CN104803380A - Preparation method of graphene - Google Patents
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- CN104803380A CN104803380A CN201510239652.5A CN201510239652A CN104803380A CN 104803380 A CN104803380 A CN 104803380A CN 201510239652 A CN201510239652 A CN 201510239652A CN 104803380 A CN104803380 A CN 104803380A
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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, particularly relate to a kind of preparation method of Graphene.
Background technology
Since Graphene is in the news for 2004, because of the conduction of its excellence, heat conduction, mechanical propertys etc. receive much concern, especially conductivity, causes huge great waves at electron device and energy storage field, and associated specialist thinks that Graphene is expected to cause a field technology revolution at hyundai electronics sciemtifec and technical sphere.Therefore the market requirement of Graphene is increasing, and this just requires that the preparation industry of Graphene large batch ofly can provide high-quality Graphene.But current Graphene is prepared industry and still have some problem demanding prompt solutions in volume production.First, in the past 10 years, chemistry redox method prepares the main method of Graphene on a large scale, because this method large-scale production cost is low, obtains sample oxy radical controlled, can disperse in multi-solvents.Conventional oxidation method has Hummers, Staudenmair and Brodie and improving one's methods.Recently, superb seminar of Zhejiang University is published on Nat.Commun. " An iron-based green approach to 1-h productionof single-layer graphene oxide " proposes a kind of new oxygenant K
2feO
4prepare graphene oxide, this oxygenant is than traditional KMnO
4security is high, and the reaction times is faster, is more suitable for extensive preparation.But graphene oxide prepared by which kind of oxidation style all needs further reduction to reduce oxy radical, repairs oxidation and peels off the defect brought.Conventional method of reducing has rapid thermal process, microwave method, reductibility chemical reagent reduction etc.Regrettably these method of reducing are difficult to thoroughly repair the defect introduced when being oxidized, because oxy radicals a large amount of in the process of Strong oxdiative destroys sp in graphite
2structure, forms a large amount of sp
3structure, these sp
3structure is difficult to be repaired in reduction.Therefore oxidation reduction process obtain with sp
3the electric property reducing intrinsic Graphene of the Graphene order of magnitude of structure, greatly limit the application in a lot of field.
Therefore, the scale preparation of intrinsic Graphene needs the novel method developing a kind of non-Strong oxdiative.According to the non-oxidation of bibliographical information or weak oxide prepare the method for Graphene, the investigators of Graphene find to peel off from natural graphite liquid phase that to prepare high-quality graphene be prepare intrinsic Graphene the best way on a large scale.Liquid phase is peeled off and is referred in some solvent, such as N-Methyl pyrrolidone, N, dinethylformamide and N, N-N,N-DIMETHYLACETAMIDE equal solvent, or be added with in the aqueous solution of tensio-active agent, utilize the process that graphite flake is successively peeled off by equipment or intercalation technique from graphite block body.Directly at present peel off from natural graphite liquid phase the method preparing Graphene and have: electrochemical stripping method, melting salt intercalation stripping method, ultrasonic stripping method, interlayer reaction stripping method and mechanical shearing stripping method.Nat.Mater. " the Scalable production of large quantities ofdefect-free few-layergraphene by shearexfoliation in liquids " of upper report proposes to utilize mechanical shearing to peel off the method for graphite, obtain the graphene film of lattice perfection, shortcoming is lateral dimension less (500nm); " the Interlayer catalyticexfoliation realizingscalable production of large-size pristinefew-layer graphene " of Suzhou nanometer Suo Liuliwei seminar report utilizes the stripping of interlayer catalyzed reaction to prepare Graphene, obtain graphene sheet layer larger, lattice perfection, but the intercalation condition of presoma is harsher, wayward and consume energy high.In general, ultrasonic and shearing method obtains Graphene size (hundreds of nanometer) less than normal, electrochemical stripping, although melting salt intercalation and interlayer reaction stripping method can obtain the Graphene of large-size, but intercalator is complicated, severe reaction conditions, solvent has pollution and consumes energy high, the most important thing is that the Graphene obtained can only be scattered in organic solvent and can not be scattered in water.Chinese patent CN201410111450.8 " a kind of mass-producing aqueous phase prepares the method for Graphene " proposes a kind of strong acid oxygenant intercalation; strong alkali environment ultrasonic disperse; aqueous phase prepares the method for Graphene, obtains the Graphene in the dispersion of water middle and high concentration, breaks through a difficult problem for the dispersion of Graphene in water.But still use strong acid, highly basic and high-power ultrasonic technology, make aftertreatment complicated, environment is unfriendly, consumes energy high.
