CN104803380B - Preparation method of graphene - Google Patents
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- CN104803380B CN104803380B CN201510239652.5A CN201510239652A CN104803380B CN 104803380 B CN104803380 B CN 104803380B CN 201510239652 A CN201510239652 A CN 201510239652A CN 104803380 B CN104803380 B CN 104803380B
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Abstract
The invention provides a preparation method of graphene. Natural graphite or synthetic graphite is used as a raw material; edge oxidation intercalation is carried out in an aqueous environment; an in-plane graphite structure is not destroyed; the edge interlayer distance of a graphite flake is increased; the graphite flake is stripped by adopting a gas bubble stripping method; the interlayer distance between every two layers of the graphite flake is gradually increased from an edge, so that the every two layers of the graphite flake are separated from each other, so as to achieve a stripping effect, and to obtain water-soluble graphene. The preparation method of the graphene is simple, safe and pollution-free in operation procedure; the prepared graphene is high in quality; as the graphene obtained by using the preparation method of the graphene has the advantages of water solubility, perfect structure and controllable size, the preparation method of the graphene can be applied to the fields of transparent conducting thin films, heat-conducting glue, electrocondution slurry, high-resistance composite materials and the like.
Description
Technical field
The present invention relates to technical field of graphene preparation, more particularly to a kind of preparation method of Graphene.
Background technology
Since Graphene is reported for 2004, because of its excellent conduction, heat conduction, mechanical performance etc. receives much concern, especially
It is electric conductivity, causes huge great waves in electronic device and energy storage field, associated specialist thinks that Graphene is expected in modern electricity
Sub- sciemtifec and technical sphere causes a field technology revolution.The market demand of therefore Graphene is increasing, and this requires the preparation of Graphene
Industry being capable of the high-quality Graphene of large batch of offer.But current Graphene preparation industry still has some urgently to solve in volume production
Problem certainly.First, at 10 years of the past, chemistry redox method is to prepare the main method of Graphene on a large scale, because this
Method large-scale production low cost, it is controlled to obtain sample oxy radical, can disperse in multi-solvents.Conventional oxidation method has
Hummers, Staudenmair and Brodie and its improved method.Recently, superb seminar of Zhejiang University is published in
Nat.Commun. " the An iron-based green approach to 1-h productionof single-layer going up
Graphene oxide " proposes a kind of new oxidant K2FeO4Prepare graphene oxide, this oxidant is than traditional KMnO4Peace
Quan Xinggao, the response time faster, is more suitable for preparing on a large scale.But the graphene oxide no matter prepared by which kind of oxidizing process is required for
Further reduction could reduce oxy radical, repair oxidation and peel off the defect brought.Conventional method of reducing has at fast speed heat
Logos, microwave method, reproducibility chemical reagent reduction etc..Regrettably these method of reducing are difficult to thoroughly repair and introduce in oxidation
Defect because substantial amounts of oxy radical destroys sp in graphite during Strong oxdiative2Structure, forms substantial amounts of sp3Knot
Structure, these sp3Structure hardly results in reparation in reduction.Therefore oxidation-reduction method obtain with sp3The Graphene quantity of structure
The electric property reducing intrinsic Graphene of level, greatly limit the application in a lot of fields.
