CN107324319A - A kind of large stretch of layer graphene and preparation method thereof - Google Patents
A kind of large stretch of layer graphene and preparation method thereof Download PDFInfo
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- CN107324319A CN107324319A CN201610270886.0A CN201610270886A CN107324319A CN 107324319 A CN107324319 A CN 107324319A CN 201610270886 A CN201610270886 A CN 201610270886A CN 107324319 A CN107324319 A CN 107324319A
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Abstract
The invention provides a kind of large stretch of layer graphene and preparation method thereof, the preparation method of large stretch of layer graphene is：Using graphite intercalation compound as raw material, under turbulent-flow conditions generated reactive gas occurs for the intercalator and reaction reagent for making graphite intercalation compound interlayer, shearing force and the gas that turbulent flow is produced peel off the graphite flake layer in graphite intercalation compound jointly, obtain large stretch of layer graphene.The preparation method, which has merged physics, to be peeled off with two kinds of chemical stripping while the process carried out, large stretch of layer graphene that lamella size is 1 50 μm, thickness is 18 atomic layers can be obtained, and less than ten layers of graphene yield intimate 100%, in addition, the preparation method is simple, easily-controllable, reaction condition is gentle, method is simple, and cost is low, suitable for industrial.
Description
Technical field
The invention belongs to technical field of graphene, it is related to a kind of graphene and preparation method thereof, more particularly to one
The method planted large stretch of layer high-quality graphene and efficiently prepare large stretch of layer high-quality graphene.
Background technology
Since being found from 2004, graphene receives much concern as a kind of new carbon.It is one to finish
The thickness being made up of entirely the carbon atom of sp2 hydridization is only the quasi- two dimensional crystal of monoatomic layer or several monoatomic layers
Material, it is but also most hard nano material that graphene, which is currently world most thin, and it is almost fully transparent
, thermal conductivity factor is high, and its electron mobility is high under normal temperature, and resistivity ratio copper or silver are lower, are world resistance
The minimum material of rate.Because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, therefore is expected to can be used to send out
Exhibition is thinner, conductive speed faster electronic component or transistor of new generation.Because it is a kind of transparent, good
Conductor, also is adapted for for manufacturing transparent touch screen, even tabula rasa, solar cell.While graphene
Material also can be in high-performance nanometer electronic device, photoelectric device, gas sensor, composite, Flied emission material
The field such as material and energy stores obtains extensive use.But, inexpensive, a large amount of preparations of high-quality graphene
Still face adverse conditions, constrain the development and application of the material.
Up to the present, the preparation on graphene has had been developed that many methods：Micromechanics partition method,
Graphite oxide reducing process, chemical vapour deposition technique, solvent stripping method etc..
The method for most starting to use is micromechanics partition method, by mechanical force mono-layer graphite piece from graphite wafer
It is stripped out in body, the mono-layer graphite piece that this method is obtained is than more complete, uncontrollable mono-layer graphite
Size, this method is by manually operating, and became uneven one.
Graphite oxide reducing process is to be mainly based upon Hummer methods graphite is carried out into oxidation processes, obtains oxygen
After graphite, then it peel off to obtain graphene oxide, eventually pass reduction treatment and obtain graphene.
Due to oxidizing process would generally heavy damage graphene sheet layer structure, although pass through reduction treatment, gained stone
Still there is larger gap with high-quality graphene in the property indices of black alkene material.In addition, graphite
Oxidizing process usually requires a large amount of highly acid oxidants such as concentrated sulfuric acid, concentrated nitric acid, dichromic acid and permanganic acid
Potassium, sodium nitrate etc.；And high-temperature process is needed in mesh reduction process or toxic using hydrazine, dimethylhydrazine etc.
Chemical substance, not only energy consumption is big, efficiency is low, cost is high but also pollution environment.
