible is placed in Muffle furnace
Middle heating 60s, it is rapid to take out, it is positioned in drier and cools down.After room temperature is cooled to, weighs and measure volume.Through high temperature mistake
Cheng Hou, the volumetric expansion of graphite about 42 times.After expanded, the metallic luster of original graphite disappears, and is changed into very from flakey
Fluffy vermiform, turn into the cinerous slice that length reaches 0.3cm.
Fig. 1 is the XRD spectrum of original graphite and expanded graphite, it can be seen that after expanded, the characteristic diffraction peak of graphite
(26.5 °) intensity is obviously reduced, and 26.5 ° of peak areas of expanded graphite are about the 1/6.23 of original graphite, are shown by expanding it
Afterwards, the crystallographic disorder degree of graphite flake dramatically increases, and the crystallinity of graphite flake is obviously reduced.
Embodiment 2~6
1.5g expanded graphites accurately are weighed, are separately added into 5mL benzene (embodiment 2), toluene (embodiment 3), ethylbenzene (embodiment
4), dimethylbenzene (embodiment 5), DBSA (embodiment 6), then weigh the anhydrous FeCl of 26.2g3It is dissolved in 75mL acetonitriles
In, by FeCl3Solution is added in expanded graphite, and ultrasonic 10min makes it well mixed.24h is reacted under the conditions of being then refluxed for, instead
After should terminating, remaining reactant is filtered out using vacuum filtration method, then cleaned one time with 95% ethanol, then it is anti-with deionized water
After backwashing is washed, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+And Fe2+Presence.Obtain head product again
It is dispersed in absolute ethyl alcohol and collects upper strata suspension after ultrasonic 40min, standing 3h, dries to obtain black graphene powder, yield
It is followed successively by 10.9% (embodiment 2), 8.9% (embodiment 3), 9.1% (embodiment 4), 8.3% (embodiment 5), 7.9% (implementation
Example 6).
Embodiment 7~13
7 parts of 1.5g expanded graphites accurately are weighed, add 5mL dimethylbenzene, then 4 parts weigh the anhydrous FeCl of 26.2g3It is molten respectively
In 75mL acetonitriles (embodiment 7), dimethyl sulfoxide (embodiment 8), 1-METHYLPYRROLIDONE (embodiment 9), N, N- dimethyl formyls
In amine (embodiment 10), DMA (embodiment 11), hexane (embodiment 12), nitro hexane (embodiment 13),
By FeCl3Solution is added in expanded graphite, and ultrasonic 10min makes it well mixed.24h is reacted under the conditions of being then refluxed for, is reacted
After end, remaining reactant is filtered out using vacuum filtration method, then cleaned one time with 95% ethanol, then with deionized water repeatedly
Washing, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+And Fe2+Presence.Head product is obtained again to divide
Be dispersed in absolute ethyl alcohol and ultrasonic 40min, upper strata suspension collected after standing 3h, dry to obtain black graphene powder, yield according to
Secondary is 5.7% (embodiment 7), 8.3% (embodiment 8), 6.1% (embodiment 9), 5.2% (embodiment 10), 5.8% (embodiment
11), 6.7% (embodiment 12), 9.7% (embodiment 13).
Embodiment 14~17
4 parts of 1.5g expanded graphites accurately are weighed, are separately added into 5mL benzene, then weigh the anhydrous FeCl of 26.2g3It is dissolved in 75mL nitre
In methylmethane, by FeCl3Solution is added in expanded graphite, and ultrasonic 10min makes it well mixed.Then in magnetic agitation and cold
It is respectively placed under solidifying counterflow condition in water bath with thermostatic control and reacts 20h, the bath temperature of embodiment 14~17 is followed successively by 93,95,97 and 99
℃.Reaction terminate after, remaining reactant is filtered out using vacuum filtration method, then cleaned one time with 95% ethanol, then spend from
Sub- water washs repeatedly, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+And Fe2+Presence.Then will
Head product is dispersed in absolute ethyl alcohol again, and proportioning is about 1.2mg head products/1mL absolute ethyl alcohols, and 3h is stood after ultrasonic 40min,
Collect upper strata suspension, 24h dried in 120 DEG C of air atmospheres, obtain black graphene powder, the yield of embodiment 14~17 according to
Secondary is 14.9%, 12.1%, 13.1% and 10.1%, and electrical conductivity is followed successively by 21.6,27.1,27.8 and 22.2S/cm.
