CN102502612B - Method for preparing grapheme through oxidation reduction - Google Patents
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Abstract
The invention relates to a method for preparing grapheme through oxidation reduction and belongs to grapheme preparation technique. The method specifically comprises the following steps: a modified Hummer method is used for preparing graphite oxide, and an oscillator is adopted for shaking and peeling off single layer graphite oxide softly. During the step of preparing grapheme through reduction, compared with kinds of conventional major reducing agents, the method has the advantages that the reduction procedures and conditions are optimized, and further the grapheme with excellent performance is obtained. In the invention, by optimizing the preparation technique and conditions, the grapheme, which is large in size, is single-layered, is excellent in electrical conductivity and has high quality is obtained, and the method has the characteristics of low cost, high product yield and easiness in industrialization.
Description
Technical field:
The present invention relates to a kind of method of preparing grapheme through oxidation reduction, belong to the technology of preparing of Graphene.
Background technology:
Term Graphene refers to the monolayer carbon atom of the cellular crystalline network of two-dimentional six side of tightly packed one-tenth.Two scientists of the Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselov have obtained initiative progress (K.S.Novoselov preparing aspect two-dimensional space material Graphene (Graphene), A.K.Geim et al Science 306,666 (2004)), obtained the Nobel Prize in physics of 2010.The discovery of Graphene has caused the sensation of scientific circles immediately, and Graphene is a kind of brand-new material, and it is unprecedented little that its thickness reaches, and also unusual height of physical strength.Simultaneously, it also has the satisfactory electrical conductivity more taller than copper, aspect heat conduction, surmounted especially current other known all materials, can predict at following nano electron device and unicircuit, flexible electronic device, ultra-high sensitive sensor novel electron device, matrix material, solar cell, super capacitor, the aspects such as hydrogen storage material are with a wide range of applications.
Since Graphene is found, about the preparation research of Graphene, constantly obtained important progress.It is several that the preparation method who has reported at present mainly contains that micromechanics is peeled off, prepared by epitaxy, chemical vapour deposition and solution phase etc., particularly chemical Vapor deposition process and solution chemical method (graphite oxide method) make scale prepare Graphene has become possibility, but compare solution chemical method, additive method is lowly difficult to be applied among the scale operation and application of Graphene because of its complicated operation, condition harshness or productive rate.
Oxidation reduction process is mainly to utilize strong oxidizer to carry out obtaining graphite oxide after intercalation oxidation to natural graphite, then by graphite oxide by ultrasonic, stir or concussion is carried out individual layer and peeled off and obtain graphene oxide, finally by reduction, obtain Graphene.Oxidation reduction process can be prepared Graphene in a large number, efficiently, and process is simple, so graphene oxide is an effective approach preparing on a large scale grapheme material.
But oxide-reduction method still has the deficiency on a lot of theory and technologies at present, hindered its large-scale industrial production, still there is very large arguement in the reaction mechanism of oxidation stage, the chemical structure of graphite oxide, and the Graphene size obtaining less (conventionally only having several microns), preparation cycle are long, and production concentration is low, from scale operation, still have larger distance, seriously hindered follow-up large-scale application.Therefore, preparing and synthesize large-sized grapheme material how efficiently, on a large scale, cheaply, is controllably still one of the research in this field and key of application.Secondly at reduction phase, recover the perfect crystalline network of Graphene, be exactly fundamentally the various groups (hydroxyl, carboxyl, epoxy group(ing), carbonyl) of removing above graphene oxide, and this process generally will be used very strong reductive agent.Current oxidizing reaction mainly contains reductive agent method and thermal reduction method.Reductive agent used mainly contains hydrazine hydrate, sodium borohydride, Ursol D etc. at present, although these reductive agents can be effectively by graphite oxide reduction, its huge toxicity has limited promotion and application.Recently, have people again successively with Green Oxidants such as xitix, glucose, citric acid, amino acid, sulfide, but their reduction effect there is no hydrazine hydrate good, reunites serious.Therefore finding effective and green reductive agent, is the another important trend that Graphene is prepared in reduction.