Therefore, the scale preparation of intrinsic Graphene needs to develop a kind of new method of non-Strong oxdiative.According to document report
Non-oxidation or the weak oxide method of preparing Graphene, the researchers of Graphene find to peel off preparation from native graphite liquid phase high
Quality Graphene is to prepare intrinsic Graphene the best way on a large scale.Liquid phase is peeled off and is referred in some solvents, such as N- first
Base ketopyrrolidine, DMF and N,N-dimethylacetamide equal solvent, or the water added with surfactant
In solution, the process graphite flake successively peeled off from graphite block body using equipment or intercalation technique.At present directly from natural stone
The method that Graphene is prepared in black liquid phase stripping has：Electrochemical stripping method, melting salt intercalation stripping method, ultrasonic stripping method, interlayer is anti-
Answer stripping method and mechanical shearing stripping method.Nat.Mater. above report《Scalable production of large
quantities ofdefect-free few-layer graphene by shearexfoliation in liquids》Carry
Go out the method peeling off graphite using mechanical shearing, obtain the complete graphene film of lattice, shortcoming is that lateral dimension is less
(500nm)；Suzhou nanometer Suo Liuliwei seminar report《Interlayer catalytic exfoliation
realizingscalable production of large-size pristinefew-layer graphene》Using layer
Between catalytic reaction stripping prepare Graphene, it is larger to obtain graphene sheet layer, and lattice is complete, but the intercalation condition of presoma is more severe
Carve, the wayward and height that consumes energy.In general, ultrasonic and shearing method obtains Graphene size (hundreds of nanometer) less than normal, electrochemistry
Peel off, although melting salt intercalation and interlayer react the Graphene that stripping method can obtain large-size, intercalator is complicated, reaction
Condition is harsh, and solvent has pollution and the height that consumes energy is it is most important that the Graphene obtaining can only be scattered in organic solvent and can not divide
Dissipate in water.Chinese patent CN201410111450.8《A kind of method that scale aqueous phase prepares Graphene》A kind of strong acid is proposed
Oxidant intercalation, strong alkali environment ultrasonic disperse, the method that aqueous phase prepares Graphene, obtain graphite scattered in water middle and high concentration
Alkene, breaks through a scattered difficult problem in water for the Graphene.But still use strong acid, highly basic and high-power ultrasonic technology so that after
Process complicated, environment is unfriendly, power consumption is high.
Content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of preparation method of Graphene,
Solve existing Graphene to prepare in strong acid-base and toxic organic solvents, and can not in water scattered shortcoming, this
Bright intercalation technique and bubble lift-off technology are aoxidized by graphite edge realize pollution-free, low energy consumption, high yield, high-quality and big advise
Modelling prepares water-soluble graphene.
For achieving the above object, the present invention provides a kind of preparation method of Graphene, and the method at least comprises the following steps：
(1) graphite is mixed with intercalator, carry out edge oxidation intercalation, form the graphite layers with edge intercalation
Compound；
(2) compound between graphite layers carrying edge intercalation described in step (1) are put into bubble reactant, carry out bubble
Stripping reaction, forms the graphene dispersing solution with Graphene aggregation.
Preferably, graphite described in step (1) is native graphite or Delanium, and the particle size range of described graphite is 1-
100μm.
Preferably, in step (1), reaction temperature is 30-200 DEG C, and the response time is 1-24h.
Preferably, the mass ratio 1 of graphite described in step (1) and described intercalator：(1-10).
Preferably, intercalator described in step (1) is persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4), [N
(C4H9)4]5·2HSO5·HSO4·SO4One of or the mixture of the two.
Preferably, intercalator described in step (1) is one or two kinds of in conventional oxidant, described conventional oxidant bag
Include KMnO4、K2FeO4、KClO3.
Preferably, in step (2), reaction temperature is 30-100 DEG C, and soak time is 4-24h.
Preferably, bubble reactant described in step (2) includes hydrogen peroxide and ammonium oxalate mixed solution, hydrogen peroxide and carbonic acid
One or more of sodium mixed solution, hydrogen peroxide and this several mixed solution of ammonia mixed solution.
Preferably, described in step (2), bubble stripping reaction is carried out in water or in low-toxic organic solvent, and described is low
Toxic organic solvent is N,N-dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) solvent
In any one.
Preferably, after forming the described graphene dispersing solution with Graphene aggregation, also include to described with stone
The graphene dispersing solution of black alkene aggregation carries out weak supersound process, the step obtaining Graphene aqueous dispersion liquid.
Preferably, in described weak supersound process, ultrasonic power scope is 50-100W, and the time of described weak supersound process is
10-30min.
Preferably, obtain described Graphene aqueous dispersion liquid after, also include to described Graphene aqueous dispersion liquid filter or
Centrifugation, to obtain the step that Graphene concentrates slurry.
Preferably, after obtaining described Graphene concentration slurry, also include concentrating slurry sucking filtration, drying to described Graphene,
Step to obtain graphene film.
