CN107324319B - A kind of big lamella graphene and preparation method thereof - Google Patents
A kind of big lamella graphene and preparation method thereof Download PDFInfo
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- CN107324319B CN107324319B CN201610270886.0A CN201610270886A CN107324319B CN 107324319 B CN107324319 B CN 107324319B CN 201610270886 A CN201610270886 A CN 201610270886A CN 107324319 B CN107324319 B CN 107324319B
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Abstract
The present invention provides a kind of big lamella graphenes and preparation method thereof, the big lamella graphene the preparation method comprises the following steps: 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, the shearing force and the gas that turbulent flow generates remove the graphite flake layer in graphite intercalation compound jointly, obtain big lamella graphene.The preparation method has merged physics removing and two kinds of processes carried out simultaneously of chemical stripping, can obtain lamella size is 1-50 μm, with a thickness of the big lamella graphene of 1-8 atomic layer, and ten layers of graphene yield intimate 100% below, in addition, the preparation method is simple, easily-controllable, reaction condition is mild, method is simple, at low cost, 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 a kind of sheet
Layer high-quality graphene and the method for efficiently preparing big lamella high-quality graphene.
Background technique
Since 2004 are found, graphene is concerned as a kind of new carbon.It is one kind completely by sp2
The thickness that the carbon atom of hydridization is constituted is only the quasi- two dimensional crystal material of monoatomic layer or several monoatomic layers, and graphene is currently
Most thin in the world is but also most hard nano material, it is almost fully transparent, thermal coefficient height, its electron transfer under room temperature
Rate is high, and resistivity ratio copper or silver are lower, is the smallest material of world resistivity.Because its resistivity is extremely low, the speed of electron transfer
It is exceedingly fast, therefore is expected to can be used to develop thinner, conductive speed electronic component or transistor of new generation faster.Because it is a kind of
Transparent, good conductor is also adapted to manufacture transparent touch screen, tabula rasa, even solar battery.Graphene material simultaneously
Material can also be in high-performance nanometer electronic device, photoelectric device, gas sensor, composite material, field emmision material and energy stores etc.
Field is widely applied.But inexpensive, a large amount of preparations of high-quality graphene are still faced adverse conditions, and the material is constrained
Development and application.
Up to the present, many methods: micromechanics partition method, graphite oxide have been had been developed that about the preparation of graphene
Reduction method, chemical vapour deposition technique, solvent stripping method etc..
The method for most starting to use is micromechanics partition method, and mono-layer graphite piece is shelled from graphite crystal by mechanical force
It separates out and, the mono-layer graphite piece that this method obtains but is unable to control the size of mono-layer graphite, this method than more complete
By manual operation, and became uneven one.
Graphite oxide reduction method is to be mainly based upon Hummer method graphite is carried out oxidation processes, obtains graphite oxide
Afterwards, then it is removed to obtain graphene oxide, finally obtains graphene by reduction treatment.Since oxidation process would generally
The serious structure for destroying graphene sheet layer, although by reduction treatment, the performance indexes of gained grapheme material still with height
There are biggish gaps for the graphene of quality.In addition, the oxidation process of graphite usually requires for example dense sulphur of a large amount of highly acid oxidants
Acid, concentrated nitric acid, dichromic acid and potassium permanganate, sodium nitrate etc.；And high-temperature process is needed in mesh reduction process or uses hydrazine, two
The toxic chemical substance such as methyl hydrazine, not only energy consumption is high, low efficiency, at high cost but also pollution environment.
Chemical vapour deposition technique is that metal or metallic compound is used to be placed on various substrates surface as catalyst, in reaction chamber
It is filled with carbon containing gas in vivo, and graphene is deposited to the method on substrate at high temperature, this method may be implemented to advise greatly
Prepared by the graphene of mould, but there are still some shortcomingss, such as the graphene of this method preparation not to show quantum
The shortcomings that Hall effect, how to choose suitable substrate is also a problem, exists simultaneously higher cost, complex process.
