CN102502612A - 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 the method that a kind of redox prepares Graphene, belong to the technology of preparing of Graphene.
Background technology:
The term Graphene is meant the monolayer carbon atom of the cellular crystalline network of tightly packed two dimension six sides of one-tenth.Two scientists of the Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselov are obtaining initiative progress (K.S.Novoselov aspect the preparation two-dimensional space material Graphene (Graphene); A.K.Geim et al Science 306; 666 (2004)), obtained Nobel Prize in physics in 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 present known other all materials especially, can predict nano electron device and unicircuit, flexible electronic device in future; Novel electron devices such as ultra-high sensitive transmitter, matrix material, solar cell; Super capacitor, aspects such as hydrogen storage material are with a wide range of applications.
Since Graphene comes to light, constantly obtained important progress about the preparation research of Graphene.The preparation method who has reported at present mainly contains that micromechanics is peeled off, epitaxy, chemical vapour deposition and solution prepare mutually etc. several kinds; Particularly chemical Vapor deposition process and solution chemistry method (graphite oxide method) make the macro preparation Graphene become possibility; But compare the solution chemistry method, additive method lowly is 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 mainly is to utilize strong oxidizer that natural graphite is carried out obtaining graphite oxide after the intercalation oxidation, then with graphite oxide through ultrasonic, stir or concussion is carried out individual layer and peeled off and obtain graphene oxide, after reduction obtains Graphene.Oxidation reduction process can be prepared Graphene in a large number, efficiently, and process is simple, so graphene oxide is a valid approach of mass preparation 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 are very big arguement in the reaction mechanism of oxidation stage, the chemical structure of graphite oxide, and the Graphene size that obtains less (having only several microns usually), preparation cycle are long, and production concentration is low; Still have bigger distance from scale operation, seriously hindered follow-up large-scale application.Therefore, how efficiently, on a large scale, cheaply, controllably prepare and synthesize one of research that large-sized grapheme material still is this field and key in application.Secondly at reduction phase, recover the perfect crystalline network of Graphene, fundamentally be exactly the various groups of removing above the graphene oxide (hydroxyl, carboxyl, epoxy group(ing), carbonyl), and this process generally will be used very strong reductive agent.Present oxidizing reaction mainly contains reductive agent method and thermal reduction method.Used reductive agent mainly contains Hydrazine Hydrate 80, Peng Qinghuana, Ursol D etc. at present, though these reductive agents can be effectively with the graphite oxide reduction, its huge toxicity has limited promotion and application.Recently, the people is arranged again successively with green oxidation agent such as xitix, glucose, Hydrocerol A, amino acid, sulfide, but their reduction effect there is not Hydrazine Hydrate 80 good, serious agglomeration.Therefore seeking effective and green reductive agent, is the another important trend of reduction preparation Graphene.
Summary of the invention:
The object of the invention provides a kind of redox to prepare the method for Graphene for the shortcoming and defect of improving current liquid phase Graphene technology of preparing.
Technical scheme of the present invention is: a kind of redox prepares the method for Graphene, and its concrete steps are following:
1) preparation of graphite oxide:
Hummer legal system through modification is equipped with graphite oxide; By the mass ratio of the volume of strong acid and graphite is after 15ml/g-50ml/g gets natural flake graphite and strong acid solution and mixes, to add saltpetre then, and wherein saltpetre and graphite mass ratio are 1-2: 1; Be 0-20 ℃ at bath temperature and add strong oxidizer down, wherein the mass ratio of strong oxidizer and graphite is 2-6: 1, be warming up to 40-70 ℃ of reaction 1-3h down; Ratio by the volume of zero(ppm) water and graphite is 30ml/g-80ml/g; Add zero(ppm) water,, stop oxidizing reaction at 75-95 ℃ of reaction 10-30min; Filtration or centrifuge washing graphite oxide system pH are between the 5-7, obtain oxidation graphite solid 40-80 ℃ of following vacuum-drying;
2) preparation of graphene oxide:
The oxidation graphite solid that step 1) is prepared is dispersed in the water; Forming mass concentration is the graphite oxide suspension liquid of 2-7.0mg/ml, with this suspension liquid ultra-sonic dispersion, on vibrator, shakes then and peels off; The realization individual layer is peeled off, and obtains uniform and stable graphene oxide suspension liquid;
3) preparation of Graphene suspension liquid:
With step 2) adding alkali in the graphene oxide suspension liquid that makes, to regulate pH be between the 9-10; Mass ratio by graphene oxide in reductive agent and the graphene oxide suspension liquid is 2-10 then: 1; Reductive agent is joined in the graphene oxide suspension liquid; The mass ratio that adds graphene oxide again is 0-2: 1 tensio-active agent is 90-96 ℃ of reaction 20min-3h down in temperature, obtains uniform and stable Graphene dispersion liquid.