Chemical vapour deposition technique is that various substrates surface is placed on metal or metallic compound as catalyst,
Carbon containing gas, and the method that graphene is deposited on substrate at high temperature are filled with reaction cavity, it is this
Method can realize prepared by large-scale graphene, but in place of still suffering from some shortcomings, such as this method
The graphene of preparation does not show quantum hall effect, and how to choose suitable substrate is also a problem,
While existing, cost is higher, the shortcoming of complex process.
The principle of solvent stripping method is the dispersion liquid that low concentration is formed by a small amount of graphite dispersion in solvent,
Using the Van der Waals force of the action breaks down graphite layers of ultrasonic wave, now solvent may be inserted into graphite layers, enter
Row is peeled off layer by layer, prepares graphene.The method will not destroy the knot of graphene as oxidation-reduction method
Structure, can prepare high-quality graphene, and the yield highest of graphene (is about in N-methyl pyrrolidones
8%), electrical conductivity is 6500S/m；Have the disadvantage that yield is very low.Liquid phase ultrasound, which is peeled off, to be generally required to surpass for a long time
Sound, the even up to hundreds of hours having, inevitably destroys the integrality of graphene, so as to influence it
Performance.
In addition, D.A.Bennetts and L.M.Hocking on Proc.R.Soc.Lond magazines from fluid
Aerodynamic point, which explains high speed inclination angle and rotated, causes the generation of turbulent flow in container, and Xianjue Chen et al. exist
Chem.Commun. the method that graphite and boron nitride are peeled off using turbulent flow has been delivered on magazine；
A kind of turbulent method for preparing high-quality graphene is described in CN103350995.But, rely solely on thing
The difficulty that reason peels off preparing graphite alkene is larger, and the yield of obtained graphene is relatively low.
The drawbacks of existing due to above-mentioned preparation method, in field of preparation of graphene in the urgent need to exploitation one kind can be big
Amount, the inexpensive and environment-friendly new method for preparing high-quality graphene.
The content of the invention
For prepared present in existing graphene preparation method cost height, graphene of poor quality, low yield and
The problems such as lamella is small, it is an object of the invention to provide a kind of efficient side for preparing large stretch of layer high-quality graphene
Method, methods described fusion physics and chemical two kinds of processes, can obtain lamella size be 1-50 μm, thickness be
Large stretch of layer graphene of 1-8 atomic layer, and less than ten layers of graphene yield intimate 100%, method letter
It is single, suitable for industrial.
Large stretch of layer graphene of the present invention each means the graphite that lamella size is 1-50 μm unless otherwise specified
Alkene.
For up to this purpose, the present invention uses following technical scheme：
An object of the present invention is to provide a kind of preparation method of large stretch of layer graphene, and methods described is：
Using graphite intercalation compound as raw material, make the intercalator and reaction reagent of graphite intercalation compound interlayer in turbulent flow
Under the conditions of react generation gas, the shearing force and the gas that turbulent flow is produced peel off graphite intercalation jointly
Graphite flake layer in compound, obtains large stretch of layer graphene.
The graphite intercalation compound is the material that intercalator inserts graphite layers formation.
In the preparation method for the graphene that the present invention is provided, the intercalator in graphite intercalation compound is tried with reaction
Agent is reacted under turbulent-flow conditions, and the turbulent flow is a kind of flow regime of fluid, and fluid makees irregular fortune
It is dynamic, there is the component velocity generation perpendicular to flow tube axis direction.
The preparation method fusion physics for the graphene that the present invention is provided and chemical two kinds of processes.Methods described is used
Liquid flowing provides peeling force, meanwhile, the graphite intercalation compound disperseed in a solvent is on the basis of graphite
Upper insertion alkali metal, alkali metal alloy or metal halide, the intercalators of graphite layers can with solvent or
The liquid substance added in solvent reacts, and produces gas, destroys intercalation configuration, plays chemical stripping
The physical process that the shearing of effect, the i.e. convection current of liquid to graphite flake layer is peeled off is produced with intercalator with solvent reaction
The chemical process of angry body, forms complete one and carries out simultaneously.