Fig. 2 (a) and Fig. 2 (b) is purple of the gained graphene of embodiment 14~17 in absolute ethyl alcohol and 98% sulfuric acid respectively
There is the absworption peak of high intensity in 260 and 262nm opening positions respectively in outer collection of illustrative plates, Fig. 2 (a) and Fig. 2 (b), corresponding to graphene
Typical absorption peak.Fig. 3 (a) and Fig. 3 (b) is the XRD spectrum of the gained graphene of embodiment 14~17 and expanded graphite, wherein Fig. 3
(b) diffraction peak intensity of the gained graphene of embodiment 14~17 is multiplied by 60 times in.From Fig. 3 (a), it can be seen that, expanded graphite exists
26.5 ° of opening positions have very sharp absworption peak, corresponding to the characteristic diffraction peak of graphite, by contrast, the institute of embodiment 14~17
Graphene diffraction maximum force the way across it is very weak, almost into horizontal line, by amplifying 60 times (Fig. 3 (b)), it can be seen that diffraction maximum is moved
The position to 25.8 ° is moved, but intensity is still far less than expanded graphite, and occur new diffraction maximum, table 16 ° of position
It is bright by after disassembling reaction, the crystallographic disorder degree of graphite flake layer significantly increases, crystallinity much lower, graphite flake layer quilt really
Effectively disassemble, obtain graphene.
Embodiment 18~20
3 parts of 1.5g expanded graphites accurately are weighed, are separately added into 5mL benzene, then weigh 23.1g (embodiment 18), 29.3g respectively
(embodiment 19) and 32.4g (embodiment 20) anhydrous FeCl375mL N are dissolved in, if in N- dimethyl pyrazole alkanones, by FeCl3Solution
It is added in expanded graphite, ultrasonic 10min makes it well mixed.Then it is respectively placed under the conditions of magnetic agitation and condensing reflux
20h is reacted in 97 DEG C of waters bath with thermostatic control.After reaction terminates, remaining reactant is filtered out using vacuum filtration method, then with 95% second
Alcohol cleans one time, then is washed repeatedly with deionized water, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+
And Fe2+Presence.Then head product being dispersed in absolute ethyl alcohol again, proportioning is about 1.2mg head products/1mL absolute ethyl alcohols,
3h is stood after ultrasonic 40min, upper strata suspension is collected, dries 24h in 120 DEG C of air atmospheres, obtain black graphene powder,
The yield of embodiment 18~20 is followed successively by 9.5%, 12.7% and 14.5%, and electrical conductivity is followed successively by 21.6,21.8 and 22.3S/cm.
Fig. 4 is uv-spectrogram of the gained graphene of embodiment 18~20 in 98% sulfuric acid, and it occurs in 262nm opening positions
The absworption peak of high intensity, corresponding to the typical absorption peak of graphene.Fig. 5 (a) and Fig. 5 (b) is the gained graphite of embodiment 18~20
The diffraction peak intensity of the gained graphene of embodiment 18~20 is multiplied by 60 in the XRD spectrum of alkene and expanded graphite, wherein Fig. 5 (b)
Times.From Fig. 5 (a), it can be seen that, expanded graphite has very sharp absworption peak in 26.5 ° of opening positions, corresponding to the feature of graphite
Diffraction maximum, by contrast, the gained graphene diffraction maximum of embodiment 18~20 force the way across it is very weak, almost into horizontal line, by amplification
60 times (Fig. 5 (b)), it can be seen that diffraction maximum is moved to 25.8 ° of position, but intensity is still far less than expanded graphite, and
Occur new diffraction maximum 16 ° of position, show after disassembling reaction, the crystallographic disorder degree of graphite flake layer significantly increases
Greatly, crystallinity much lower, graphite flake layer are effectively disassembled really, obtain graphene.
Embodiment 21-22
1.5g expanded graphites accurately are weighed, are separately added into 10mL benzene, then weigh the anhydrous FeCl of 26.2g320mL is dissolved in respectively
In (embodiment 21), 50mL (embodiment 22) acetonitrile, by FeCl3Solution is added in expanded graphite, and ultrasonic 10min makes its mixing
Uniformly.24h is reacted under the conditions of being then refluxed for, after reaction terminates, remaining reactant is filtered out using vacuum filtration method, then used
95% ethanol cleans one time, then is washed repeatedly with deionized water, until being detected in cleaning solution with the potassium ferricyanide and potassium ferrocyanide
Less than Fe3+And Fe2+Presence.Head product is obtained to be dispersed in again in absolute ethyl alcohol and collect upper strata after ultrasonic 40min, standing 3h
Suspension, dries to obtain black graphene powder, and yield is followed successively by 7.6% (embodiment 21), 7.8% (embodiment 22).