The present invention can be carried out in aqueous phase, reduces environmental pollution, reduces the injury to staff's body.The present invention operates
Flow process is simple, safety, and pollution-free, overcoming Graphene must prepare in strong acid-base and toxic organic solvents, and can not be
Scattered shortcoming in water；Because the present invention makes Graphene lateral dimension controlled using gentle bubble lift-off technology, permissible
Obtain big size graphene film.The present invention prepares high-quality water-soluble graphene by simple operationss it is adaptable to Graphene
Large-scale production, there is extensive prospects for commercial application.The Graphene material obtaining compared to existing graphene product, the present invention
Material has fabulous water solublity due to edge oxidation, and the lattice structure due to most Graphenes is not subject to Oxidative demage
And there is superelevation conductance and thermal conduction characteristic.Because the grapheme material that the present invention obtains has water solublity, perfect structure and size
Controlled advantage, present invention can apply to each neck such as transparent conductive film, heat-conducting glue, electrocondution slurry, high-barrier composite material
Domain.
Brief description
Fig. 1 is shown as the schematic diagram of the preparation method of Graphene of present invention offer；
Fig. 2 is shown as the SEM figure of raw material in technical scheme in embodiment one；
Fig. 3 is shown as the SEM figure that technical scheme in embodiment one is obtained the compound between graphite layers with edge intercalation；
Fig. 4 is shown as the SEM figure of the low resolution of the obtained Graphene of technical scheme in embodiment one；
Fig. 5 is shown as the high-resolution SEM figure of the obtained Graphene of technical scheme in embodiment one；
Fig. 6 is shown as the AFM figure of the Graphene that technical scheme is obtained in embodiment one；
Fig. 7 is shown as the TEM figure of the low resolution of the Graphene that technical scheme is obtained in the present embodiment one
Fig. 8 is shown as the high-resolution TEM figure of the Graphene that in the present embodiment one, technical scheme is obtained.
In figure, component label instructions
S10～S50 step
Specific embodiment
It is complete that the present invention proposes one kind no strong acid, no highly basic, no high-power equipment, simple to operate, Graphene crystal structure
Green technology route, using edge oxidation intercalation combine bubble lift-off technology, efficiently solve high-quality graphene scale
The difficult problems such as high-quality, low cost, high efficiency, environmental friendliness, large scale how are realized in preparation process.The green oxidation of the present invention
Intercalation principle：Intercalator is persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4), [N (C4H9)4]5·2HSO5·HSO4·SO4
In any one or the two mixture, the active ingredient list persulfate ion (HSO of intercalator5 -), be dissolved in after water through by
Chain reaction discharges active oxygen [O], and forms the various active composition such as hydroxyl radical free radical, Both peroxyl radical.Single over cure
The standard electrode EMF of acid group is 1.82V, higher than chlorine (1.36V) and chlorine dioxide (1.5V), aoxidizes potential energy height, has exceeded chlorine
Compound, potassium permanganate, hydrogen peroxide etc..Graphite has certain stability in itself, but the carbon ratio at graphite edge is more active, activity
Oxygen [O] can graphite oxide edge active carbon, by controlling the amount of intercalator, obtain edge oxidation, the complete stone of lattice in face
Black intercalation compound.The present invention adopts gentle bubble lift-off technology, makes Graphene and not suffer from Gao Gong when graphite surface is peeled off
Rate is ultrasonic, the destructive very strong technical process such as microwave or high speed shear, thus can obtain more large scale, microstructure more
Perfect high-quality graphene material.This grapheme material contains substantial amounts of-COOH ,-COH, C-O-C because its edge is oxidized
And the oxygen-containing organic group such as-OH and carry negative charge, this grapheme material has preferable hydrophilic.
Below by way of specific instantiation, embodiments of the present invention are described, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also be by addition different concrete realities
The mode of applying is carried out or applies, and the every details in this specification can also be based on different viewpoints and application, without departing from
Carry out various modifications and changes under the spirit of the present invention.
Refer to Fig. 1 to Fig. 8.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, only shows the assembly relevant with the present invention rather than then according to package count during actual enforcement in schema
Mesh, shape and size are drawn, and during its actual enforcement, the kenel of each assembly, quantity and ratio can be a kind of random change, and its
Assembly layout kenel is likely to increasingly complex.
The preparation method of the Graphene providing with reference to Fig. 1, the present invention, including：
Step S10：Graphite is mixed with intercalator, carries out edge oxidation intercalation, form the stone with edge intercalation
Black intercalation compound.
Step S20：The described compound between graphite layers with edge intercalation are put into bubble reactant, carries out bubble stripping
Reaction, forms the graphene dispersing solution with Graphene aggregation.