The principle of solvent stripping method be by a small amount of graphite dispersion in solvent, the dispersion liquid of low concentration is formed, using super
The Van der Waals force of the action breaks down graphite layers of sound wave, graphite layers can be inserted in solvent at this time, are removed layer by layer, prepare
Graphene.The method will not destroy the structure of graphene as oxidation-reduction method, can prepare the graphene of high quality, In
The yield highest (about 8%) of graphene, conductivity 6500S/m in N-methyl pyrrolidones；The disadvantage is that yield is very low.Liquid
Mutually ultrasound removing generally requires ultrasound for a long time, and some is even up to hundreds of hours, inevitably destroys the complete of graphene
Whole property, to influence its performance.
In addition, D.A.Bennetts and L.M.Hocking on Proc.R.Soc.Lond magazine hydrodynamically
Explaining the rotation of high speed inclination angle leads to the generation of turbulent flow in container, and Xianjue Chen et al. is sent out on Chem.Commun. magazine
Table using turbulent flow removing graphite and boron nitride method；A kind of high-quality graphene for preparing is described in CN103350995
Turbulent method.But the difficulty for relying solely on physics removing preparing graphite alkene is larger, and the yield of graphene obtained
It is lower.
Due to above-mentioned preparation method there are the drawbacks of, field of preparation of graphene there is an urgent need to develop one kind can be a large amount of, low
Cost and the environmental-friendly new method for preparing high-quality graphene.
Summary of the invention
For preparation cost present in existing graphene preparation method is high, graphene is of poor quality, low yield and lamella are small
The problems such as, the purpose of the present invention is to provide the method that one kind efficiently prepares big lamella high-quality graphene, the method fusions
Physics and chemical two kinds of processes, can obtain lamella size is 1-50 μm, with a thickness of the big lamella graphene of 1-8 atomic layer,
And ten layers of graphene yield intimate 100% below, method is simple, suitable for industrial.
Big lamella graphene of the present invention each means that lamella size is 1-50 μm of graphene unless otherwise specified.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of preparation method of big lamella graphene, the methods are as follows: with graphite
Intercalation compound is raw material, and the intercalator of graphite intercalation compound interlayer and reaction reagent is made to react under turbulent-flow conditions production
Angry body, the shearing force and the gas that turbulent flow generates remove the graphite flake layer in graphite intercalation compound jointly, obtain sheet
Layer graphene.
The graphite intercalation compound is the substance that intercalator is inserted into that graphite layers are formed.
In the preparation method of graphene provided by the invention, the intercalator and reaction reagent in graphite intercalation compound are in rapids
It is reacted under the conditions of stream, the turbulent flow is a kind of flow regime of fluid, and fluid makees irregular movement, is had perpendicular to flow tube axis
The component velocity in line direction generates.
The preparation method fusion physics of graphene provided by the invention and chemical two kinds of processes.The method uses liquid flow
Dynamic offer peeling force, meanwhile, the graphite intercalation compound dispersed in a solvent is that alkali metal, alkali gold are inserted on the basis of graphite
Belong to alloy perhaps metal halide graphite layers intercalator can occur with the liquid substance that is added in solvent or solvent it is anti-
It answers, generates gas, destroy intercalation configuration, play the role of chemical stripping, is i.e. the shearing of graphite flake layer is removed in the convection current of liquid
Physical process and intercalator and solvent reaction generate the chemical process of gas, form complete one and carry out simultaneously.
Intercalator in graphite intercalation compound, which can increase interlamellar spacing, reduces interlaminar action power, intercalator and reaction reagent
The gas impact graphite flake layer that reaction generates tears graphene sheet layer to further decrease lamella active force for turbulent shear force
Help is provided, physical process and chemical process complement each other to achieve the purpose that prepare the big lamella graphene of high quality.
The preparation method of fusion physics provided by the invention and the big lamella graphene of chemical two kinds of processes, compare forefathers
Work, the generation of chemical gas and the increase of interlamellar spacing cause physics removing to become more to be easy, the production of obtained graphene
Amount will be far longer than single physics stripping process, and can avoid destruction of the conventional chemical methods to graphene sheet layer completely.It is single
One physics removing graphene yield is less than 1%, and preparation method provided by the invention obtains ten layers of graphene yield below
Intimate 100%, and the graphene that obtained graphene sheet layer size is obtained considerably beyond forefathers with turbulene method, such as with 150 mesh
The graphene sheet layer size that intercalated graphite obtains is 1-50 μm, with a thickness of 1-8 atomic layer.