Embodiment 23-24
1.5g expanded graphites accurately are weighed, are separately added into 8mL benzene, then weigh the anhydrous FeCl of 20g respectively3(embodiment 23),
The anhydrous FeCl of 40g3(embodiment 24) is dissolved in 75mL acetonitriles, by FeCl3Solution is added in expanded graphite, and ultrasonic 10min makes it
It is well mixed.24h is reacted under the conditions of being then refluxed for, after reaction terminates, remaining reactant is filtered out using vacuum filtration method, then
Cleaned one time with 95% ethanol, then washed repeatedly with deionized water, until being examined in cleaning solution with the potassium ferricyanide and potassium ferrocyanide
Fe is not detected3+And Fe2+Presence.Head product is obtained to be dispersed in absolute ethyl alcohol and collect after ultrasonic 40min, standing 3h again
Layer suspension, dries to obtain black graphene powder, yield is followed successively by 9.2% (embodiment 23), 9.8% (embodiment 24).
Embodiment 25-28
It is accurate to weigh 1.5g expanded graphites, add 5mL benzene, then weigh respectively the anhydrous dichloride copper (embodiment 25) of 26.2g,
Aluminum trichloride (anhydrous) (embodiment 26), anhydrous molybdenum pentachloride (embodiment 27), anhydrous Antimony pentachloride (embodiment 28) are dissolved in 75mL
In acetonitrile, each oxidizing agent solution is added in expanded graphite respectively, ultrasonic 10min makes it well mixed.It is then refluxed for condition
Lower reaction 24h, after reaction terminates, remaining reactant is filtered out using vacuum filtration method, then cleaned one time with 95% ethanol, then
Washed repeatedly with deionized water, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+And Fe2+Presence.
Obtain head product to be dispersed in again in absolute ethyl alcohol and collect upper strata suspension after ultrasonic 40min, standing 3h, dry to obtain black graphite
Alkene powder, yield are followed successively by 5.1% (embodiment 25), 4.7% (embodiment 26), 3.0% (embodiment 27), 4.4% (embodiment
28)。
Embodiment 29
Embodiment 16 is repeated, after reaction terminates, remaining reactant is filtered out using vacuum filtration method, then with 95% ethanol
Cleaning one time, then washed repeatedly with deionized water, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+With
Fe2+Presence.Then head product is dispersed in absolute ethyl alcohol again, proportioning is about 1.2mg head products/1mL absolute ethyl alcohols, is surpassed
3h is stood after sound 40min, collects upper strata suspension, adds absolute ethyl alcohol, repeats ultrasonic standing process, is carried out 6 times altogether, will
Collected upper strata suspension is concentrated, and is dried 24h in 120 DEG C of air atmospheres, is obtained black graphene powder, ultimate yield is
42.6%, electrical conductivity 27.8S/cm.
Fig. 6 (a), Fig. 6 (b) and Fig. 6 (c) are respectively the graphene of gained in embodiment 29 in 98% sulfuric acid, absolute ethyl alcohol
With the ultraviolet-visible spectrum in three kinds of media of water, three figures have obvious absorption peaks, corresponding graphite at 262,260 and 268nm respectively
The typical absorption peak of alkene.
Fig. 7 (a) is dispersiveness of the graphene in different solvents of gained in embodiment 29, be followed successively by from left to right water,
Methyl pyrrolidone, dimethyl sulfoxide (DMSO), tetrahydrofuran and absolute ethyl alcohol, the dispersion liquid concentration in rear three kinds of solvents respectively reach
0.34th, 0.53 and 0.57mg/mL；Fig. 7 (b) and Fig. 7 (c) is respectively two kinds of solvents of dimethyl sulfoxide (DMSO) and absolute ethyl alcohol in Fig. 7 (a)
In Tyndall effect.Show the colloidal solution feature of stable dispersion.
Embodiment 30
Embodiment 19 is repeated, after reaction terminates, remaining reactant is filtered out using vacuum filtration method, then with 95% ethanol
Cleaning one time, then washed repeatedly with deionized water, until can't detect Fe with the potassium ferricyanide and potassium ferrocyanide in cleaning solution3+With
Fe2+Presence.Then head product is dispersed in absolute ethyl alcohol again, proportioning is about 1.2mg head products/1mL absolute ethyl alcohols, is surpassed
3h is stood after sound 40min, collects upper strata suspension, adds absolute ethyl alcohol, repeats ultrasonic standing process, is carried out 6 times altogether, will
Collected upper strata suspension is concentrated, and is dried 24h in 120 DEG C of air atmospheres, is obtained black graphene powder, final product
Yield is 40.3%, electrical conductivity 21.8S/cm.