Intercalator in graphite intercalation compound can increase interlamellar spacing reduction interlaminar action power, intercalator with it is anti-
Answer the gas impact graphite flake layer that reagent reacting is produced so as to further reduce lamella active force, be turbulent shear
Power tears graphene sheet layer and provides help, and physical process complements each other to reach preparation with chemical process
The purpose of high-quality large stretch of layer graphene.
The preparation method of the fusion physics that the present invention is provided and large stretch of layer graphene of chemical two kinds of processes, is compared
Compared with the work of forefathers, the generation of chemical gas and the increase of interlamellar spacing cause physics stripping to become more easy,
The yield of obtained graphene will be far longer than single physics stripping process, and can avoid completely traditional
Destruction of the method to graphene sheet layer.Single physics peels off graphene yield and is less than 1%, and the present invention is carried
The preparation method of confession obtains less than ten layers of graphene yield intimate 100%, and obtained graphene sheet layer
The graphene that size is obtained considerably beyond forefathers with turbulene method, the graphene such as obtained with 150 mesh intercalated graphites
Lamella size is 1-50 μm, and thickness is 1-8 atomic layer.
The graphite intercalation compound is first scattered in solvent formation dispersion liquid, then is reacted with reaction reagent.
Preferably, the concentration of graphite intercalation compound is 0.1-1000mg/mL in the dispersion liquid, such as 0.5
mg/mL、1mg/mL、2mg/mL、3mg/mL、5mg/mL、8mg/mL、10mg/mL、15
mg/mL、20mg/mL、25mg/mL、30mg/mL、50mg/mL、100mg/mL、200
mg/mL、300mg/mL、400mg/mL、500mg/mL、600mg/mL、700mg/mL、800
Mg/mL, 900mg/mL or 950mg/mL etc..
The solvent is organic solvent and/or water, preferably organic solvent.
Preferably, the organic solvent is 8-14 for that can dissolve graphene and/or Hansen solubility parameters
(cal/cm3)1/2Organic solvent, such as Hansen solubility parameters be 8.1-8.5 (cal/cm3)1/2、
8.6-8.9(cal/cm3)1/2、9.1-9.5(cal/cm3)1/2、10-10.5(cal/cm3)1/2、11-12(cal/cm3)1/2Or
12.5-13.5(cal/cm3)1/2Deng.
Preferably, the organic solvent be aldehyde, organic acid, 1-METHYLPYRROLIDONE, dimethylformamide,
In dimethyl acetamide, chlorobenzene or dichloro-benzenes any one or at least two combination.It is typical but unrestricted
The combination of property such as, aldehyde and organic acid, 1-METHYLPYRROLIDONE, dimethylformamide and dimethyl acetamide,
Chlorobenzene and dichloro-benzenes, organic acid, 1-METHYLPYRROLIDONE and dimethylformamide, dimethyl acetamide, chlorine
Benzene and dichloro-benzenes.
The reason for selecting organic solvent one is that organic solvent can stay hydrophobic graphene in the solution；
Two are, organic solvent is peeled off with dispersion effect more preferably.
The graphite intercalation compound is prepared using intercalator and graphite as raw material by mixing method.
Preferably, the mass ratio of the intercalator and graphite is 1:20-20:1, such as 1:15、1:12、1:10、1:8、
1:5、1:3、1:1、3:1、5:1、10:1、12:1、15:1 or 18:1 etc..The mixing method can be by intercalation
Agent is entirely insertable in graphite, therefore, and the mass ratio of intercalator and graphite is also in graphite intercalation compound
1:20-20:1。
Preferably, the mixing method is：The intercalator of molten condition is mixed with graphite, graphite intercalation is obtained
Compound；Or, mix intercalator with graphite, under the conditions of vacuum tightness, intercalator is warming up in molten
State, is incubated, and washs, and drying obtains graphite intercalation compound.