The graphite intercalation compound is first scattered in solvent and forms dispersion liquid, then reacts with reaction reagent.
Preferably, in the dispersion liquid graphite intercalation compound concentration be 0.1-1000mg/mL, as 0.5mg/mL,
1mg/mL、2mg/mL、3mg/mL、5mg/mL、8mg/mL、10mg/mL、15mg/mL、20mg/mL、25mg/mL、30mg/mL、
50mg/mL、100mg/mL、200mg/mL、300mg/mL、400mg/mL、500mg/mL、600mg/mL、700mg/mL、800mg/
ML, 900mg/mL or 950mg/mL etc..
The solvent is organic solvent and/or water, preferably organic solvent.
Preferably, the organic solvent is that can dissolve graphene and/or Hansen solubility parameter is 8-14 (cal/
cm3)1/2Organic solvent, as Hansen solubility parameter 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)1/2
Deng.
Preferably, the organic solvent is aldehyde, organic acid, N-Methyl pyrrolidone, dimethylformamide, dimethylacetamide
In amine, chlorobenzene or dichloro-benzenes any one or at least two combination.It is typical but non-limiting combination such as, aldehyde with it is organic
Acid, N-Methyl pyrrolidone, dimethylformamide and dimethyl acetamide, chlorobenzene and dichloro-benzenes, organic acid, N- crassitude
Ketone and dimethylformamide, dimethyl acetamide, chlorobenzene and dichloro-benzenes.
Select organic solvent the reason of first is that, organic solvent can stay hydrophobic graphene in the solution；Second is that having
Solvent removing and dispersion effect are 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 be 1:20-20:1, 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..Intercalator can be entirely insertable in graphite by the mixing method,
Therefore, the mass ratio of intercalator and graphite is also 1:20-20:1 in graphite intercalation compound.
Preferably, the mixing method are as follows: the intercalator of molten condition is mixed with graphite, obtains graphite intercalation compound；
Or, intercalator is mixed with graphite, under the conditions of vacuum tightness, intercalator is warming up in molten condition, keeps the temperature, washs, drying obtains
To graphite intercalation compound.
Preferably, the temperature of the molten condition is 15-450 DEG C, such as 20 DEG C, 30 DEG C, 50 DEG C, 80 DEG C, 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., preferably 20 DEG C -380 DEG C.
There are many preparation method of the graphite intercalation compound, and those skilled in the art can select different systems as needed
Preparation Method.Mixing method is one of those relatively simple method, therefore preferred mixing method.
The intercalator is metal and/or metal halide.Others can be with respective reaction reagent generated reactive gas
Intercalator can use herein.
Preferably, the intercalator is potassium, sodium, lithium, potassium sodium alloy, lodine chloride, aluminium chloride, nickel chloride, antimony chloride, chlorination
In iron or antimony fluoride any one or at least two combination.Typical but non-limiting combination such as potassium and sodium, lithium and potassium sodium
Alloy, lodine chloride and aluminium chloride, nickel chloride, antimony chloride and iron chloride, antimony fluoride, lodine chloride, aluminium chloride and nickel chloride.
Preferably, the graphite is in expanded graphite, crystalline flake graphite, micro crystal graphite, pyrolytic graphite or expansible 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 DEG C,
50℃、80℃、100℃、120℃、150℃、200℃、230℃、280℃、300℃、320℃、350℃、380℃、400℃、
420 DEG C, 450 DEG C or 480 DEG C etc..
The reaction reagent is any one in water, alcohol, sodium borohydride solution, hydrazine hydrate solution or hydrogenperoxide steam generator
Or at least two combination.Typical but non-limiting combination such as water and alcohol, sodium borohydride solution and hydrazine hydrate solution, water, alcohol
With hydrogenperoxide steam generator.As long as the reaction reagent can react life with the intercalated material of graphite layers in graphite intercalation compound
At gaseous product.It is also possible to other substances.Those skilled in the art can be according to intercalation in graphite intercalation compound
The different specific reaction reagents of type selection of agent.
Preferably, the sodium borohydride solution is the alkaline solution that pH is 9-13, if pH value is 9.3,9.8,10,11,12
Or 12.5 etc..