Embodiment 31
The graphene dispersion prepared on a small quantity in ethanol and is subjected to short time supersound process, makes sample dispersion uniform, is fitted
Drawn and dripped on clean silicon chip with dropper after dilution, metal spraying processing is carried out after drying, is placed under ESEM and is observed,
Gained stereoscan photograph is shown in Fig. 8.It can be seen that transparent yarn account shape lamellar structure.
Embodiment 32
The graphene dispersion prepared on a small quantity in ethanol and is subjected to short time supersound process, makes sample dispersion uniform, is fitted
Drawn and dripped on copper mesh with dropper after dilution, be observed and imaged with transmission electron microscope after drying.Gained transmission electron microscope (TEM)
Photo is shown in Fig. 9.Wherein right figure is the SEAD collection of illustrative plates in blue line region in left figure, it can be seen that the graphene film of individual layer,
SEAD is presented regular hexagon and shows that gained graphene has complete lattice structure.
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using invention.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel do not depart from improvement that scope made and modification all should be the present invention's according to the announcement of the present invention
Within protection domain.
Claims (6)
1. a kind of large-scale preparation method of high-quality graphene, it is characterised in that comprise the following steps：
Aromatic hydrocarbons reagent is added into expanded graphite and obtains expanded graphite solution, oxidant is dissolved in organic solvent oxidant is made
Solution, then oxidizing agent solution is added in expanded graphite solution, ultrasound makes it well mixed, and mixed solution is in certain temperature
After being reacted completely in water bath, product is separated, that is, obtains graphene；
Described oxidant, expanded graphite, aromatic hydrocarbons, the ratio range of organic solvent are（20~40）g：1.5g：（5 ~10）mL：
（20~75）mL；
Described oxidant is anhydrous ferric trichloride, anhydrous dichloride copper, aluminum trichloride (anhydrous), anhydrous molybdenum pentachloride or anhydrous five
Antimony chloride；
Described aromatic hydrocarbons reagent is selected from least one of toluene, ethylbenzene, dimethylbenzene, benzene, isopropylbenzene or detergent alkylate or more
The mixture of kind；
Described organic solvent is selected from nitromethane or nitroethane.
A kind of 2. large-scale preparation method of high-quality graphene according to claim 1, it is characterised in that described oxygen
Agent, expanded graphite, aromatic hydrocarbons, the ratio range of organic solvent are（23.1~32.4）g：1.5g：5 mL：75mL.
A kind of 3. large-scale preparation method of high-quality graphene according to claim 2, it is characterised in that described oxygen
Agent, expanded graphite, aromatic hydrocarbons, the ratio range of organic solvent are 26.2g：1.5g：5 mL：75mL.
A kind of 4. large-scale preparation method of high-quality graphene according to claim 1, it is characterised in that reaction temperature
For room temperature ~ 99 DEG C.
A kind of 5. large-scale preparation method of high-quality graphene according to claim 4, it is characterised in that reaction temperature
For 93 ~ 99 DEG C.
6. the large-scale preparation method of a kind of high-quality graphene according to claim 1, it is characterised in that graphene
Separate mode is：It is dispersed in again in absolute ethyl alcohol again after solution after reaction is washed with deionized water, ethanol, it is quiet after ultrasound
Put, upper strata suspension is removed and collected, then absolute ethyl alcohol is added into precipitation, more than repetition operation is multiple, and suspension is collected
Afterwards, drying obtains graphene.
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| CN103253661A (en) * | 2013-05-27 | 2013-08-21 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder at large scale |
| EP2719662A1 (en) * | 2007-08-09 | 2014-04-16 | Centre National de la Recherche Scientifique (CNRS) | Graphene solutions |
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| CN103253661A (en) * | 2013-05-27 | 2013-08-21 | 中国科学院上海微系统与信息技术研究所 | Method for preparing graphene powder at large scale |
Non-Patent Citations (1)
| Title |
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| High-throughput Production of High-quality Graphene by Exfoliation of Expanded Graphite in Simple Liquid Benzene Derivatives;Zhen Liu等;《Journal of Nanoscience and Nanotechnology》;20101130;第10卷(第11期);第7382-7385页 * |
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