Preferably, the temperature of the molten condition be 15-450 DEG C, such as 20 DEG C, 30 DEG C, 50 DEG C, 80 DEG C,
It is 100 DEG C, 150 DEG C, 200 DEG C, 230 DEG C, 280 DEG C, 300 DEG C, 350 DEG C, 400 DEG C or 420 DEG C etc., excellent
Elect 20 DEG C -380 DEG C as.
The preparation method of the graphite intercalation compound is a lot, and those skilled in the art can select not as needed
Same preparation method.Mixing method is one of those relatively simple method, therefore preferably mixing method.
The intercalator is metal and/or metal halide.Others can be produced with respective reaction reagent reacting
The intercalator of gas can be used herein.
Preferably, the intercalator is potassium, sodium, lithium, sodium-potassium eutectic, lodine chloride, aluminium chloride, chlorination
In nickel, antimony chloride, iron chloride or antimony fluoride any one or at least two combination.It is typical but unrestricted
The combination such as potassium and sodium of property, lithium and sodium-potassium eutectic, lodine chloride and aluminium chloride, nickel chloride, antimony chloride and chlorination
Iron, antimony fluoride, lodine chloride, aluminium chloride and nickel chloride.
Preferably, the graphite is expanded graphite, crystalline flake graphite, micro crystal graphite, pyrolytic graphite or inflatable
In graphite any one or at least two combination, preferably 10-150 mesh expanded graphite, such as 20 mesh, 30
Mesh, 50 mesh, 80 mesh, 100 mesh, 120 mesh or 140 mesh etc..
The quality of the reaction reagent be graphite intercalation compound quality 10%-500%, such as 15 DEG C, 20 DEG C,
30℃、50℃、80℃、100℃、120℃、150℃、200℃、230℃、280℃、300℃、320℃、
350 DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 450 DEG C or 480 DEG C etc..
The reaction reagent is in water, alcohol, sodium borohydride solution, hydrazine hydrate solution or hydrogenperoxide steam generator
Any one or at least two combination.Typical but non-limiting combination such as water and alcohol, sodium borohydride solution
With hydrazine hydrate solution, water, alcohol and hydrogenperoxide steam generator.As long as the reaction reagent can be with graphite intercalation
The intercalated material reaction generation gaseous product of graphite layers in compound.It can also be other materials.
Those skilled in the art can select different specific reactions to try according to the species of intercalator in graphite intercalation compound
Agent.
Preferably, the sodium borohydride solution is the alkaline solution that pH is 9-13, such as pH value be 9.3,9.8,
10th, 11,12 or 12.5 etc..
Preferably, the weight/mass percentage composition of hydrazine hydrate is 30%-80% in the hydrazine hydrate solution, such as 32%,
35%th, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 60%, 70% or 75% etc..
Preferably, the weight/mass percentage composition of hydrogen peroxide is 30%-80% in the hydrogenperoxide steam generator, such as
32%th, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 60%, 70% or
75% etc..
The turbulent environment is produced by high speed rotation, and the rotating speed of the high speed rotation is
3500-10000r/min, such as 4000r/min, 4500r/min, 5000r/min, 6000r/min, 6500
r/min、7000r/min、7500r/min、7800r/min、8200r/min、8500r/min、9000
R/min or 9500r/min etc., preferably 7000-8000r/min.The rotary speed can be provided accordingly
Peeling force ensures that the graphite flake layer in graphite intercalation compound is effectively peeled off.
Preferably, the time of the turbulent flow is 0.5-1h, such as 0.6h, 0.7h, 0.8h or 0.9h.
The turbulent flow is produced by supercentrifuge.The turbulent flow can also be carried out on other devices, as long as
The rotary speed of high speed can be provided to provide enough shearing peeling forces.
As preferred technical scheme, methods described comprises the following steps：
(1) graphite intercalation compound is scattered in solvent, the concentration for obtaining graphite intercalation compound is
0.1-1000mg/mL dispersion liquid；
(2) reaction reagent and dispersion liquid are reacted under conditions of rotary speed is 3500-10000r/min,
Rotate after 0.5-1h, obtain large stretch of layer graphene, wherein, the reaction is：Reaction reagent and graphite intercalation
Intercalator in compound is reacted, and generates gaseous product；The quality of the reaction reagent is graphite intercalation
The 10%-500% of compound quality.