Preferably, in the hydrazine hydrate solution hydrazine hydrate mass percentage be 30%-80%, such as 32%, 35%,
38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 60%, 70% or 75% etc..
Preferably, the mass percentage of hydrogen peroxide is 30%-80% in the hydrogenperoxide steam generator, such as 32%,
35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 60%, 70% or 75% etc..
The turbulent environment is generated by high speed rotation, and the high-speed rotating revolving speed is 3500-10000r/min, such as
4000r/min、4500r/min、5000r/min、6000r/min、6500r/min、7000r/min、7500r/min、7800r/
Min, 8200r/min, 8500r/min, 9000r/min or 9500r/min etc., preferably 7000-8000r/min.The rotation
Speed is capable of providing corresponding peeling force and guarantees 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 generated by supercentrifuge.The turbulent flow can also carry out on other devices, as long as can mention
Rotation speed for high speed is to provide enough shearing peeling forces.
Described method includes following steps as a preferred technical solution:
(1) it disperses graphite intercalation compound in solvent, the concentration for obtaining graphite intercalation compound is 0.1-1000mg/
The dispersion liquid of mL；
(2) reaction reagent is reacted under conditions of rotation speed is 3500-10000r/min with dispersion liquid, rotates 0.5-
After 1h, big lamella graphene is obtained, wherein the reaction are as follows: the intercalator in reaction reagent and graphite intercalation compound carries out
Reaction generates gaseous product；The quality of the reaction reagent is the 10%-500% of graphite intercalation compound quality.
The second object of the present invention is to provide a kind of big lamella graphene that method as described above is prepared, described
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., with a thickness of 1-8 atomic layer, such as 2 atomic layers, 3 atomic layers, 4 atomic layers or 5 atomic layers.
Compared with prior art, the invention has the benefit that
1, the preparation method of big lamella graphene provided by the invention removes stone using physical process and chemical process simultaneously
Ink；Physical process is that the shearing force that liquid motion generates and impact force remove the shearing of graphite flake layer, and chemical process is intercalation
Agent and solvent reaction generate gas.The physics to work simultaneously, which is torn, may be implemented graphite maximum journey with chemical gas expansion process
The removing of degree obtains ten layers of graphene yield intimate 100% below.This is that the first can be with graphite oxide method yield phase
The method to match in excellence or beauty.Solvent supersonic removing and the removing of other turbulent methods are unable to get big lamella graphene provided by the invention.
2, influence very little of its whole preparation process of the preparation method of big lamella graphene provided by the invention to environment, and
The processing cost of waste liquid is low.
3, the preparation method whole preparation process of big lamella graphene provided by the invention is 13h or so, reaction time ratio
Ultrasonic method or oxide-reduction method are easy to be many, and react easily-controllable, and reaction condition is mild, is easy expansion scale, realize
Industrialization.
4, big lamella graphene defect provided by the invention is few, and quality is high, and lamella is big, and (graphene sheet layer size is 1-50 μ
M), graphene sheet layer is distributed in 1-8 layers.
Detailed description of the invention
Fig. 1 is the SEM figure of graphene made from embodiment 1.
Fig. 2 is the XRD diagram of graphene made from embodiment 1.
Fig. 3 is the TEM figure of graphene made from embodiment 1.
Fig. 4 is the TEM High-Resolution Map of graphene made from embodiment 1.
Fig. 5 is the electron diffraction diagram of graphene made from embodiment 1.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.The present invention provides
Following examples just for the sake of clearly illustrating technical solution of the present invention, rather than limitation of the invention.It is mentioned in the present invention
Many kinds of various forms of variations or variation can be made on the basis of the technical solution of confession, obvious variation changes still
Among present invention protection.
Embodiment 1:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 81.4mg metallic potassium is mixed, 200 DEG C of heating 12h with 200mg expanded graphite, prepares golden yellow graphite
Intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in 50mL organic solvent N-Methyl pyrrolidone, is obtained
The dispersion liquid for being 3mg/mL to graphite intercalation compound concentration；
(3) 1mL ethanol solution is added in the dispersion liquid obtained to step (2), and runs supercentrifuge immediately, revolving speed is
7000r/min, end of reaction after 0.5 hour clean reaction product, dry, obtain graphene powder aggregation.
