CN102275908B - Preparation method of graphene material - Google Patents
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Abstract
The invention discloses a preparation method of a graphene material. The preparation method comprises the following steps of: with graphite carbon as a raw material, adding potassium hypermanganate and concentrated sulfuric acid in batches in different stages to control an oxidation process of graphite; adjusting the pH value of the oxidized solution to obtain graphene oxide colloidal dispersing solutions (GOS) with different concentrations; dropwise adding the GOS on the surface of a carrier or spreading out the GOS on a non-intersolubility liquid/liquid interface and drawing into a graphene oxide thin-film (GOF); carrying out high-speed centrifugation and drying treatment on the GOS to obtain graphene oxide solid powder (GOP); reducing the GOS by selecting an appropriate reducing agent, and centrifugally drying to obtain reduced graphene solid powder (GRP); dispersing a proper amount of GRP in an organic solvent to prepare a reduced graphene oxide colloidal dispersing solution (GRS); and dropwise adding the GRS on the surface of the carrier or spreading out on the non-intersolubility liquid/liquid interface and drawing into the reduced graphene thin-film (GRF). Various graphene materials prepared by the invention are easy to mutually transform; and the concentration of the colloidal solution and the thickness of the thin-film can be controlled in a certain range.
Description
Technical field
What the present invention relates to is a kind of method of preparing grapheme material relevant with technical field of nano material, is specifically related to a kind of method that obtains grapheme material with new processing mode.
Background technology
Graphene, the two-dimentional atomic crystal material that a kind of carbon atom close-packed arrays of individual layer consists of.2004 by people such as scientist Geim A K by the adhesive tape plumbago single slice that obtains of exfoliated graphite repeatedly.Before Graphene is found, theoretical and experimentally all think perfect two-dirnentional structure all can't be under non-zero absolute temperature stable existence, so the discovery of Graphene caused global concern, its discoverer has obtained Nobel Prize in physics in 2010 simultaneously.
In fact, Graphene is the composition unit of other dimension carbon-based materials.The soccerballene of zero dimension can be regarded as the reunion of particular graphite alkene shape and forms; The carbon nanotube of one dimension can be regarded as the curling structure that forms of Graphene; Three-dimensional graphite can be regarded as by Graphene and forms through piling up.Although Graphene only has the thickness of a carbon atom, and be the thinnest a kind of in the known materials, its hardness ratio is taller 100 times of best iron and steel in the world.Electroconductibility also is best in the present known materials, and the movement velocity of electronics has reached 1/300 of the light velocity, considerably beyond the movement velocity of electronics in general conductor.The character that these are superior and special two-dirnentional structure are so that Graphene has fine development prospect.
Because the quantum effect of Graphene uniqueness and excellent chemical property.When the electronics in the Graphene moves in track, can or not introduce foreign atom because of lattice imperfection scattering occurs.Because reactive force is very strong between its atom, at normal temperatures, even carbon atom telescopes on every side, the interference that the electronics in the Graphene is subject to is also very little.Be with a wide range of applications at aspects such as electron device and transistor, photon sensor, matrix material, solar cell, ultracapacitor, hydrogen storage materials.As the New Type of Carbon sill that stores electric charge in the ultracapacitor element, the theoretical specific surface area of Graphene can reach 2630m
2g
-1, this means that positive and negative charge ions a large amount of in the electrolytic solution can be stored in thin layer of formation in the Graphene monolithic, thereby reach high Charge Storage level, increased electrical capacity.This can significantly improve efficient and the performance of electric power and hybrid vehicles.
The preparation method of Graphene mainly contains numerous preparation methods such as mechanically peel method, crystal epitaxy method, heating SiC method, chemistry redox method, chemical gas sedimentation, chemical template method and organic synthesis at present.
Patent US7824651B2 has described a kind of method that obtains being dispersed in the Graphene in the tensio-active agent based on the supersound process graphite flake.The method is by adding dispersion agent sodium lauryl sulphate (SDS), and ultrasonic 2h obtains the graphene suspension of stable dispersion; In patent US2798878, use chemical oxidization method, by adding potassium permanganate, the vitriol oil, SODIUMNITRATE etc. pyrolytic graphite is carried out the strong oxide treatment of low temperature, obtain graphite oxide, supersound process obtains the method for graphene oxide; Among the patent CN101549864A, disclose and a kind ofly prepared graphite oxide by traditional Hummers method, in supersound process, obtained the mono-layer graphite oxide sheet, be dispersed in the reductive agent hydrothermal method pyroreaction and process and obtain graphene film; Among the patent CN101367516A, under vacuum condition, use the conventional oxidation method to obtain graphite oxide and carry out pyroprocessing, the preparation graphene oxide.