Summary of the invention
The shortcoming of prior art in view of the above; the object of the present invention is to provide a kind of preparation method of Graphene; solve existing Graphene to prepare in strong acid-base and toxic organic solvents; and the shortcoming can not disperseed in water, the present invention realizes pollution-free, less energy-consumption, high yield, high quality and large-scale by graphite edge oxidation intercalation technique and bubble lift-off technology and prepares water-soluble graphene.
For achieving the above object, the invention provides a kind of preparation method of Graphene, the method at least comprises the following steps:
(1) graphite is mixed with intercalator, carry out edge oxidation intercalation, form the compound between graphite layers with edge intercalation;
(2) drop into bubble reagent by described in step (1) with the compound between graphite layers of edge intercalation, carry out bubble stripping reaction, form the graphene dispersing solution with Graphene aggregate.
Preferably, described in step (1), graphite is natural graphite or synthetic graphite, and the particle size range of described graphite is 1-100 μm.
Preferably, in step (1), temperature of reaction is 30-200 DEG C, and the reaction times is 1-24h.
Preferably, the mass ratio 1:(1-10 of graphite and described intercalator described in step (1)).
Preferably, intercalator described in step (1) is persulfuric acid composite salt (2KHSO
5kHSO
4k
2sO
4), [N (C
4h
9)
4]
52HSO
5hSO
4sO
4in the mixture of one or both.
Preferably, intercalator described in step (1) is a kind of in conventional oxidant or two kinds, and described conventional oxidant comprises KMnO
4, K
2feO
4, KClO
3.
Preferably, in step (2), temperature of reaction is 30-100 DEG C, and soak time is 4-24h.
Preferably, bubble reagent described in step (2) comprise hydrogen peroxide and ammonium oxalate mixing solutions, hydrogen peroxide and sodium carbonate mixture, hydrogen peroxide and this several mixing solutions of ammoniacal liquor mixing solutions one or more.
Preferably, described in step (2), bubble stripping reaction carries out in water or in low-toxic organic solvent, described low-toxic organic solvent be in DMF (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) solvent any one.
Preferably, after forming the described graphene dispersing solution with Graphene aggregate, also comprise and weak supersound process is carried out to the described graphene dispersing solution with Graphene aggregate, obtain the step of 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, after obtaining described Graphene aqueous dispersion liquid, also comprise described Graphene aqueous dispersion liquid filtration or centrifugal, to obtain the step that Graphene concentrates slurry.
Preferably, obtain after described Graphene concentrates slurry, also comprise and slurry suction filtration, drying are concentrated to described Graphene, to obtain the step of graphene film.
The present invention can carry out at aqueous phase, reduces environmental pollution, reduces the injury to staff's health.Operating process of the present invention is simple, safety, and pollution-free, overcoming Graphene must prepare in strong acid-base and toxic organic solvents, and the shortcoming can not disperseed in water; Make Graphene lateral dimension controlled because the present invention adopts gentle bubble lift-off technology, big size graphene film can be obtained.The present invention prepares high-quality water-soluble graphene by simple operations, is applicable to the scale operation of Graphene, has prospects for commercial application widely.Compared to existing graphene product, the grapheme material that the present invention obtains has fabulous water-soluble due to edge oxidation, and the crystalline network due to most Graphene is not subject to Oxidative demage and has superelevation conductance and thermal conduction characteristic.The grapheme material obtained due to the present invention has water-soluble, perfect structure and the controlled advantage of size, and the present invention can be applicable to the every field such as transparent conductive film, heat-conducting glue, electrocondution slurry, high-barrier composite material.