In specific embodiment mode, the method also includes：
Step S30：The described graphene dispersing solution with Graphene aggregation is carried out weak supersound process, obtains Graphene
Aqueous dispersion liquid.
Step S40：Described Graphene aqueous dispersion liquid is filtered or is centrifuged, obtain Graphene and concentrate slurry.
Step S50：After described Graphene is concentrated slurry sucking filtration, is dried, obtain graphene film.
Specifically, the preparation method of the Graphene that the present invention provides can be：
First, execution step S10：It is dispersed in after graphite is mixed with intercalator in aqueous environment, carry out edge oxidation and insert
Layer reaction, stirring reaction 1-24h at 30-200 DEG C, flushed three times with water filtration after the completion of reaction, obtain with edge intercalation
Compound between graphite layers.
It is simply that in the presence of intercalator, chemical reaction substance invades graphite edge to described compound between graphite layers, and
Edge and C atomistic binding, form a kind of compound not destroying graphite laminate structure.Graphite has excellent plasticity, belongs to
Hexagonal layered structure.In the layer carbon atom is bonded with C-C σ and closes, and interlayer is then combined with faint Van der Waals force, in oxidation
In the presence of agent, the edge of native graphite or Delanium is oxidized.Edge oxide group causes graphite layers distance to increase, shape
Become the compound between graphite layers of edge intercalation.
Described graphite is native graphite or Delanium, and the particle size range of described native graphite or Delanium is 1-100 μ
M, described native graphite or Delanium are 1 with the mass ratio of described intercalator:1-1:10.
Described intercalator can be persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4), [N (C4H9)4]5·2HSO5·
HSO4·SO4In any one or the two mixture；Described intercalator be alternatively in conventional oxidant any one or
Two kinds it is preferable that such as KMnO4, K2FeO4, KClO3Deng oxidant.
The mode of described stirring is：Graphite is put in container, is then placed in described intercalator, then adding water, it is molten to be configured to
Liquid, is then stirred with magnetic stirring apparatuss, and the mixing speed of described magnetic agitation is 200r/min～300r/min.
Next, execution step S20：The described compound between graphite layers with edge intercalation are put into bubble reaction
Agent, carries out bubble stripping reaction.Setting temperature 30-100 DEG C, in 4 hours to 24 hours response time, forms and carries a small amount of vermiform
The graphene dispersing solution of Graphene aggregation.Wherein, Graphene aggregation refers to that interlamellar spacing increases, the graphite not yet stripping down
Alkene intermediate.
The interlamellar spacing at the compound between graphite layers edge with edge intercalation is in previous step edge oxidation intercalation
It is increased, through this step, bubble reactant reacts in edge interlayer and produces gas and assemble increase, in air accumulation shape
Become bubble, the process that bubble volume increases, the interfloor distance between graphite flake layer is also gradually increased, and bubble is greatly to a certain extent
After explosion, new bubble re-forms, then explosion, until graphite flake is stripped, forms the graphite with Graphene aggregation
Alkene dispersion liquid.
This step adopts gentle bubble lift-off technology, makes Graphene when graphite surface is peeled off and do not suffer from high power to surpass
The destructive very strong technical process such as sound, microwave or high speed shear, not graphite-structure in surface of fracture, increase graphite flake edge interlayer
Distance.
Described bubble reactant refers to the reagent of a large amount of bubble of product in water, mixes molten with ammonium oxalate including hydrogen peroxide
In this several mixed solution of liquid, hydrogen peroxide and sodium carbonate mixture, hydrogen peroxide and ammonia mixed solution any one or a few.
Described bubble stripping reaction both can be carried out in water, also can carry out in low-toxic organic solvent, described low toxicity
Property organic solvent be N,N-dimethylformamide (DMF), N-Methyl pyrrolidone (NMP), in dimethyl sulfoxide (DMSO) solvent
Any one.
Compound between graphite layers with edge intercalation and bubble reactant are placed on thermostat by this step, by controlling
The temperature of thermostat is realizing controlling the temperature with bubble reaction reaction for the compound between graphite layers of edge intercalation.Described perseverance
Warm device can be water-bath, oil bath etc..In this step, with respect to other reaction conditions, the shadow to course of reaction for the temperature
Ring also more gentle, therefore in specific embodiment, reaction temperature can also exceed this scope, then the response time also can be corresponding
Change.