Summary of the invention:
Object of the present invention provides a kind of method of preparing grapheme through oxidation reduction in order to improve the shortcoming and defect of current liquid phase Graphene technology of preparing.
Technical scheme of the present invention is: a kind of method of preparing grapheme through oxidation reduction, and its concrete steps are as follows:
1) preparation of graphite oxide:
Hummer legal system by modification is for graphite oxide, by the volume of strong acid and the mass ratio of graphite, be after 15ml/g-50ml/g gets natural flake graphite and mixes with strong acid solution, then add saltpetre, wherein saltpetre and graphite mass ratio are 1-2: 1, at bath temperature, be to add strong oxidizer at 0-20 ℃, wherein the mass ratio of strong oxidizer and graphite is 2-6: 1, be warming up at 40-70 ℃ and react 1-3h, by the volume of distilled water, be 30ml/g-80ml/g with the ratio of graphite, add distilled water, at 75-95 ℃ of reaction 10-30min, stop oxidizing reaction, filtration or centrifuge washing graphite oxide system pH are between 5-7, at 40-80 ℃, vacuum-drying obtains oxidation graphite solid,
2) preparation of graphene oxide:
By step 1) oxidation graphite solid for preparing is dispersed in water, the graphite oxide suspension liquid that formation mass concentration is 2-7.0mg/ml by the ultrasonic dispersion of this suspension liquid, then shakes and peels off on vibrator, realize individual layer and peel off, obtain uniform and stable graphene oxide suspension liquid;
3) preparation of Graphene suspension liquid:
By step 2) to add alkali to regulate pH in the graphene oxide suspension liquid that makes be between 9-10, then by the mass ratio of graphene oxide in reductive agent and graphene oxide suspension liquid, be 2-10: 1, reductive agent is joined in graphene oxide suspension liquid, the mass ratio that adds again graphene oxide is 0-2: 1 tensio-active agent, in temperature, be to react 20min-3h at 90-96 ℃, obtain uniform and stable graphene dispersing solution.
Sulfuric acid, mass concentration that preferably above-mentioned strong acid mass concentration is 98% are the mixing acid of 60-67% nitric acid or both arbitrary proportions; Preferably described strong oxidizer is at least a kind of in potassium permanganate, potassium perchlorate or Vanadium Pentoxide in FLAKES; Preferred steps 3) reductive agent described in is at least a kind of in xitix, sodium bisulfite or oxammonium hydrochloride.
Step 1) the termination oxidizing reaction described in is; If the strong oxidizer adding is potassium permanganate, first add distilled water then to add hydrogen peroxide to stop oxidizing reaction, wherein adding the volume of distilled water and the ratio of graphite is 50ml/g-200ml/g, the mass concentration of hydrogen peroxide is 30%, and adding the volume of hydrogen peroxide and the mass ratio of potassium permanganate is 1ml/g-3ml/g; If the strong oxidizer adding is potassium perchlorate or Vanadium Pentoxide in FLAKES, add distilled water to stop oxidizing reaction, wherein adding the volume of distilled water and the ratio of graphite is 50ml/g-200ml/g.
Preferred steps 2) in, ultrasonic frequency is 40-80KHz, and ultrasonic time is 5-10 minute; Vibrator speed is 160-200rpm, and concussion splitting time is 6-12h.The pH alkali used of the adjusting graphene oxide solution preferred steps 3) is that mass concentration is the ammoniacal liquor of 10-28%.Preferred steps 3) tensio-active agent described in is polyoxyethylene laurel ether or triton X-100.