Accompanying drawing explanation
Fig. 1 is shown as the schematic diagram of the preparation method of Graphene provided by the invention;
Fig. 2 is shown as the SEM figure of technical scheme Raw in embodiment one;
Fig. 3 to be shown as in embodiment one technical scheme the SEM obtained with the compound between graphite layers of edge intercalation scheme;
Fig. 4 be shown as technical scheme in embodiment one obtain the SEM figure of the low resolution of Graphene;
Fig. 5 be shown as technical scheme in embodiment one obtain the high-resolution SEM figure of Graphene;
Fig. 6 is shown as the AFM figure of the Graphene that technical scheme obtains in embodiment one;
Fig. 7 is shown as the TEM figure of the low resolution of the Graphene that technical scheme obtains 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 obtains.
In figure, element numbers explanation
S10 ~ S50 step
Embodiment
The present invention proposes a kind of without strong acid, without highly basic, without high-power equipment, the green technology route that simple to operate, Graphene crystalline structure is complete; use edge oxidation intercalation in conjunction with bubble lift-off technology, efficiently solve in high-quality graphene mass-producing preparation process how to realize the difficult problems such as high quality, low cost, high-level efficiency, environmental friendliness, large size.Green oxidation Intercalation principle of the present invention: intercalator is persulfuric acid composite salt (2KHSO
5kHSO
4k
2sO
4), [N (C
4h
9)
4]
52HSO
5hSO
4sO
4in the mixture of any one or the two, the effective ingredient list persulfate ion (HSO of intercalator
5 -), through discharging active oxygen [O] by chain reaction after water-soluble, and form the various active such as hydroxyl radical free radical, Both peroxyl radical composition.The Standard Electrode Potentials of single persulfate is 1.82V, and higher than chlorine (1.36V) and dioxide peroxide (1.5V), oxidation potential energy is high, has exceeded muriate, potassium permanganate, hydrogen peroxide etc.Graphite itself has certain stability, but the carbon ratio at graphite edge is comparatively active, the active carbon at active oxygen [O] meeting graphite oxide edge, by controlling the amount of intercalator, obtains the compound between graphite layers of lattice perfection in edge oxidation, face.The present invention adopts gentle bubble lift-off technology, make Graphene when graphite surface is peeled off, not experience the destructive very strong technological process such as high-power ultrasonic, microwave or high speed shear, thus can obtain more large size, microtexture more perfectly high-quality graphene material.This grapheme material contains a large amount of-COOH ,-COH, C-O-C and-OH etc., and containing oxygen organic group, with negative charge, this grapheme material has better wetting ability because its edge is oxidized.
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art the content disclosed by this specification sheets can understand other advantages of the present invention and effect easily.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under 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 basic conception of the present invention in a schematic way, then only the assembly relevant with the present invention is shown in graphic but not component count, shape and size when implementing according to reality is drawn, it is actual when implementing, and the kenel of each assembly, quantity and ratio can be a kind of change arbitrarily, and its assembly layout kenel also may be more complicated.
With reference to figure 1, the preparation method of Graphene provided by the invention, comprising:
Step S10: mixed with intercalator by graphite, carries out edge oxidation intercalation, forms the compound between graphite layers with edge intercalation.
Step S20: the described compound between graphite layers with edge intercalation is dropped into bubble reagent, carries out bubble stripping reaction, form the graphene dispersing solution with Graphene aggregate.
In specific embodiment mode, the method also comprises:
Step S30: the described graphene dispersing solution with Graphene aggregate is carried out weak supersound process, obtains Graphene aqueous dispersion liquid.
Step S40: carried out by described Graphene aqueous dispersion liquid filtering or centrifugal, obtains Graphene and concentrates slurry.
Step S50: after described Graphene is concentrated slurry suction filtration, drying, obtains graphene film.
Concrete, the preparation method of Graphene provided by the invention can be:
First, perform step S10: be dispersed in after being mixed with intercalator by graphite in aqueous environment, carry out edge oxidation intercalation, stirring reaction 1-24h at 30-200 DEG C, react rear water filtration and rinsed three times, obtain the compound between graphite layers with edge intercalation.
Described compound between graphite layers is exactly under the effect of intercalator, and chemical reaction substance invades graphite edge, and at edge and C atomic linkage, forms a kind of compound not destroying graphite laminate structure.Graphite has excellent plasticity-, belongs to hexagonal layered structure.Carbon atom in layer closes with C-C σ bond, and interlayer then combines with faint Van der Waals force, and under the effect of oxygenant, the edge of natural graphite or synthetic graphite is oxidized.Edge oxide group causes graphite layers distance to strengthen, and forms the compound between graphite layers of edge intercalation.