Next, execution step S30, the described graphene dispersing solution with Graphene aggregation is carried out weak ultrasonic place
Reason, the graphene film under making not being completely exfoliated thoroughly is peeled off, and obtains Graphene aqueous dispersion liquid.Wherein, weak supersound process is super
Acoustical power controls in 50-100W, and this power, both so that graphene film is thoroughly peeled off, prevents supersound process from Graphene is tied again
It is configured to destroy, the time control of weak supersound process is in 10-30min.
Next, execution step S40, described Graphene aqueous dispersion liquid is filtered or is centrifuged, obtained Graphene
Concentrate slurry, dispersion concentration reaches 10mg/ml.
Next, execution step S50：Described Graphene is concentrated slurry sucking filtration film forming, then 30- in drying baker
After 5-6h being dried at a temperature of 120 DEG C, obtain graphene film.The surface resistance that four probe method records described graphene film reaches 3-
10ohm/sq, illustrates the conductance good stability of Graphene, the quality height obtaining.The number of plies of the Graphene being obtained is 1-10 layer,
In face, lattice is complete, and yield is up to 55%.
Embodiment 1
(1) native graphite and the persulfuric acid complex salt (2KHSO being 100 μm by particle diameter5·KHSO4·K2SO4) according to 1:1
Quality than proportioning, be mixedly configured into 200ml aqueous solution after weighing corresponding quality, carry out edge oxidation intercalation, 50
At DEG C, magnetic agitation reaction 4h, obtains mixed solution.Fig. 2 is the SEM figure of graphite it can be seen that the accumulation of graphite edge is regular closely.
(2), after the mixed solution sucking filtration that will obtain in step (1), with distilled water flushing 3 times, obtain with edge intercalation
Compound between graphite layers.Fig. 3 is the SEM figure of the compound between graphite layers with edge intercalation it can be seen that carrying edge intercalation
The marginal portion of compound between graphite layers is opened it will be apparent that fold, piles up loose.
(3) by ammonia and hydrogen peroxide according to 1:1 volume ratio mixing is made into bubble reactant, will carry edge in step (2)
The compound between graphite layers of intercalation put in this mixed solvent, soak 6h at 40 DEG C, and ammonia and dioxygen hydrone pass through oxidation
Graphite edge enter graphite flake layer between fully react, produce gas, air accumulation expand so that graphite flake layer peel off.Reaction
After the completion of obtain with Graphene aggregation graphene dispersing solution.
(4) graphene dispersing solution in step (3) is carried out weak supersound process 10min under 50-100W power, make incomplete
Graphene sheet layer under peeling off thoroughly is peeled off, that is, obtain Graphene aqueous dispersion liquid.
(5) described for step (4) Graphene aqueous dispersion liquid is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) in step (5), described Graphene will be concentrated slurry sucking filtration, in 120 DEG C of holding 5h of drying baker, obtain graphite
Alkene film, the room temperature square resistance that four probe method records graphene film is 3.89ohm/sq.Fig. 4, Fig. 5 are respectively obtained graphite
The low resolution of alkene, high-resolution SEM figure, its pattern yarn shape as can be seen from FIG., curling.It is the AFM of Graphene in Fig. 6
Figure is it can be seen that Graphene thickness is between 1-3nm；Fig. 7, Fig. 8 are the low resolution of Graphene, high-resolution TEM figure respectively,
Can be seen that this piece Graphene is 3 layers from high-resolution TEM in figure.
Embodiment 2
(1) electrographite and the [N (C being 5 μm by particle diameter4H9)4]5·2HSO5·HSO4·SO4According to 1:3 quality is joined
Ratio is mixedly configured into 200ml aqueous dispersion liquid after weighing corresponding quality, carries out edge oxidation intercalation, magnetic at 30 DEG C
Power stirring reaction 10h, obtains mixed solution.
(2) by the mixed solution filtering and washing obtaining in step (1) 3 times, the graphite layers with edge intercalation are obtained
Compound.
(3) by hydrogen peroxide and ammonium oxalate solution according to 3:1 volume ratio mixing is made into bubble reactant, by band in step (2)
The compound between graphite layers having edge intercalation put in this mixed solvent, soak 4h, hydrogen peroxide and ammonium oxalate molecule at 60 DEG C
Enter the abundant generated reactive gas of graphite edge interlayer, so that graphite flake layer expands peeling off.Obtain with stone after the completion of reaction
The graphene dispersing solution of black alkene aggregation.