The present invention, by the mutual comparison of several green non-poisonous reductive agent relative merits, optimizes condition and the technique of reaction, seeks best, applicable industrialized technique.Xitix, acidity, has stronger reductibility, and heating or oxidizable decomposition in solution are more easily oxidized under alkaline condition, are hexose derivative.In the process of redox graphene, generate Try, tryptophane has the effect of dispersed graphite alkene simultaneously, stops the reunion of Graphene, so make reductive agent with xitix, no longer need to add unnecessary tensio-active agent to carry out the reunion of dispersed graphite alkene, prevention Graphene.But xitix is due to expensive, and industrially scalable becomes to produce cost relatively high.Oxammonium hydrochloride, mainly, as reductive agent and developer, toxicity is little.In preparing the process of Graphene suspension liquid, be that to utilize the reaction of ammoniacal liquor and oxammonium hydrochloride be to discharge free azanol, in 90 ℃ of water-baths, azanol, as reductive agent and graphite oxide alkene reaction, obtains graphene solution.With respect to xitix, oxammonium hydrochloride is cheap, and industrial production cost is low, is easy to scale operation.But graphene solution concentration prepared by oxammonium hydrochloride is very low, concentration is high easily to be produced and reunites.Optimize and add tensio-active agent, stop agglomeration, the high graphene solution of preparation concentration.Sodium pyrosulfate, with respect to existing reductive agent, sodium pyrosulfate substitutes large, the dangerous reagent of toxicity such as hydrazine, and preparation method is safety and environmental friendliness more.Secondly, compare with other reductive agents, the Graphene that sodium bisulfite is prepared has higher electroconductibility and quality, has well recovered the perfect crystalline network of Graphene.Finally, sodium pyrosulfate raw material is cheap and easy to get, preparation technology is simple, is applicable to large-scale industrial production, can be widely used in the preparation of novel grapheme material and device.
Beneficial effect:
The technique that the present invention prepares Graphene is simple, and preparation efficiency is high, with low cost, and the Graphene size of preparation is large, and quality is high, is easy to industrial scale operation.
The present invention adopts the use of combining of ultrasonic and concussion, wherein adopt the ultrasonic prestripping that can realize graphite oxide, its effect not only makes graphite oxide peel off into the graphene oxide of individual layer or few layer, and significantly having suppressed piling up between graphene layer, these can be owing to the active cavatition of ultrasonic radiation.But long ultrasonic meeting smashes large sheet graphite oxide, so for the large Graphene of preparation size, introduced oscillator, vibrator be the graphene oxide that a kind of very soft concussion separates individual layer, its advantage can be prepared large-sized Graphene exactly, and size and initial natural flake graphite are very nearly the same.
Accompanying drawing explanation:
Fig. 1 is initial graphite (a), the graphite oxide (b) of embodiment 1 preparation and the XRD figure of Graphene (c);
Fig. 2 is initial graphite (a), the graphene oxide (b) of embodiment 1 preparation and Raman (Raman) spectrogram of graphite oxide (c);
Fig. 3 is the graphite oxide (b) of embodiment 1 preparation and fourier-transform infrared (FTIR) spectrogram of Graphene (d) prepared by Graphene (c), embodiment 2;
Fig. 4 is transmission electron microscope (TEM) photo that embodiment 1 prepares the Graphene (d) of Graphene (c) and embodiment 2 preparations.
Embodiment:
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
1) preparation of graphite oxide:
Getting 1g (83 order) natural flake graphite is, after 98% sulfuric acid mixes, to add 1.0g saltpetre with 50ml mass concentration, adds fast 6g potassium permanganate in the water-bath of 15 ℃, mixes, and adds the process of potassium permanganate to keep system temperature 0-20 ℃.Then system temperature is elevated to 40 ℃, reaction 3h, then add 30ml water, system is warming up to 80 ℃ of reaction 30min simultaneously, use again 50ml distilled water and 10ml hydrogen peroxide (30wt%) to reduce excessive potassium permanganate, centrifuge washing is that 5,40 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.XRD characterizes as shown in Fig. 1 curve b, can be 0.863nm in the hope of the interfloor distance of graphite oxide, compares the interlamellar spacing 0.34nm of initial graphite (a), has greatly increased, and illustrates that the effect of intercalation graphite oxide is very good.As shown in Figure 2 b, the G peak of graphite oxide is obviously better than D peak to Raman spectrum, illustrates that oxidation effectiveness is very good.As shown in Figure 3 b, each peak is respectively C-0:1052cm to fourier-transform infrared (FTIR) spectrum
-1, C-0-C:1283cm
-1, 0-H:1385cm
-1, C=C:1635cm
-1and C=O:1715cm
-1, each characteristic peak intensity is high, illustrates that surperficial oxy radical content is many, consistent with the result that Raman characterizes with XRD.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dissolved in water, being configured to mass concentration is the graphite oxide suspension liquid of 7mg/ml, by this suspension liquid ultrasonic under 40KHZ frequency 10min, be then placed on vibrator, under 160rpm/min speed, shake 12h, obtain uniform and stable graphite oxide suspension liquid.