Described graphite is natural graphite or synthetic graphite, and the particle size range of described natural graphite or synthetic graphite is 1-100 μm, and the mass ratio of described natural graphite or synthetic graphite and described intercalator is 1:1-1:10.
Described intercalator can be persulfuric acid composite salt (2KHSO
5kHSO
4k
2sO
4), [N (C
4h
9)
4]
52HSO
5hSO
4sO
4in the mixture of any one or the two; It is any one or two kinds in conventional oxidant that described intercalator also can be, preferably, and such as KMnO
4, K
2feO
4, KClO
3in oxygenant.
The mode of described stirring is: graphite is put into container, then puts into described intercalator, and then adding water is configured to solution, then stirs with magnetic stirring apparatus, and the stirring velocity of described magnetic agitation is 200r/min ~ 300r/min.
Next, step S20 is performed: the described compound between graphite layers with edge intercalation is dropped into bubble reagent, carries out bubble stripping reaction.Set temperature 30-100 DEG C, the reaction times 4 is little of 24 hours, forms the graphene dispersing solution with a small amount of quasiflake graphite alkene aggregate.Wherein, Graphene aggregate refers to that interlamellar spacing increases, the Graphene intermediate not yet stripped down.
Interlamellar spacing with the compound between graphite layers edge of edge intercalation is increased in previous step edge oxidation intercalation, through this step, bubble reagent reacts and produces gas and assemble increase between marginal layer, bubble is formed at gas accumulation, the process that bubble volume increases, interfloor distance between graphite flake layer is also increased gradually, after the large explosion to a certain extent of bubble, new bubble is formed again, explosion again, until graphite flake is stripped, form the graphene dispersing solution with Graphene aggregate.
This step adopts gentle bubble lift-off technology, makes Graphene when graphite surface is peeled off, not experience the destructive very strong technological process such as high-power ultrasonic, microwave or high speed shear, not graphite-structure in surface of fracture, increases graphite flake marginal layer spacing.
Described bubble reagent refer to can in water the reagent of a large amount of bubble of product, to comprise in hydrogen peroxide and this several mixing solutions of ammonium oxalate mixing solutions, hydrogen peroxide and sodium carbonate mixture, hydrogen peroxide and ammoniacal liquor mixing solutions any one or a few.
Described bubble stripping reaction both can carry out in water, also can carry out in low-toxic organic solvent, described low-toxic organic solvent be in DMF (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) solvent any one.
This step is placed on thermostat by with the compound between graphite layers of edge intercalation and bubble reagent, realizes controlling the compound between graphite layers of edge intercalation and the temperature of bubble reaction reaction by the temperature controlling thermostat.Described thermostat can be water-bath, oil bath etc.In this step, relative to other reaction conditions, temperature is also comparatively gentle on the impact of reaction process, therefore in embodiment, temperature of reaction also can exceed this scope, then the reaction times also can change accordingly.
Next, perform step S30, the described graphene dispersing solution with Graphene aggregate is carried out weak supersound process, the graphene film under not peeling off completely is thoroughly peeled off, obtain Graphene aqueous dispersion liquid.Wherein, the ultrasonic power of weak supersound process controls at 50-100W, and this power both can make graphene film thoroughly peel off, and prevent again supersound process from damaging graphene-structured, the time controling of weak supersound process is at 10-30min.
Next, perform step S40, carried out by described Graphene aqueous dispersion liquid filtering or centrifugal, obtain Graphene and concentrate slurry, dispersion concentration reaches 10mg/ml.
Next, perform step S50: described Graphene is concentrated slurry suction filtration film forming, then in loft drier, at 30-120 DEG C of temperature after dry 5-6h, obtain graphene film.The surface resistance that four probe method records described graphene film reaches 3-10ohm/sq, illustrates that the conductance good stability of the Graphene obtained, quality are high.The number of plies of the Graphene obtained is 1-10 layer, lattice perfection in face, and productive rate can reach 55%.