Graphene powder aggregation is distributed in organic solvent, it is characterized.
Fig. 1 is the SEM figure of graphene obtained, and graphene powder aggregation shows lamellar structure flexible, is different from
The smooth laminated structure of graphite rule.Fig. 2 is the XRD diagram of graphene obtained, shows that graphene powder has not had significantly
Crystal peak occurs, and only unformed bulge occurs at 26 ° or so.Fig. 3 is the TEM figure of graphene obtained, the TEM of graphene
Show its size at 10 μm or more.Fig. 4 is the TEM High-Resolution Map of graphene obtained, shows it with a thickness of monoatomic layer.Fig. 5
It is the electron diffraction diagram of graphene obtained, shows its intact crystal structure.
Embodiment 2:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It being mixed with 0.05g expanded 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, is filtered, drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, obtains stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) 1mL sodium borohydride alkaline solution is added in the dispersion liquid obtained to step (2), and runs high speed centrifugation immediately
Machine, revolving speed 7000r/min, end of reaction after centrifugation 0.5 hour clean reaction product, dry, obtain graphene powder aggregation
Body.
The sodium borohydride solution is the alkaline solution that pH is 9-13, such as pH value is 11 or 12.
By the sodium borohydride alkaline solution in embodiment 2 replace with hydrazine hydrate mass percentage be 30%-80% (such as
50% or 65% etc.) hydrazine hydrate solution can equally obtain graphene powder aggregation.
Embodiment 3:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It being mixed with 0.05g expanded 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, is filtered, drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, obtains stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) hydrogen peroxide solution that 1mL mass fraction is 30% is added in the dispersion liquid obtained to step (2), is stood after addition
Supercentrifuge, revolving speed 7000r/min are run, end of reaction after centrifugation 0.5 hour cleans reaction product, and it is dry, it obtains
Graphene powder aggregation.
Embodiment 4:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 81.4mg metallic potassium is mixed, 200 DEG C of heating 12h with 200mg graphite, prepares golden yellow graphite intercalation
Compound；
(2) graphite intercalation compound that step (1) obtains is distributed in 50mL organic solvent N-Methyl pyrrolidone, is obtained
The dispersion liquid for being 3mg/mL to graphite intercalation compound concentration；
(3) 1mL ethanol solution is added in the dispersion liquid obtained to step (2), and after ethanol solution is added, runs immediately
Supercentrifuge, revolving speed 7000r/min, end of reaction after centrifugation 0.5 hour clean reaction product, dry, obtain graphene
Powder aggregates.
Embodiment 5:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It is mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C, maintains 12h, obtains
Product is dissolved in dilute hydrochloric acid solution by product, is filtered, and drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, obtains stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) the sodium borohydride alkaline solution of 1mL is added in the dispersion liquid obtained to step (2), and sodium borohydride is being added
Supercentrifuge, revolving speed 7000r/min, end of reaction after centrifugation 0.5 hour, cleaning reaction production are run after alkaline solution immediately
Object, it is dry, obtain graphene powder aggregation.
Embodiment 6:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It is mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C, maintains 12h, obtains
Product is dissolved in dilute hydrochloric acid solution by product, is filtered, and drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, obtains stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) 1mL mass fraction is added in the dispersion liquid obtained to step (2) and is 30% hydrogen peroxide solution, and be added
After the hydrogen peroxide solution that mass fraction is 30%, supercentrifuge, revolving speed 7000r/min, after centrifugation 0.5 hour are run immediately
End of reaction cleans reaction product, dry, obtains graphene powder aggregation.
Embodiment 7:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 81.4mg metallic potassium is mixed, 200 DEG C of heating 12h with 200mg graphite, prepares golden yellow graphite intercalation
Compound；
(2) graphite intercalation compound that step (1) obtains is distributed in 50mL organic solvent N-Methyl pyrrolidone, is obtained
To the dispersion liquid of 3mg/mL；
(3) 1mL ethanol solution is added in the dispersion liquid obtained to step (2), and after ethanol solution is added, runs immediately
Supercentrifuge, revolving speed 10000r/min, end of reaction after centrifugation 0.5 hour clean reaction product, dry, obtain graphite
Alkene powder aggregates.