The second object of the present invention is to provide the big Sheet Graphite that a kind of method as described above is prepared
Alkene, the graphene sheet layer size be 1-50 μm, such as 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm,
18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 45 μm etc., thickness is 1-8 atomic layer,
Such as 2 atomic layers, 3 atomic layers, 4 atomic layers or 5 atomic layers.
Compared with prior art, beneficial effects of the present invention are：
1st, the preparation method for large stretch of layer graphene that the present invention is provided uses physical process and chemical process simultaneously
Peel off graphite；Physical process is that the shearing force that liquid motion is produced is shelled with impact force to the shearing of graphite flake layer
From chemical process is that intercalator produces gas with solvent reaction.The physics worked simultaneously is torn and chemical gas
Volume expansion process can realize that graphite is farthest peeled off, and the graphene yield that it obtains less than ten layers is intimate
100%.This is the method that the first can compare favourably with graphite oxide method yield.Solvent supersonic is peeled off and other
Turbulent method, which is peeled off, can not obtain large stretch of layer graphene that the present invention is provided.
2nd, influence of the preparation method of large stretch of layer graphene its whole preparation process that the present invention is provided to environment
Very little, and the processing cost of waste liquid is low.
3rd, the preparation method whole preparation process for large stretch of layer graphene that the present invention is provided is 13h or so, reaction
Time is easier than ultrasonic method or oxide-reduction method many, and easy control of reaction, and reaction condition is gentle,
Easily expand scale, realize industrialization.
4th, large stretch of layer graphene defect that the present invention is provided is few, and quality is high, big (the graphene sheet layer size of lamella
For 1-50 μm), graphene sheet layer is distributed in 1-8 layers.
Brief description of the drawings
Fig. 1 schemes for the SEM of graphene made from embodiment 1.
Fig. 2 is the XRD of graphene made from embodiment 1.
Fig. 3 schemes for the TEM of graphene made from embodiment 1.
Fig. 4 is the TEM High-Resolution Maps of graphene made from embodiment 1.
Fig. 5 is the electron diffraction diagram of graphene made from embodiment 1.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.This hair
The following examples of bright offer are used for the purpose of clearly illustrating technical scheme, rather than to the present invention's
Limit.The various forms of changes of many kinds or change can be made on the basis of the technical scheme that the present invention is provided
Dynamic, its obvious change is changed still among present invention protection.
Embodiment 1：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) 81.4mg metallic potassiums are mixed with 200mg expanded graphites, 200 DEG C of heating 12h prepare gold
The graphite intercalation compound of yellow；
(2) graphite intercalation compound for obtaining step (1) is distributed to 50mL organic solvent N- methyl pyrroles
In pyrrolidone, the dispersion liquid that graphite intercalation compound concentration is 3mg/mL is obtained；
(3) add 1mL ethanol solutions in the dispersion liquid obtained to step (2), and operation immediately at a high speed from
Scheming, rotating speed is 7000r/min, and reaction is finished after 0.5 hour, cleans reaction product, is dried, is obtained stone
Black alkene powder aggregates.
Graphene powder aggregation is distributed in organic solvent it is characterized.
Fig. 1 is the SEM figures of obtained graphene, and graphene powder aggregation shows the lamella knot of flexibility
Structure, different from the laminated structure that graphite rule is smooth.Fig. 2 is the XRD of obtained graphene, shows stone
Black alkene powder occurs without obvious crystal peak, and only unformed bulge is in 26 ° or so appearance.Fig. 3
It is the TEM figures of obtained graphene, the TEM of graphene shows its size more than 10 μm.Fig. 4 is
The TEM High-Resolution Maps of obtained graphene, it is monoatomic layer to show its thickness.Fig. 5 is obtained graphene
Electron diffraction diagram, show its intact crystal structure.