(4) by the graphene dispersing solution in step (3) under 50-100W power weak supersound process 30min, make not shell completely
From under graphene sheet layer thoroughly peel off, that is, obtain the complete Graphene aqueous dispersion liquid of the lattice of 1-10 layer.
(5) Graphene aqueous dispersion liquid described in step (4) is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry sucking filtration film forming, after vacuum drying oven is dried 30 DEG C of holding 6h, four
The room temperature square resistance that sonde method records graphene film is 10ohm/sq.
Embodiment 3
(1) by particle diameter be 100 μm native graphite, persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4) and [N
(C4H9)4]5·2HSO5·HSO4·SO4According to 1:1:Than proportioning, mixing after weighing corresponding quality is made into 200ml to 1 quality
Aqueous solution, carries out edge oxidation intercalation, magnetic agitation reaction 10h, obtains mixed solution at 80 DEG C.
(2) by the mixed solution filtering and washing obtaining in step (1) 3 times, the graphite layers with edge intercalation are obtained
Compound.
(3) by hydrogen peroxide and sodium carbonate liquor according to 1:3 volume ratio mixing are made into bubble reactant, by band in step (2)
The compound between graphite layers having edge intercalation put in this mixed solvent, soak 4h, hydrogen peroxide and sodium carbonate molecule at 100 DEG C
Enter the abundant generated reactive gas in graphite edge, so that graphite flake layer expands peeling off.So that graphite flake layer expands peeling off.Instead
The graphene dispersing solution with Graphene aggregation is obtained after the completion of answering.
(4) by the graphene dispersing solution in step (3) under 50-100W power weak supersound process 30min, make not shell completely
From under graphene sheet layer thoroughly peel off, that is, obtain the complete Graphene aqueous dispersion liquid of the lattice of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry sucking filtration film forming, after 120 DEG C of holding 6h of drying baker, four probe method is surveyed
The room temperature square resistance obtaining graphene film is 5.69ohm/sq.
Embodiment 4
(1) by particle diameter be 45 μm native graphite, persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4) and [N
(C4H9)4]5·2HSO5·HSO4·SO4According to 1:2:Than proportioning, mixing after weighing corresponding quality is made into 200ml to 1 quality
Aqueous solution, carries out edge oxidation intercalation, magnetic agitation reaction 5h, obtains mixed solution at 100 DEG C.
(2) by the mixed solution filtering and washing obtaining in step (1) 3 times, the graphite layers with edge intercalation are obtained
Compound.
(3) by hydrogen peroxide, ammonia and sal volatile are according to 1:1:1 volume ratio mixing is made into bubble reactant, by step
(2) compound between graphite layers carrying edge intercalation in put in this mixed solvent, soak 4h, bubble reactant at 100 DEG C
Fully react in the graphite edge interlayer of oxidation, produce gas, so that graphite flake layer is expanded and peel off.Obtain with stone after the completion of reaction
The graphene dispersing solution of black alkene aggregation.
(4) by the graphene dispersing solution in step (3) under 50-100W power weak supersound process 30min, make not shell completely
From under graphene sheet layer thoroughly peel off, that is, obtain the complete Graphene aqueous dispersion liquid of the lattice of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry sucking filtration film forming, after 60 DEG C of holding 6h of vacuum drying oven, four probes
The room temperature square resistance that method records graphene film is 6.31ohm/sq.
Embodiment 5
(1) native graphite being 10 μm by particle diameter, persulfuric acid complex salt (2KHSO5·KHSO4·K2SO4) according to 1:4
Quality, than proportioning, is mixedly configured into 200ml aqueous dispersion liquid after weighing corresponding quality, carries out edge oxidation intercalation,
At 80 DEG C, magnetic agitation reaction 6h, obtains mixed solution.
(2) by the mixed solution filtering and washing obtaining in step (1) 3 times, the graphite layers with edge intercalation are obtained
Compound.
(3) by hydrogen peroxide, ammonia and sodium carbonate liquor are according to 1:3:1 volume ratio is made into bubble reactant, by step (2)
Compound between graphite layers with edge intercalation put in this mixed solvent, soak 6h, bubble reactant is in oxidation at 30 DEG C
Graphite edge interlayer fully react, produce gas, make graphite flake layer expand peel off.Obtain after the completion of reaction gathering with Graphene
The graphene dispersing solution of collective.