At present, the method for using chemistry redox to obtain Graphene is the most general and widely, namely prolongs and has held the Hummers oxidation style, has obtained graphene oxide through ultra-sonic dispersion again, and last reductive agent reduces, and obtains Graphene.The degree of oxidation of graphite oxide has determined the quality of graphene oxide.Degree of oxidation is higher, and is more favourable for peeling off graphite oxide.Adopt oxidation-dispersion-three steps of reduction to obtain Graphene among the patent CN101786620A, process is simple, and the time is shorter, but is difficult to guarantee that graphite oxide fully expands, so the graphene oxide thickness of gained is difficult to control.
The present invention, in the graphene oxide preparation process, simplified traditional Hummers oxidation style, at a lower temperature, by different steps product being carried out step-by-step oxidation processes, obtain the sufficient graphite oxide of oxidation, finally prepare high-quality GOP, GOS, GOF, GRP, GRS and GRF material.
Summary of the invention
The objective of the invention is the deficiency that exists for prior art, provide that a kind of cost is low, productive rate is high, quality is good, simple possible, and the preparation method of more controlled grapheme material.
The present invention is achieved by the following technical solutions,
A kind of preparation method of grapheme material comprises the steps:
1) under-10～0 ℃ (can be that ice-water bath or cryosel are bathed), 1～50g graphite be joined in 80～1200ml, 98% vitriol oil, after stirring, add 1～30g solid nitric acid sodium, fully stir after 0.5～3h, add in batches 2～150g potassium permanganate, each 0.1～5g, be 5-10 minute each pitch time, the control temperature is no more than 20 ℃, fully stirs reaction 4～12h, temperature is risen to 35～50 ℃, reaction 24～36h; And then adding 3～150g potassium permanganate (each 0.1～5g, be 5-10 minute each pitch time, controls temperature and be no more than 20 ℃, fully stirs) in batches, reaction 4～12h obtains sticky substance A;
2) constantly stirring is lower, in A, add 80～1200ml, 98% vitriol oil, reaction 24～36h, the sticky substance B that obtains pours into and contains in the ice or frozen water that 10～100ml mass percent is 30% hydrogen peroxide, perhaps directly under ice bath, substance B poured into and contain in the aqueous solution that 10～100ml mass percent is 30% hydrogen peroxide, obtain graphite oxide suspension C;
3) with the C hold over night, obtain stratified mixture, filter, through acid elution, further wash with deionized water again, use at last absolute ethanol washing, centrifugal treating, drying obtains oxidation graphite solid D;
Described acid elution refers to 10%HCl washing, until in the filtrate without SO
4 2-Till; Described deionized water wash refers to be washed till without Cl
-Till the existence; Described drying treatment refers to 50 ℃ of vacuum-drying 24～36h in vacuum drying oven;
4) D that drying is obtained is distributed in the solvent, and supersound process 0.5～2h obtains homodisperse oxidized graphite flake E; By regulating pH value 2～14, obtain the graphene oxide colloidal solution of different graphene oxide concentration.
The A that occurs in the above-mentioned reaction is green for soil, and B is khaki color, and C is glassy yellow, and D and E are isabelline.
The described graphite of step 1) is one or more in natural flake graphite, gac, Graphite Powder 99 or the pyrolytic graphite.
The described solvent of step 4) refers to water, dehydrated alcohol, acetone, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, NVP, l-vinyl-2-pyrrolidone, Virahol or one or both mixed solution wherein.It is 80～200W that the described supersound process of step 4) refers to adopt power, and operating frequency is the ultrasound intensity of 30～150kHz.
Graphene oxide colloidal solution high speed centrifugation, the drying treatment that step 4) can be obtained obtain the graphene oxide pressed powder.
The graphene oxide colloidal solution that also step 4) can be obtained is added drop-wise to carrier surface or launches to be drawn into graphene oxide film at immiscible property liquid/liquid interface.Film balance is used in described graphene oxide film preparation, and described immiscible property liquid/liquid interface comprises the immiscible property liquid/liquid interface that methylene dichloride, trichloromethane, methyl alcohol, ethanol or acetone form.
Add reductive agent in the graphene oxide colloidal solution that can also obtain to step 4), reacting by heating obtains being dispersed in the Graphene colloidal solution in the organic solvent at last.Described reductive agent is hydrazine hydrate, sodium borohydride, POTASSIUM BOROHYDRIDE, Sulfothiorine, Potassium Thiosulphate, Hydrogen bromide, hydroiodic acid HI, ethylene glycol or quadrol; Reacting by heating refers to react 24～72h under 70～250 ℃ of oil baths.