Embodiment 2：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g expanded graphites, vacuum tightness, 1h is warming up to
380 DEG C, 12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains stone
Black intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, obtain the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) 1mL sodium borohydride alkaline solutions are added in the dispersion liquid obtained to step (2), and transported immediately
Row supercentrifuge, rotating speed is 7000r/min, and centrifugation is reacted after 0.5 hour to be finished, and cleans reaction product,
Dry, obtain graphene powder aggregation.
The sodium borohydride solution is the alkaline solution that pH is 9-13, and such as pH value is 11 or 12.
The weight/mass percentage composition that sodium borohydride alkaline solution in embodiment 2 is replaced with into hydrazine hydrate is
30%-80% (such as 50% or 65%) hydrazine hydrate solution can equally obtain graphene powder aggregation.
Embodiment 3：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g expanded graphites, vacuum tightness, 1h is warming up to
380 DEG C, 12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains stone
Black intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, obtain the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) hydrogen peroxide solution that 1mL mass fractions are 30% is added in the dispersion liquid obtained to step (2),
Supercentrifuge is run after addition immediately, rotating speed is 7000r/min, centrifugation is reacted after 0.5 hour to be finished, clearly
Reaction product is washed, dries, obtains graphene powder aggregation.
Embodiment 4：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) 81.4mg metallic potassiums are mixed with 200mg graphite, 200 DEG C of heating 12h prepare golden yellow
Graphite intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to 50mL organic solvent N- methyl pyrroles
In pyrrolidone, the dispersion liquid that graphite intercalation compound concentration is 3mg/mL is obtained；
(3) 1mL ethanol solutions are added in the dispersion liquid obtained to step (2), and are adding ethanol solution
Afterwards, supercentrifuge is run immediately, rotating speed is 7000r/min, centrifugation is reacted after 0.5 hour to be finished, and is cleaned
Reaction product, dries, obtains graphene powder aggregation.
Embodiment 5：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C,
12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains graphite intercalation
Compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, obtain the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) 1mL sodium borohydride alkaline solution is added in the dispersion liquid obtained to step (2), and added
Enter and run supercentrifuge after sodium borohydride alkaline solution immediately, rotating speed is 7000r/min, centrifuge 0.5 hour
Reaction is finished afterwards, cleans reaction product, is dried, is obtained graphene powder aggregation.
Embodiment 6：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C,
12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains graphite intercalation
Compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, obtain the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) hydrogen peroxide solution that 1mL mass fractions are 30% is added in the dispersion liquid obtained to step (2),
And after mass fraction is added for 30% hydrogen peroxide solution, supercentrifuge is run immediately, rotating speed is
7000r/min, centrifugation is reacted after 0.5 hour to be finished, and is cleaned reaction product, is dried, obtain graphene powder
Aggregation.
Embodiment 7：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) 81.4mg metallic potassiums are mixed with 200mg graphite, 200 DEG C of heating 12h prepare golden yellow
Graphite intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to 50mL organic solvent N- methyl pyrroles
In pyrrolidone, 3mg/mL dispersion liquid is obtained；
(3) 1mL ethanol solutions are added in the dispersion liquid obtained to step (2), and are adding ethanol solution
Afterwards, supercentrifuge is run immediately, rotating speed is 10000r/min, centrifugation is reacted after 0.5 hour to be finished, and is cleaned
Reaction product, dries, obtains graphene powder aggregation.
Embodiment 8：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C,
12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains graphite intercalation
Compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, obtain the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) 1mL sodium borohydride alkaline solutions are added in the dispersion liquid obtained to step (2), and are being added
Supercentrifuge is run after sodium borohydride alkaline solution immediately, rotating speed is 10000r/min, after centrifuging 0.5 hour
Reaction is finished, and cleans reaction product, is dried, is obtained graphene powder aggregation.
The pH value of sodium borohydride alkaline solution can be 9-13, such as 11 or 12 in embodiment 8.