Embodiment 1
(1) by particle diameter be natural graphite and the persulfuric acid composite salt (2KHSO of 100 μm
5kHSO
4k
2sO
4) according to the quality of 1:1 than proportioning, be mixedly configured into the 200ml aqueous solution after weighing corresponding quality, carry out edge oxidation intercalation, at 50 DEG C of lower magnetic force stirring reaction 4h, obtain mixing solutions.Fig. 2 is the SEM figure of graphite, can find out that graphite edge is piled up closely regular.
(2) by after the mixing solutions suction filtration that obtains in step (1), with distilled water flushing 3 times, the compound between graphite layers with edge intercalation is obtained.Fig. 3 schemes with the SEM of the compound between graphite layers of edge intercalation, can see that the edge section of the compound between graphite layers with edge intercalation is opened, obvious fold, piles up loose.
(3) ammoniacal liquor and hydrogen peroxide are mixed according to 1:1 volume ratio be made into bubble reagent, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, 6h is soaked at 40 DEG C, ammoniacal liquor and hydrogen peroxide molecule lead to snperoxiaized graphite edge and enter between graphite flake layer and fully react, produce gas, gas accumulation expands thus graphite flake layer is peeled off.The graphene dispersing solution with Graphene aggregate is obtained after having reacted.
(4) graphene dispersing solution in step (3) is carried out weak supersound process 10min under 50-100W power, the graphene sheet layer under not peeling off completely is thoroughly peeled off, namely obtains Graphene aqueous dispersion liquid.
(5) step (4) described Graphene aqueous dispersion liquid is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) by step (5), described Graphene is concentrated slurry suction filtration, keep 5h in 120 DEG C, loft drier, obtain graphene film, the room temperature square resistance that four probe method records graphene film is 3.89ohm/sq.Fig. 4, Fig. 5 are respectively the low resolution of obtained Graphene, high-resolution SEM schemes, and its pattern yarn shape, curling as can be seen from FIG..Be the AFM figure of Graphene in Fig. 6, can find out that Graphene thickness is between 1-3nm; Fig. 7, Fig. 8 are the low resolution of Graphene respectively, high-resolution TEM schemes, and can see that this sheet Graphene is 3 layers from high resolving power TEM figure.
Embodiment 2
(1) by particle diameter be the electrographite of 5 μm and [N (C
4h
9)
4]
52HSO
5hSO
4sO
4according to the quality proportioning of 1:3, after weighing corresponding quality, be mixedly configured into 200ml aqueous dispersion liquid, carry out edge oxidation intercalation, at 30 DEG C of lower magnetic force stirring reaction 10h, obtain mixing solutions.
(2) by the mixing solutions filtering and washing that obtains in step (1) 3 times, the compound between graphite layers with edge intercalation is obtained.
(3) hydrogen peroxide and ammonium oxalate solution are mixed according to 3:1 volume ratio be made into bubble reagent, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, 4h is soaked at 60 DEG C, hydrogen peroxide and ammonium oxalate molecule enter abundant generated reactive gas between graphite marginal layer, thus graphite flake layer expansion is peeled off.The graphene dispersing solution with Graphene aggregate is obtained after having reacted.
(4) by the weak supersound process 30min under 50-100W power of the graphene dispersing solution in step (3), the graphene sheet layer under not peeling off completely is thoroughly peeled off, namely obtains the Graphene aqueous dispersion liquid of the lattice perfection of 1-10 layer.
(5) Graphene aqueous dispersion liquid described in step (4) is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry suction filtration film forming, after the dry 30 DEG C of maintenance 6h of vacuum drying oven, the room temperature square resistance that four probe method records graphene film is 10ohm/sq.
Embodiment 3
(1) by particle diameter be natural graphite, the persulfuric acid composite salt (2KHSO of 100 μm
5kHSO
4k
2sO
4) and [N (C
4h
9)
4]
52HSO
5hSO
4sO
4according to the quality of 1:1:1 than proportioning, after weighing corresponding quality, mixing is made into the 200ml aqueous solution, carries out edge oxidation intercalation, at 80 DEG C of lower magnetic force stirring reaction 10h, obtains mixing solutions.
(2) by the mixing solutions filtering and washing that obtains in step (1) 3 times, the compound between graphite layers with edge intercalation is obtained.
(3) hydrogen peroxide and sodium carbonate solution are mixed according to 1:3 volume ratio be made into bubble reagent, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, 4h is soaked at 100 DEG C, hydrogen peroxide and sodium carbonate molecule enter the abundant generated reactive gas in graphite edge, thus graphite flake layer expansion is peeled off.Thus graphite flake layer expansion is peeled off.The graphene dispersing solution with Graphene aggregate is obtained after having reacted.