With the Graphene colloidal solution that is dispersed in the organic solvent, use the millipore filtration suction filtration, obtain graphene film.
Graphene colloidal solution is centrifugal, drying obtains graphene powder.
The present invention as raw material, adds strong oxidizer in the differential responses stage with graphite, obtains the sufficient graphite oxide of oxidation.Do not adding under any tensio-active agent condition, can in organic solvent, obtain finely dispersed Graphene colloidal sol.
Compared with prior art, the invention has the advantages that:
(1) traditional Hummers graphite oxide method is optimized improvement, the graphite oxide degree of oxidation that obtains is higher, corresponding graphene oxide colloidal solution GOS, graphene oxide film GOF, graphene oxide pressed powder GOP, Graphene colloidal solution GRS, graphene film GRF and graphene powder GRP better quality.
(2) preparation technology is simple, and is with low cost, avoided pyroreaction, is beneficial to large-scale industrialized production.
(3) the equal recoverable of solvent that uses is saved cost.
(4) product of a series of relevant graphene oxides of preparation is realized efficient utilization of resource.
(5) productive rate is high, is beneficial to industrialization.
(6) related products of preparation can use about electrode material for super capacitor fuel cell material, the aspects such as catalysis.
Description of drawings
The state graph of the various products of Fig. 1 the present invention preparation;
(a) the GOS picture, (c) that were respectively 2～12 o'clock for graphite oxide picture of the present invention, (b) pH are that 7 o'clock GOS picture, (d) is the GRP picture for GRS picture, (e) for pH;
Fig. 2 is the GOS that the inventive method and traditional Hummers method obtain;
(a) GOS that obtains for the inventive method, the GOS that (b) obtains with traditional Hummers method;
Fig. 3 is the TGA figure of graphene oxide of the present invention and Graphene;
(a) be the TGA figure of graphene oxide of the present invention, (b) TGA for Graphene of the present invention schemes;
Fig. 4 is the AFM figure of graphite oxide of the present invention.
Embodiment
The below is described in detail embodiments of the invention, and can not limit the present invention.Present embodiment is all implemented under the prerequisite of the technical program, and describes in conjunction with figure, has provided detailed embodiment and concrete operating process, without specifying, is routine operation.
Embodiment 1
Present embodiment is described preparation method may further comprise the steps:
1, adds the 2g crystalline flake graphite in the beaker that oven dry is cleaned, under condition of ice bath, add the 100ml98% vitriol oil of measuring, fully stir, graphite and the vitriol oil are mixed, then add 1.5g SODIUMNITRATE solid, stir 30min, fully dissolving.Then slowly add 6g potassium permanganate solid in batches, (each 0.5g, be 10min each pitch time), the control temperature of reaction system is no more than 20 ℃, reaction 6h.Afterwards, remove ice bath, heating in water bath for reaction makes temperature rise to 35 ℃, reaction 24h.Add again 9g potassium permanganate, (each 0.5g, be 10min each pitch time), reaction 4h.
2, add subsequently 100ml98% strong sulfuric acid response 24h, obtain the sorrel thick liquid.With the thick liquid cool to room temperature, add quencher reaction in the 400ml ice that contains 10ml 30% hydrogen peroxide, obtain jonquilleous graphite oxide suspension.
3, with graphite oxide suspension hold over night, filter, obtain the tawny filter cake.Be that 10% dilute hydrochloric acid washing leaching cake is until no longer contain SO in the filtrate with massfraction
4 2-Till.Then use deionized water wash, until in the filtrate without Cl
-Till.Filter cake is placed 60 ℃ of vacuum-drying 24h of vacuum drying oven, obtain isabelline oxidation graphite solid.
4, graphite oxide is distributed in the deionized water ultrasonic 1h(power 200W, operating frequency 120kHz), be mixed with the dispersion liquid of 1mg/ml, regulate the pH value and be respectively 2～12, obtained the GOS of different concns, high speed centrifugation, drying obtains GOP, and the GOS membrane is prepared into GOF.GOS adds hydrazine hydrate 0.1ml, and ammoniacal liquor is regulated about pH to 9, at 95 ℃ of lower reaction 24h of oil bath, obtains Graphene colloidal solution GRS, filters.With the deionized water repetitive scrubbing for several times, until filtrate is neutrality.The filter cake of gained places 80 ℃ of vacuum-drying 24h of vacuum drying oven, obtains GRP.With Graphene colloidal solution filtering with microporous membrane, obtain GRF.