Embodiment 9：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the anhydrous FeCl of 0.3g3Mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C,
12h is maintained, product is obtained, product is dissolved in dilute hydrochloric acid solution, suction filtration, drying obtains graphite intercalation
Compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, prepare the dispersion liquid that graphite intercalation compound concentration is 5mg/mL；
(3) hydrogen peroxide solution that 1mL mass fractions are 30% is added in the dispersion liquid obtained to step (2),
And after mass fraction is added for 30% hydrogen peroxide solution, supercentrifuge is run immediately, rotating speed is
10000r/min, centrifugation is reacted after 0.5 hour to be finished, and is cleaned reaction product, is dried, obtain graphene powder
Aggregation.
Embodiment 10
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) 400mg metals sodium-potassium eutectic is mixed with 20mg graphite, 200 DEG C of heating 12h prepare gold
The graphite intercalation compound of yellow；
(2) graphite intercalation compound for obtaining step (1) is added in 52.5mL ethanol solutions, and is being added
After entering, supercentrifuge is run immediately, rotating speed is 3500r/min, centrifugation is reacted after 1 hour to be finished, and is cleaned
Reaction product, dries, obtains graphene powder aggregation.
Embodiment 11：
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) 10mg metallic potassiums are mixed with 200mg 10-150 mesh expanded graphites, 200 DEG C of heating 12h, system
For the graphite intercalation compound for going out golden yellow；
(2) graphite intercalation compound for obtaining step (1) is distributed to 100mL dimethylformamides and chlorine
In the mixed liquor of benzene, the dispersion liquid that graphite intercalation compound concentration is 1000mg/mL is obtained；
(3) 1312mL ethanol solutions are added in the dispersion liquid obtained to step (2), and operation immediately is at a high speed
Centrifuge, rotating speed is 9000r/min, and reaction is finished after 0.8 hour, cleans reaction product, is dried, is obtained
Graphene powder aggregation.
Embodiment 12
A kind of preparation method of large stretch of layer graphene, comprises the following steps：
(1) by the mixing of the mixture of 0.3g lodine chlorides and antimony chloride and 0.05g crystalline flake graphites and pyrolytic graphite
Thing is mixed, vacuum tightness, and 1h is warming up to 380 DEG C, is maintained 12h, is obtained product, product is dissolved in into watery hydrochloric acid
In solution, suction filtration, drying obtains graphite intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is distributed to organic solvent 1-METHYLPYRROLIDONE
In, prepare the dispersion liquid that graphite intercalation compound concentration is 10mg/mL；
(3) hydrogen peroxide solution that 1mL mass fractions are 80% is added in the dispersion liquid obtained to step (2),
And after mass fraction is added for 80% hydrogen peroxide solution, supercentrifuge is run immediately, rotating speed is
8000r/min, centrifugation is reacted after 0.5 hour to be finished, and is cleaned reaction product, is dried, obtain graphene powder
Aggregation.
60% hydrogen peroxide solution can also be applied to embodiment 12, obtain graphene powder aggregation.
The graphene powder aggregation is dispersed through can obtain large stretch of layer graphene afterwards in a solvent.
Graphene made from embodiment 2-12 is carried out respectively SEM, XRD, TEM, TEM high-resolution and
Electronic diffraction is characterized, and the characterization result of each embodiment is similar to Fig. 1-5, illustrates that embodiment 2-12 is same
It can be made large stretch of layer graphene, and the lamella size of large stretch of layer graphene that embodiment 2-12 is obtained is
1-50 μm, thickness is 1-8 atomic layer.
Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention
It is not limited thereto, person of ordinary skill in the field is it will be clearly understood that any skill for belonging to the art
Art personnel the invention discloses technical scope in, the change or replacement that can be readily occurred in all fall within the present invention
Protection domain and it is open within the scope of.
Claims (10)
1. a kind of preparation method of large stretch of layer graphene, it is characterised in that methods described is：Inserted with graphite
Stratification compound is raw material, and the intercalator and reaction reagent for making graphite intercalation compound interlayer are issued in turbulent-flow conditions
Raw generated reactive gas, the shearing force and the gas that turbulent flow is produced is peeled off in graphite intercalation compound jointly
Graphite flake layer, obtains large stretch of layer graphene.