(4) by the graphene dispersing solution in step (3) under 50-100W power weak supersound process 30min, make not shell completely
From under graphene sheet layer thoroughly peel off, that is, obtain the complete Graphene aqueous dispersion liquid of the lattice of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry sucking filtration film forming, after 60 DEG C of vacuum drying oven is dried 6h, four probes
The room temperature square resistance that method records graphene film is 10ohm/sq.
Embodiment 6
(1) native graphite being 45 μm by particle diameter, persulfuric acid complex salt [N (C4H9)4]5·2HSO5·HSO4·SO4According to
1:2 quality proportioning, is mixedly configured into 200ml aqueous solution after weighing corresponding quality, carries out edge oxidation intercalation,
At 120 DEG C, magnetic agitation reaction 2h, obtains mixed solution.
(2) by the mixed solution filtering and washing obtaining in step (1) 3 times, the graphite layers with edge intercalation are obtained
Compound.
(3) by hydrogen peroxide and ammonium oxalate solution according to 1:4 volume ratio mixing are made into bubble reactant, by band in step (2)
The compound between graphite layers having edge intercalation put in this mixed solvent, soak 10h bubble reactant in oxidation at 30 DEG C
Graphite edge interlayer fully reacts, and produces gas, so that graphite flake layer is expanded and peels off, forms the Graphene with Graphene aggregation
Dispersion liquid.
(4) by the graphene dispersing solution in step (3) under 50-100W power weak supersound process 30min, that is, obtain 1-10
The complete Graphene aqueous dispersion liquid of lattice of layer.
(5) Graphene aqueous dispersion liquid in step (4) is filtered or be centrifuged, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry sucking filtration film forming, after 60 DEG C of holding 6h of vacuum drying oven, four probes
The room temperature square resistance that method records graphene film is 8.6ohm/sq.
The present invention has the advantages that operating process is simple, safe and pollution-free, and overcoming Graphene in strong acid-base and must have
In malicious organic solvent prepare, and can not in water scattered shortcoming.The grapheme material that the present invention obtains is aoxidized due to edge
And there is fabulous water solublity, because the lattice structure of most Graphenes is not subject to Oxidative demage to have superelevation simultaneously
Conductance and thermal conduction characteristic, have controlled lateral dimension because gentle bubble is peeled off, it is possible to obtain big size graphene film.
The grapheme material that the present invention obtains, due to having water solublity, perfect structure and controlled dimensions, can apply to electrically conducting transparent thin
Film, heat-conducting glue, electrocondution slurry, high-barrier composite material etc..
Above-described embodiment only principle of the illustrative present invention and its effect, not for the restriction present invention.Any ripe
The personage knowing this technology all can carry out modifications and changes without prejudice under the spirit and the scope of the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
All equivalent modifications becoming or change, must be covered by the claim of the present invention.
Claims (13)
1. a kind of preparation method of Graphene is it is characterised in that the method at least comprises the following steps：
(1) graphite is mixed with intercalator, carry out edge oxidation intercalation, form the graphite layers chemical combination with edge intercalation
Thing；
(2) compound between graphite layers carrying edge intercalation described in step (1) are put into bubble reactant, carry out bubble stripping
Reaction, forms the graphene dispersing solution with Graphene aggregation.
2. Graphene according to claim 1 preparation method it is characterised in that：Graphite described in step (1) is natural
Graphite or Delanium, the particle size range of described graphite is 1-100 μm.
3. Graphene according to claim 1 preparation method it is characterised in that：In step (1), reaction temperature is 30-
200 DEG C, the response time is 1-24h.
4. Graphene according to claim 1 preparation method it is characterised in that：Graphite described in step (1) with described
The mass ratio of intercalator is 1:(1-10).
5. Graphene according to claim 1 preparation method it is characterised in that：Described in step (1), intercalator was
Sulphuric acid complex salt (2KHSO5·KHSO4·K2SO4), [N (C4H9)4]5·2HSO5·HSO4·SO4One of or the two mixed
Compound.
6. Graphene according to claim 1 preparation method it is characterised in that：Described in step (1), intercalator is normal
One or two kinds of in rule oxidant, described conventional oxidant includes KMnO4、K2FeO4And KClO3.