Embodiment 2-10
Operation steps is with embodiment 1, and condition control and graphite oxide colloid product the results are shown in following table:
* resulting graphite oxide colloid is the same manner as in Example 1, is easy to be converted into other grapheme material.
Claims (10)
1. the preparation method of a grapheme material is characterized in that, comprises the steps:
1) under-10～0 ℃, 1～50g graphite is joined in 80～1200ml, 98% vitriol oil, after stirring, add 1～30g solid nitric acid sodium, fully stir after 0.5～3h, add in batches 2～150g potassium permanganate, each 0.1～5g, be 5-10 minute each pitch time, the control temperature is no more than 20 ℃, fully stirs reaction 4～12h, temperature is risen to 35～50 ℃, reaction 24～36h; And then add 3～150g potassium permanganate reaction, 4～12h in batches, and each 0.1～5g, be 5-10 minute each pitch time, obtains sticky substance A;
2) constantly stirring is lower, in A, add 80～1200ml, 98% vitriol oil, reaction 24～36h, the sticky substance B that obtains pours into and contains in the ice or frozen water that 10～100ml mass percent is 30% hydrogen peroxide, perhaps directly under ice bath, substance B poured into and contain in the aqueous solution that 10～100ml mass percent is 30% hydrogen peroxide, obtain graphite oxide suspension C;
3) with the C hold over night, obtain stratified mixture, filter, through acid elution, further wash with deionized water again, use at last absolute ethanol washing, centrifugal treating, drying obtains oxidation graphite solid D;
4) D that drying is obtained is distributed in the solvent, and supersound process 0.5～2h obtains homodisperse oxidized graphite flake E; By regulating the pH value 2～14, obtain the graphene oxide colloidal solution of different graphene oxide concentration.
2. preparation method according to claim 1 is characterized in that, graphene oxide colloidal solution high speed centrifugation, drying treatment that step 4) is obtained obtain the graphene oxide pressed powder.
3. preparation method according to claim 1 is characterized in that, the graphene oxide colloidal solution that step 4) is obtained is added drop-wise to carrier surface or launches to be drawn into graphene oxide film at immiscible property liquid/liquid interface.
4. preparation method according to claim 3, it is characterized in that, film balance is used in described graphene oxide film preparation, and described immiscible property liquid/liquid interface comprises the immiscible property liquid/liquid interface that methylene dichloride, trichloromethane, methyl alcohol, ethanol or acetone form.
5. preparation method according to claim 1 is characterized in that, adds reductive agent in the graphene oxide colloidal solution that obtains to step 4), and reacting by heating obtains being dispersed in the Graphene colloidal solution in the solvent at last.
6. preparation method according to claim 5 is characterized in that, described reductive agent is hydrazine hydrate, sodium borohydride, POTASSIUM BOROHYDRIDE, Sulfothiorine, Potassium Thiosulphate, Hydrogen bromide, hydroiodic acid HI, ethylene glycol or quadrol; Reacting by heating refers to react 24～72h under 70～250 ℃ of oil baths.
7. according to claim 5 or 6 described preparation methods, it is characterized in that, Graphene colloidal solution is used the millipore filtration suction filtration, obtain graphene film; Or Graphene colloidal solution is centrifugal, drying obtains graphene powder.
8. preparation method according to claim 1 is characterized in that, the described graphite of step 1) is one or more in natural flake graphite, Graphite Powder 99 and the pyrolytic graphite.
9. preparation method according to claim 1, it is characterized in that, the described solvent of step 4) refers to water, dehydrated alcohol, acetone, N, the mixed solution of one or both in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, NVP, l-vinyl-2-pyrrolidone, the Virahol.
10. preparation method according to claim 1 is characterized in that, it is 80～200W that the described supersound process of step 4) refers to adopt power, and operating frequency is the ultrasound intensity of 30～150kHz.
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| CN101602504B (en) * | 2009-07-16 | 2011-04-13 | 上海交通大学 | Preparation method of graphene based on ascorbic acid |
| CN101774574A (en) * | 2010-01-22 | 2010-07-14 | 湘潭大学 | Preparation method of graphene inorganic nanocomposite |
| CN101786620B (en) * | 2010-03-30 | 2011-12-28 | 武汉大学 | Method for chemical synthesis of graphene |
| CN101830458B (en) * | 2010-05-06 | 2012-01-04 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
| CN101966988B (en) * | 2010-11-17 | 2012-07-04 | 哈尔滨工业大学 | Method for preparing graphene powder |
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