2. according to the method described in claim 1, it is characterised in that the graphite intercalation compound first divides
Dissipate in solvent formation dispersion liquid, then reacted with reaction reagent；
Preferably, the concentration of graphite intercalation compound is 0.1-1000mg/mL in the dispersion liquid.
3. method according to claim 2, it is characterised in that the solvent be organic solvent and/or
Water, preferably organic solvent；
Preferably, the organic solvent is 8-14 for that can dissolve graphene and/or Hansen solubility parameters
(cal/cm3)1/2Organic solvent；
Preferably, the organic solvent be aldehyde, organic acid, 1-METHYLPYRROLIDONE, dimethylformamide,
In dimethyl acetamide, chlorobenzene or dichloro-benzenes any one or at least two combination.
4. the method according to one of claim 1-3, it is characterised in that the graphite intercalation compound
Prepared using intercalator and graphite as raw material by mixing method；
Preferably, the mass ratio of the intercalator and graphite is 1:20-20:1；
Preferably, the mixing method is：The intercalator of molten condition is mixed with graphite, graphite intercalation is obtained
Compound；Or, mix intercalator with graphite, under the conditions of vacuum tightness, intercalator is warming up in molten
State, is incubated, and washs, and drying obtains graphite intercalation compound；
Preferably, the temperature of the molten condition is 15-450 DEG C, preferably 20 DEG C -380 DEG C.
5. utilize the method described in one of claim 1-4, it is characterised in that the intercalator be metal and
/ or metal halide；
Preferably, the intercalator is potassium, sodium, lithium, sodium-potassium eutectic, lodine chloride, aluminium chloride, chlorination
In nickel, antimony chloride, iron chloride or antimony fluoride any one or at least two combination；
Preferably, the graphite is expanded graphite, crystalline flake graphite, micro crystal graphite, pyrolytic graphite or inflatable
In graphite any one or at least two combination, preferably 10-150 mesh expanded graphite.
6. utilize the method described in one of claim 1-5, it is characterised in that the quality of the reaction reagent
For the 10%-500% of graphite intercalation compound quality；
Preferably, the reaction reagent is water, alcohol, sodium borohydride solution, hydrazine hydrate solution or hydrogen peroxide
In solution any one or at least two combination；
Preferably, the sodium borohydride solution is the alkaline solution that pH is 9-13；
Preferably, the weight/mass percentage composition of hydrazine hydrate is 30%-80% in the hydrazine hydrate solution；
Preferably, the weight/mass percentage composition of hydrogen peroxide is 30%-80% in the hydrogenperoxide steam generator.
7. the method according to one of claim 1-6, it is characterised in that the turbulent environment passes through height
Speed rotation is produced, and the rotating speed of the high speed rotation is 3500-10000r/min, is preferably
7000-8000r/min；
Preferably, the time of the turbulent flow is 0.5-1h.
8. the method according to one of claim 1-5, it is characterised in that the turbulent environment passes through height
Fast centrifuge is produced.
9. the method according to one of claim 1-8, it is characterised in that methods described includes following step
Suddenly：
(1) graphite intercalation compound is scattered in solvent, the concentration for obtaining graphite intercalation compound is
0.1-1000mg/mL dispersion liquid；
(2) reaction reagent and dispersion liquid are reacted under conditions of rotary speed is 3500-10000r/min,
Rotate after 0.5-1h, obtain large stretch of layer graphene, wherein, the reaction is：Reaction reagent and graphite intercalation
Intercalator in compound is reacted, and generates gaseous product；The quality of the reaction reagent is graphite intercalation
The 10%-500% of compound quality.
10. large stretch of layer graphene that the method according to one of claim 1-9 is obtained, its feature exists
In the graphene sheet layer size is 1-50 μm, and thickness is 1-6 atomic layer.
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