7. Graphene according to claim 1 preparation method it is characterised in that：In step (2), reaction temperature is 30-
100 DEG C, soak time is 4-24h.
8. Graphene according to claim 1 preparation method it is characterised in that：Bubble reactant described in step (2)
Including hydrogen peroxide and ammonium oxalate mixed solution, hydrogen peroxide and sodium carbonate mixture, hydrogen peroxide and ammonia mixed solution, this is several
One or more of mixed solution.
9. Graphene according to claim 1 preparation method it is characterised in that：Bubble described in step (2) is peeled off anti-
Carry out in Ying Shui or in low-toxic organic solvent, described low-toxic organic solvent is DMF (DMF), N-
In methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) solvent any one.
10. Graphene according to claim 1 preparation method it is characterised in that：Carry Graphene aggregation being formed
Graphene dispersing solution after, also include the graphene dispersing solution with Graphene aggregation is carried out weak supersound process, obtain stone
The step of black alkene aqueous dispersion liquid.
The preparation method of 11. Graphenes according to claim 10 it is characterised in that：Ultrasonic work(in described weak supersound process
Rate scope is 50-100W, and the time of described weak supersound process is 10-30min.
The preparation method of 12. Graphenes according to claim 10 or 11 it is characterised in that：Obtain described Graphene aqueous phase
After dispersion liquid, also include described Graphene aqueous dispersion liquid being filtered or being centrifuged, to obtain the step that Graphene concentrates slurry.
The preparation method of 13. Graphenes according to claim 12 it is characterised in that：Obtain described Graphene and concentrate slurry
Afterwards, also include concentrating slurry sucking filtration, drying, the step to obtain graphene film to described Graphene.
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| CN105271202B (en) * | 2015-11-16 | 2018-01-16 | 江苏城工建设科技有限公司 | A kind of preparation method and applications of graphene |
| CN106882801A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院上海高等研究院 | A kind of preparation method of the controllable graphene oxide of interlamellar spacing and graphene oxide frame structure material |
| CN107235485B (en) * | 2016-03-23 | 2019-09-10 | 上海新池能源科技有限公司 | The preparation method of graphene |
| CN107235486B (en) * | 2016-03-23 | 2019-11-29 | 上海新池能源科技有限公司 | The preparation method of water-soluble graphene |
| CN107235487B (en) * | 2016-03-23 | 2019-09-06 | 上海新池能源科技有限公司 | The preparation method of graphene |
| CN106672957A (en) * | 2016-07-18 | 2017-05-17 | 中国科学院兰州化学物理研究所 | Method for preparing graphene oxide according to Fenton oxidation method |
| CN106744883B (en) * | 2017-01-05 | 2019-03-22 | 中山科普斯特电源技术有限公司 | The preparation method of graphene |
| CN107857254B (en) * | 2017-09-19 | 2020-07-31 | 桂林理工大学 | Preparation method of water-soluble graphene |
| CN107973293A (en) * | 2017-12-18 | 2018-05-01 | 昂星新型碳材料常州有限公司 | The preparation method and graphene of graphene |
| US20200324253A1 (en) * | 2018-01-15 | 2020-10-15 | National University Of Singapore | A Graphene-Based Membrane |
| CN109850880A (en) * | 2019-02-28 | 2019-06-07 | 宁波石墨烯创新中心有限公司 | A kind of porous ultra-thin graphene and its preparation method and application suitable for lubricating oil |
| CN110589815B (en) * | 2019-09-11 | 2021-08-10 | 北京航空航天大学 | Preparation method of graphene conductive paste |
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN111422857B (en) * | 2020-01-14 | 2022-02-01 | 昂星新型碳材料常州有限公司 | Graphene nano-bubble material, preparation method and application thereof, adsorbent, catalyst, optical material and energy storage material |
| CN111547712A (en) * | 2020-04-29 | 2020-08-18 | 深圳市优宝新材料科技有限公司 | Layered graphene and preparation method thereof |
| CN114074937B (en) * | 2020-08-19 | 2023-09-05 | 山东海科创新研究院有限公司 | Thin-layer low-defect micro-nano graphene and preparation method thereof |
| CN113563773B (en) * | 2021-07-26 | 2022-02-22 | 宝泰隆新材料股份有限公司北京技术研发中心 | Preparation method of graphene heat dissipation coating |
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