Embodiment 8:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It is mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C, maintains 12h, obtains
Product is dissolved in dilute hydrochloric acid solution by product, is filtered, and drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, obtains stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) 1mL sodium borohydride alkaline solution is added in the dispersion liquid obtained to step (2), and hydroboration soda is being added
Property solution after run supercentrifuge immediately, revolving speed 10000r/min, end of reaction after centrifugation 0.5 hour, cleaning reaction produces
Object, it is dry, obtain graphene powder aggregation.
The pH value of sodium borohydride alkaline solution can be 9-13 in embodiment 8, such as 11 or 12.
Embodiment 9:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) by the anhydrous FeCl of 0.3g3It is mixed with 0.05g graphite, vacuum tightness, 1h is warming up to 380 DEG C, maintains 12h, obtains
Product is dissolved in dilute hydrochloric acid solution by product, is filtered, and drying obtains graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, prepares stone
Black intercalation compound concentration is the dispersion liquid of 5mg/mL；
(3) 1mL mass fraction is added in the dispersion liquid obtained to step (2) and is 30% hydrogen peroxide solution, and be added
After the hydrogen peroxide solution that mass fraction is 30%, supercentrifuge is run immediately, and revolving speed 10000r/min is centrifuged 0.5 hour
End of reaction afterwards cleans reaction product, dry, obtains graphene powder aggregation.
Embodiment 10
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 400mg metal potassium sodium alloy is mixed, 200 DEG C of heating 12h with 20mg graphite, prepares golden yellow graphite
Intercalation compound；
(2) graphite intercalation compound for obtaining step (1) is added in 52.5mL ethanol solution, and after the addition, immediately
Supercentrifuge, revolving speed 3500r/min are run, end of reaction after centrifugation 1 hour cleans reaction product, and it is dry, obtain graphite
Alkene powder aggregates.
Embodiment 11:
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 10mg metallic potassium is mixed with 200mg 10-150 mesh expanded graphite, 200 DEG C of heating 12h prepare golden yellow
Graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed to the mixed liquor of 100mL dimethylformamide and chlorobenzene
In, obtain the dispersion liquid that graphite intercalation compound concentration is 1000mg/mL；
(3) 1312mL ethanol solution is added in the dispersion liquid obtained to step (2), and runs supercentrifuge immediately, turns
Speed is 9000r/min, and end of reaction after 0.8 hour cleans reaction product, dry, obtains graphene powder aggregation.
Embodiment 12
A kind of preparation method of big lamella graphene, includes the following steps:
(1) 0.3g lodine chloride is mixed with the mixture of antimony chloride with 0.05g crystalline flake graphite with the mixture of pyrolytic graphite,
Vacuum tightness, 1h are warming up to 380 DEG C, maintain 12h, obtain product, product is dissolved in dilute hydrochloric acid solution, filter, and drying obtains
Graphite intercalation compound；
(2) graphite intercalation compound that step (1) obtains is distributed in organic solvent N-Methyl pyrrolidone, prepares stone
Black intercalation compound concentration is the dispersion liquid of 10mg/mL；
(3) 1mL mass fraction is added in the dispersion liquid obtained to step (2) and is 80% hydrogen peroxide solution, and be added
After the hydrogen peroxide solution that mass fraction is 80%, supercentrifuge, revolving speed 8000r/min, after centrifugation 0.5 hour are run immediately
End of reaction cleans reaction product, dry, obtains graphene powder aggregation.
60% hydrogen peroxide solution can also be applied to embodiment 12, obtain graphene powder aggregation.
The graphene powder aggregation is dispersed can be obtained big lamella graphene afterwards in a solvent.