3) preparation of Graphene suspension liquid:
The graphene oxide liquid of getting 50ml 7mg/ml, is placed in 150ml Erlenmeyer flask, and it is 9 that the ammoniacal liquor that is 10% by mass concentration regulates pH, adds 1.0g xitix, continues to stir.Erlenmeyer flask is placed in to the water-bath heating in advance, controls temperature of reaction system at 90 ℃, the reaction times is 20min.Obtain uniform Graphene suspension liquid.XRD characterizes as shown in Fig. 1 curve c, can be 0.372nm in the hope of the interfloor distance of the Graphene of preparation, with the graphene layer spacing of former bibliographical information, comes to the same thing.Ranman spectrum is as shown in Fig. 2 spectral line c, and than G peak, D peak obviously strengthens, and illustrates and has well recovered the perfect crystalline network of Graphene, and reduction effect is good, and the Graphene of preparation is of high quality.Fourier-transform infrared (FTIR) spectrum is as shown in Fig. 3 spectral line c, than spectral line b, the peak of various oxy radicals has significantly to weaken even and disappears, illustrate that reduction reaction well removed the oxy radical on graphite oxide surface, recovered the perfect crystalline network of Graphene, reduction effect is very good, and the Graphene quality of preparation is high, consistent with the structure of Raman spectral characterization.TEM characterizes the Graphene of preparation as shown in Fig. 4 curve c, can know the Graphene of seeing individual layer, and transmitance is high, and size is large, is of high quality.
Embodiment 2:
1) preparation of graphite oxide:
Getting 1g (83 order) natural flake graphite is, after 98% sulfuric acid mixes, to add 1.2g saltpetre with 45ml mass concentration, adds fast 3g potassium permanganate in the water-bath of 10 ℃, mixes, and adds the process of potassium permanganate to keep system temperature 0-20 ℃.Then system temperature is elevated to 50 ℃, reaction 2h, then add 50ml water, system is warming up to 90 ℃ of reaction 20min simultaneously, use again 100ml distilled water and 6ml hydrogen peroxide (30wt%) to reduce excessive potassium permanganate, centrifuge washing is that 6,60 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.Similar with embodiment 1 characterization result, by XRD analysis, trying to achieve interfloor distance is 0.853nm, shows that graphite oxide oxidation effectiveness is good.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in water, being configured to concentration is the graphite oxide suspension liquid of 5mg/ml, by this suspension liquid ultrasonic 5min under 80KHZ frequency, then suspension liquid is placed on vibrator, under 180rpm/min speed, shake 8h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
The graphene oxide liquid of getting 50ml 5mg/ml, is placed in 150ml Erlenmeyer flask, and it is 10 that the ammoniacal liquor that is 20% by mass concentration regulates pH, adds the sodium pyrosulfate (NaHSO3) of 0.8g, keeps stirring.Erlenmeyer flask is placed in to the water-bath heating in advance, controls temperature of reaction system at 93 ℃, the reaction times is 2h.Obtain uniform Graphene suspension liquid.Fourier-transform infrared (FTIR) spectrum is as shown in Fig. 3 spectral line d, the peak of various oxy radicals has significantly to weaken even and disappears, illustrate that reduction reaction well removed the oxy radical on graphite oxide surface, recovered the perfect crystalline network of Graphene, reduction effect is very good, and the Graphene quality of preparation is high.TEM characterizes the Graphene of preparation as shown in Fig. 4 curve d, can know the Graphene of seeing individual layer, and transmitance is high, is of high quality.