(4) by the weak supersound process 30min under 50-100W power of the graphene dispersing solution in step (3), the graphene sheet layer under not peeling off completely is thoroughly peeled off, namely obtains the Graphene aqueous dispersion liquid of the lattice perfection of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry suction filtration film forming, after 120 DEG C, loft drier keeps 6h, the room temperature square resistance that four probe method records graphene film is 5.69ohm/sq.
Embodiment 4
(1) by particle diameter be natural graphite, the persulfuric acid composite salt (2KHSO of 45 μm
5kHSO
4k
2sO
4) and [N (C
4h
9)
4]
52HSO
5hSO
4sO
4according to the quality of 1:2:1 than proportioning, after weighing corresponding quality, mixing is made into the 200ml aqueous solution, carries out edge oxidation intercalation, at 100 DEG C of lower magnetic force stirring reaction 5h, obtains mixing solutions.
(2) by the mixing solutions filtering and washing that obtains in step (1) 3 times, the compound between graphite layers with edge intercalation is obtained.
(3) by hydrogen peroxide, ammoniacal liquor and sal volatile mix according to 1:1:1 volume ratio and are made into bubble reagent, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, 4h is soaked at 100 DEG C, bubble reagent fully reacts between the graphite marginal layer of oxidation, produce gas, graphite flake layer is expanded and peels off.The graphene dispersing solution with Graphene aggregate is obtained after having reacted.
(4) by the weak supersound process 30min under 50-100W power of the graphene dispersing solution in step (3), the graphene sheet layer under not peeling off completely is thoroughly peeled off, namely obtains the Graphene aqueous dispersion liquid of the lattice perfection of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry suction filtration film forming, after vacuum drying oven 60 DEG C keeps 6h, the room temperature square resistance that four probe method records graphene film is 6.31ohm/sq.
Embodiment 5
(1) by particle diameter be the natural graphite of 10 μm, persulfuric acid composite salt (2KHSO
5kHSO
4k
2sO
4) according to the quality of 1:4 than proportioning, be mixedly configured into 200ml aqueous dispersion liquid after weighing corresponding quality, carry out edge oxidation intercalation, at 80 DEG C of lower magnetic force stirring reaction 6h, obtain mixing solutions.
(2) by the mixing solutions filtering and washing that obtains in step (1) 3 times, the compound between graphite layers with edge intercalation is obtained.
(3) by hydrogen peroxide, ammoniacal liquor and sodium carbonate solution are made into bubble reagent according to 1:3:1 volume ratio, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, 6h is soaked at 30 DEG C, bubble reagent fully reacts between the graphite marginal layer of oxidation, produce gas, graphite flake layer is expanded and peels off.The graphene dispersing solution with Graphene aggregate is obtained after having reacted.
(4) by the weak supersound process 30min under 50-100W power of the graphene dispersing solution in step (3), the graphene sheet layer under not peeling off completely is thoroughly peeled off, namely obtains the Graphene aqueous dispersion liquid of the lattice perfection of 1-10 layer.
(5) Graphene aqueous dispersion liquid in step (4) is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry suction filtration film forming, after vacuum drying oven 60 DEG C of dry 6h, the room temperature square resistance that four probe method records graphene film is 10ohm/sq.
Embodiment 6
(1) by particle diameter be the natural graphite of 45 μm, persulfuric acid composite salt [N (C
4h
9)
4]
52HSO
5hSO
4sO
4according to the quality proportioning of 1:2, after weighing corresponding quality, be mixedly configured into the 200ml aqueous solution, carry out edge oxidation intercalation, at 120 DEG C of lower magnetic force stirring reaction 2h, obtain mixing solutions.
(2) by the mixing solutions filtering and washing that obtains in step (1) 3 times, the compound between graphite layers with edge intercalation is obtained.
(3) hydrogen peroxide and ammonium oxalate solution are mixed according to 1:4 volume ratio be made into bubble reagent, compound between graphite layers with edge intercalation in step (2) is dropped in this mixed solvent, at 30 DEG C, soak 10h bubble reagent fully react between the graphite marginal layer of oxidation, produce gas, graphite flake layer is expanded peel off, form the graphene dispersing solution with Graphene aggregate.