Carry out SEM, XRD, TEM, TEM high-resolution and electronic diffraction characterization respectively to graphene made from embodiment 2-12,
The characterization result of each embodiment is similar to Fig. 1-5, and big lamella graphene can be made by illustrating embodiment 2-12 equally, and
The lamella size for the big lamella graphene that embodiment 2-12 is obtained is 1-50 μm, with a thickness of 1-8 atomic layer.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (20)
1. a kind of preparation method of big lamella graphene, which is characterized in that the method are as follows: with graphite intercalation compound be original
Material, makes the intercalator of graphite intercalation compound interlayer and reaction reagent that generated reactive gas occur under turbulent-flow conditions, and turbulent flow produces
Raw shearing force and the gas remove the graphite flake layer in graphite intercalation compound jointly, obtain big lamella graphene；
The intercalator is metal and/or metal halide；
The reaction reagent is for any one in water, alcohol, sodium borohydride solution, hydrazine hydrate solution or hydrogenperoxide steam generator or extremely
Few two kinds of combination；
The quality of the reaction reagent is the 10%-500% of graphite intercalation compound quality,
The turbulent flow by high speed rotation generate, the high-speed rotating revolving speed be 3500-10000r/min, the turbulent flow when
Between be 0.5-1h.
2. dividing the method according to claim 1, wherein the graphite intercalation compound is first scattered in solvent and is formed
Dispersion liquid, then reacted with reaction reagent.
3. according to the method described in claim 2, it is characterized in that, the concentration of graphite intercalation compound is in the dispersion liquid
0.1-1000mg/mL。
4. according to the method described in claim 2, it is characterized in that, the solvent is organic solvent and/or water.
5. according to the method described in claim 4, it is characterized in that, the solvent is organic solvent.
6. according to the method described in claim 4, it is characterized in that, the organic solvent be can dissolve graphene and/or
Hansen solubility parameter is 8-14 (cal/cm3)1/2Organic solvent.
7. according to the method described in claim 4, it is characterized in that, the organic solvent is aldehyde, organic acid, N- crassitude
In ketone, dimethylformamide, dimethyl acetamide, chlorobenzene or dichloro-benzenes any one or at least two combination.
8. method described in one of -7 according to claim 1, which is characterized in that the graphite intercalation compound is with intercalator and stone
Ink is that raw material is prepared by mixing method.
9. according to the method described in claim 8, it is characterized in that, the mass ratio of the intercalator and graphite is 1:20-20:1.
10. according to the method described in claim 8, it is characterized in that, the mixing method are as follows: by the intercalator and stone of molten condition
Ink mixing, obtains graphite intercalation compound；Or, intercalator is mixed with graphite, under the conditions of vacuum tightness, being warming up to intercalator is in
Molten condition is kept the temperature, and is washed, and drying obtains graphite intercalation compound.
11. according to the method described in claim 10, it is characterized in that, the temperature of the molten condition is 15-450 DEG C.
12. according to the method for claim 11, which is characterized in that the temperature of the molten condition is 20 DEG C -380 DEG C.
13. utilizing method described in claim 1, which is characterized in that the intercalator is potassium, sodium, lithium, potassium sodium alloy, chlorination
In iodine, aluminium chloride, nickel chloride, antimony chloride, iron chloride or antimony fluoride any one or at least two combination.
14. according to the method described in claim 8, it is characterized in that, the graphite is expanded graphite, crystalline flake graphite, microlite
In ink, pyrolytic graphite or expansible graphite any one or at least two combination.
15. according to the method for claim 14, which is characterized in that the graphite is 10-150 mesh expanded graphite.
16. the method according to claim 1, wherein the sodium borohydride solution is that the alkalinity that pH is 9-13 is molten
Liquid.
17. the method according to claim 1, wherein the quality percentage of hydrazine hydrate contains in the hydrazine hydrate solution
Amount is 30%-80%.
18. the method according to claim 1, wherein in the hydrogenperoxide steam generator hydrogen peroxide quality hundred
Dividing content is 30%-80%.
19. the method according to claim 1, wherein the high-speed rotating revolving speed is 7000-8000r/min.
20. the method according to claim 1, wherein described method includes following steps:
(1) it disperses graphite intercalation compound in solvent, the concentration for obtaining graphite intercalation compound is 0.1-1000mg/mL's
Dispersion liquid；
(2) reaction reagent is reacted under conditions of rotation speed is 3500-10000r/min with dispersion liquid, rotates 0.5-1h
Afterwards, big lamella graphene is obtained, wherein the reaction are as follows: the intercalator in reaction reagent and graphite intercalation compound carries out anti-
It answers, generates gaseous product；The quality of the reaction reagent is the 10%-500% of graphite intercalation compound quality.
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