Embodiment 3:
1) preparation of graphite oxide:
Getting 1g (16 order) natural flake graphite is, after 98% sulfuric acid mixes, to add 1.5g saltpetre with 40ml mass concentration, adds fast 6g potassium perchlorate in the water-bath of 5 ℃, mixes, and adds the process of potassium perchlorate to keep system temperature 0-20 ℃.Then system temperature is elevated to 60 ℃, reaction 1.5h, then adds 80ml water, system is warming up to 95 ℃ of reaction 10min simultaneously, then adds 200ml distilled water termination reaction, and centrifuge washing is that 7,70 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.Consistent with embodiment 1 characterization result, the interfloor distance of graphite oxide is 0.835nm, and than initial graphite, interfloor distance has obvious increase, illustrates that graphite oxide oxidation effectiveness is fine.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in water, being configured to mass concentration is the graphite oxide suspension liquid of 3mg/ml, by this suspension liquid ultrasonic 5min under 80KHZ frequency, then suspension liquid is placed on vibrator, under 200rpm/min speed, shake 6h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
The graphene oxide liquid of getting 50ml 3mg/ml, is placed in 150ml Erlenmeyer flask, and it is 10 that the ammoniacal liquor that is 25% by mass concentration regulates pH, adds the sodium bisulfite (NaHSO of 1.5g
3), adding mass concentration is 10% polyoxyethylene laurel ether (10%Brij-35) aqueous solution 2g, keeps stirring.Erlenmeyer flask is placed in to the water-bath heating in advance, controls temperature of reaction system at 96 ℃, the reaction times is 3h.By characterizing, the Graphene of preparation is consistent with 2 result with embodiment 1, and by adding tensio-active agent, the dispersion effect of Graphene in water is better, and quality is high, and lamella size is large, and major part is all single-layer graphene.
Embodiment 4:
1) preparation of graphite oxide:
Getting 10g (83 order) natural flake graphite is, after 98% sulfuric acid mixes, to add 15g saltpetre with 400ml mass concentration, adds fast 60g potassium permanganate in the water-bath of 5 ℃, mixes, and adds the process of potassium permanganate to keep system temperature 0-20 ℃.Then system temperature is elevated to 70 ℃, reaction 1h, then add 500ml water, system is warming up to 95 ℃ of reaction 20min simultaneously, use again 2L distilled water and 100ml hydrogen peroxide (30wt%) to reduce excessive potassium permanganate, centrifuge washing is that 5,60 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.The graphite oxide that characterizes preparation, similar with the result of embodiment 1, the interfloor distance of trying to achieve graphite oxide is 0.823nm, illustrates that oxidation effectiveness is fine.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in water, being configured to concentration is the graphite oxide suspension liquid of 2mg/ml, by this suspension liquid ultrasonic 5min under 80KHZ frequency, then suspension liquid is placed on vibrator, under 200rpm/min speed, shake 6h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
The graphene oxide liquid of getting 50ml 2mg/ml, is placed in 150ml Erlenmeyer flask, and it is 9 that the ammoniacal liquor that is 28% by mass concentration regulates pH, adds 0.2g oxammonium hydrochloride, keeps stirring.Erlenmeyer flask is placed in to the water-bath heating in advance, controls temperature of reaction system at 90 ℃, the reaction times is 1h.By characterizing, the Graphene of preparation is similar with 2 result with embodiment 1, being dispersed in water of graphene uniform, and quality is high, and lamella size is large, and the number of plies is few.
Embodiment 5:
1) preparation of graphite oxide:
Getting 10g (83 order) natural flake graphite is, after 67% nitric acid mixes, to add 15g saltpetre with 150ml concentration, adds fast 20g Vanadium Pentoxide in FLAKES under water bath condition, mixes, and adds the process of Vanadium Pentoxide in FLAKES to keep system temperature at 0-20 ℃.Then system temperature is elevated to 70 ℃, reaction 1h, then adds 400ml water, system is warming up to 95 ℃ of reaction 10min simultaneously, then uses 2L distilled water, and centrifuge washing is that 6,50 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.By characterizing, the interfloor distance that obtains graphite oxide is 0.836nm, and oxidation effectiveness is fine.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in water, being configured to concentration is the graphite oxide suspension liquid of 3mg/ml, by this suspension liquid ultrasonic 10min under 40KHZ frequency, then suspension liquid is placed on vibrator, under 160rpm/min speed, shake 12h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
The graphene oxide liquid of getting 50ml 2mg/ml, is placed in 150ml Erlenmeyer flask, and it is 9,0.4g oxammonium hydrochloride that the ammoniacal liquor that is 28% by mass concentration regulates pH, and adding mass concentration is 10% triton X-100 aqueous solution 2g, keeps stirring.Erlenmeyer flask is placed in to the water-bath heating in advance, controls temperature of reaction system at 90 ℃, the reaction times is 1h.By characterizing, the Graphene of preparation is similar with 2 result with embodiment 1, being dispersed in water of graphene uniform, and quality is high, and lamella size is large, and the number of plies is few.