(4) by the weak supersound process 30min under 50-100W power of the graphene dispersing solution in step (3), the Graphene aqueous dispersion liquid of the lattice perfection of 1-10 layer is namely obtained.
(5) Graphene aqueous dispersion liquid in step (4) is carried out filter or centrifugal, obtain Graphene and concentrate slurry.
(6) Graphene in step (5) is concentrated slurry suction filtration film forming, after vacuum drying oven 60 DEG C keeps 6h, the room temperature square resistance that four probe method records graphene film is 8.6ohm/sq.
The present invention has that operating process is simple, safety, free of contamination advantage, and overcoming Graphene must prepare in strong acid-base and toxic organic solvents, and the shortcoming can not disperseed in water.The grapheme material that the present invention obtains has fabulous water-soluble due to edge oxidation, crystalline network due to most Graphene is not subject to Oxidative demage and has superelevation conductance and thermal conduction characteristic simultaneously, bubble due to gentleness is peeled off and has controlled lateral dimension, can obtain big size graphene film.The grapheme material that the present invention obtains, owing to having water-soluble, perfect structure and controlled dimensions, can be applied to transparent conductive film, heat-conducting glue, electrocondution slurry, high-barrier composite material etc.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (13)
1. a preparation method for Graphene, is characterized in that, the method at least comprises the following steps:
(1) graphite is mixed with intercalator, carry out edge oxidation intercalation, form the compound between graphite layers with edge intercalation;
(2) drop into bubble reagent by described in step (1) with the compound between graphite layers of edge intercalation, carry out bubble stripping reaction, form the graphene dispersing solution with Graphene aggregate.
2. the preparation method of Graphene according to claim 1, is characterized in that: described in step (1), graphite is natural graphite or synthetic graphite, and the particle size range of described graphite is 1-100 μm.
3. the preparation method of Graphene according to claim 1, is characterized in that: in step (1), temperature of reaction is 30-200 DEG C, and the reaction times is 1-24h.
4. the preparation method of Graphene according to claim 1, is characterized in that: described in step (1), the mass ratio of graphite and described intercalator is 1:(1-10).
5. the preparation method of Graphene according to claim 1, is characterized in that: intercalator described in step (1) is persulfuric acid composite salt (2KHSO
5kHSO
4k
2sO
4), [N (C
4h
9)
4]
52HSO
5hSO
4sO
4in the mixture of one or both.
6. the preparation method of Graphene according to claim 1, is characterized in that: intercalator described in step (1) is a kind of in conventional oxidant or two kinds, and described conventional oxidant comprises KMnO
4, K
2feO
4and KClO
3.
7. the preparation method of Graphene according to claim 1, is characterized in that: in step (2), temperature of reaction is 30-100 DEG C, and soak time is 4-24h.
8. the preparation method of Graphene according to claim 1, is characterized in that: bubble reagent described in step (2) comprise hydrogen peroxide and ammonium oxalate mixing solutions, hydrogen peroxide and sodium carbonate mixture, hydrogen peroxide and this several mixing solutions of ammoniacal liquor mixing solutions one or more.
9. the preparation method of Graphene according to claim 1, it is characterized in that: described in step (2), bubble stripping reaction carries out in water or in low-toxic organic solvent, described low-toxic organic solvent be in DMF (DMF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) solvent any one.
10. the preparation method of Graphene according to claim 1, it is characterized in that: after forming the graphene dispersing solution with Graphene aggregate, also comprise and weak supersound process is carried out to the graphene dispersing solution with Graphene aggregate, obtain the step of Graphene aqueous dispersion liquid.
The preparation method of 11. Graphenes according to claim 10, is characterized in that: in described weak supersound process, ultrasonic power 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, is characterized in that: after obtaining described Graphene aqueous dispersion liquid, also comprises filtering described Graphene aqueous dispersion liquid or centrifugal, to obtain the step that Graphene concentrates slurry.
The preparation method of 13. Graphenes according to claim 12, is characterized in that: obtain after described Graphene concentrates slurry, also comprise and concentrate slurry suction filtration, drying to described Graphene, to obtain the step of graphene film.
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