Claims (6)
1. a method for preparing grapheme through oxidation reduction, its concrete steps are as follows:
1) preparation of graphite oxide:
Hummer legal system by modification is for graphite oxide, by the volume of strong acid and the mass ratio of graphite, be after 15ml/g-50ml/g gets natural flake graphite and mixes with strong acid solution, then add saltpetre, wherein saltpetre and graphite mass ratio are 1-2:1, at bath temperature, be to add strong oxidizer at 0-20 ℃, wherein the mass ratio of strong oxidizer and graphite is 2-6:1, be warming up at 40-70 ℃ and react 1-3h, by the volume of distilled water, be 30ml/g-80ml/g with the ratio of graphite, add distilled water, at 75-95 ℃ of reaction 10-30min, stop oxidizing reaction, filtration or centrifuge washing graphite oxide system pH are between 5-7, at 40-80 ℃, vacuum-drying obtains oxidation graphite solid,
2) preparation of graphene oxide:
The oxidation graphite solid that step 1) is prepared is dispersed in water, the graphite oxide suspension liquid that formation mass concentration is 2-7.0mg/ml by the ultrasonic dispersion of this suspension liquid, then shakes and peels off on vibrator, realize individual layer and peel off, obtain uniform and stable graphene oxide suspension liquid; Wherein ultrasonic frequency is 40-80KHz, and ultrasonic time is 5-10 minute; Vibrator speed is 160-200rpm, and concussion splitting time is 6-12h;
3) preparation of Graphene suspension liquid:
By step 2) to add alkali to regulate pH in the graphene oxide suspension liquid that makes be between 9-10, then by the mass ratio of graphene oxide in reductive agent and graphene oxide suspension liquid, be 2-10:1, reductive agent is joined in graphene oxide suspension liquid, the tensio-active agent that the mass ratio that adds again graphene oxide is 0-2:1, in temperature, be to react 20min-3h at 90-96 ℃, obtain uniform and stable graphene dispersing solution; The pH alkali used of wherein said adjusting graphene oxide solution is that mass concentration is the ammoniacal liquor of 10-28%; Described reductive agent is at least a kind of in xitix, sodium bisulfite or oxammonium hydrochloride.
2. method according to claim 1, is characterized in that: the sulfuric acid that described strong acid mass concentration is 98%, mass concentration are the mixing acid of 60-67% nitric acid or both arbitrary proportions.
3. method according to claim 1, is characterized in that: described strong oxidizer is at least a kind of in potassium permanganate, potassium perchlorate or Vanadium Pentoxide in FLAKES.
4. method according to claim 3, it is characterized in that: strong oxidizer is potassium permanganate, first add distilled water then to add hydrogen peroxide to stop oxidizing reaction, wherein adding the volume of distilled water and the ratio of graphite is 50ml/g-200ml/g, the mass concentration of hydrogen peroxide is 30%, and adding the volume of hydrogen peroxide and the mass ratio of potassium permanganate is 1ml/g-3ml/g.
5. method according to claim 3, is characterized in that: strong oxidizer is potassium perchlorate or Vanadium Pentoxide in FLAKES, adds distilled water to stop oxidizing reaction, and wherein adding the volume of distilled water and the ratio of graphite is 50ml/g-200ml/g.
6. method according to claim 1, is characterized in that: the tensio-active agent described in step 3) is polyoxyethylene laurel ether or triton X-100.
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