Preferably above-mentioned strong acid mass concentration is that 98% sulfuric acid, mass concentration are the mixing acid of 60-67% nitric acid or both arbitrary proportions; Preferred described strong oxidizer is at least a kind of in potassium permanganate, potassium perchlorate or the Vanadium Pentoxide in FLAKES; Preferred steps 3) reductive agent described in is at least a kind of in xitix, sodium sulfite anhy 96 or the oxammonium hydrochloride.
Termination oxidizing reaction described in the step 1) does; If the strong oxidizer that adds is a potassium permanganate; Add zero(ppm) water earlier and add ydrogen peroxide 50 termination oxidizing reaction then; The volume that wherein adds zero(ppm) water is 50ml/g-200ml/g with the ratio of graphite; The mass concentration of ydrogen peroxide 50 is 30%, and adding the volume of ydrogen peroxide 50 and the mass ratio of potassium permanganate is 1ml/g-3ml/g; If the strong oxidizer that adds is potassium perchlorate or Vanadium Pentoxide in FLAKES, add zero(ppm) water and stop oxidizing reaction, the volume that wherein adds zero(ppm) water is 50ml/g-200ml/g with the ratio of graphite.
Preferred steps 2) ultrasonic frequency is 40-80KHz in, and ultrasonic time is 5-10 minute; Vibrator speed is 160-200rpm, and the concussion splitting time is 6-12h.The used alkali of pH 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 X100.
The present invention optimizes the condition and the technology of reaction through the mutual comparison of several kinds of green non-poisonous reductive agent relative merits, seeks best, suitable industrialized technology.Xitix, acidity has stronger reductibility, and heating or in solution, be prone to oxygenolysis more is prone to oxidizedly under alkaline condition, is the hexose verivate.In the process of redox graphene; Generate Try simultaneously, tryptophane has the effect that disperses Graphene, stops the reunion of Graphene; So make reductive agent with xitix, no longer need add the reunion that unnecessary tensio-active agent disperses Graphene, stops Graphene.But xitix is owing to cost an arm and a leg, and industrially scalable becomes to produce cost higher relatively.Oxammonium hydrochloride, mainly as reductive agent and developer, toxicity is little.In the process of preparation Graphene suspension liquid, be that to utilize ammoniacal liquor to react with oxammonium hydrochloride be to discharge the free azanol, azanol obtains Graphene solution as reductive agent and graphite oxide alkene reaction in 90 ℃ of water-baths.With respect to xitix, oxammonium hydrochloride is cheap, and industrial production cost is low, is easy to scale operation.But the Graphene strength of solution of oxammonium hydrochloride preparation is very low, and the concentration height is easy to generate reunion.Optimize and add tensio-active agent, prevention agglomeration, the high Graphene solution of preparation concentration.Sodium pyrosulfate, with respect to existing reductive agent, sodium pyrosulfate substitutes big, the dangerous reagent of toxicity such as hydrazine, and the preparation method is safety and environmental friendliness more.Secondly, compare with other reductive agents, the Graphene that sodium sulfite anhy 96 is prepared has higher electroconductibility and quality, has well recovered the perfect crystalline network of Graphene.At last, the sodium pyrosulfate low in raw material cost is easy to get, preparation technology is simple, is fit to large-scale industrial production, can be widely used in novel grapheme material and preparation of devices.
Beneficial effect:
The technology that the present invention prepares Graphene is simple, and preparation efficiency is high, with low cost, and the Graphene size of preparation is big, and quality is high, is easy to the scale operation of industry.
The present invention adopts the use of uniting 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 big sheet graphite oxide; So for the big 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, size and initial natural flake graphite are very nearly the same.
Description of drawings:
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 the Graphene (d) that Graphene (c), embodiment 2 prepare;
Fig. 4 is transmission electron microscope (TEM) photo of the Graphene (d) of embodiment 1 preparation Graphene (c) and embodiment 2 preparations.
Embodiment:
Below in conjunction with accompanying drawing and embodiment the present invention is done further explain.
Embodiment 1:
1) preparation of graphite oxide:
Getting 1g (83 order) natural flake graphite and 50ml mass concentration is after 98% sulfuric acid mixes, and adds 1.0g saltpetre, in 15 ℃ water-bath, adds 6g potassium permanganate fast, mixes, and the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 40 ℃, reaction 3h adds 30ml water then; Simultaneously system is warming up to 80 ℃ of reaction 30min; Use the excessive potassium permanganate of 50ml zero(ppm) water and 10ml ydrogen peroxide 50 (30wt%) reduction again, centrifuge washing is that 5,40 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.XRD characterizes 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 explains that the effect of intercalation graphite oxide is very good.Raman spectrum is shown in Fig. 2 b, and the G peak of graphite oxide obviously is better than the D peak, explains that oxidation effectiveness is very good.Fourier-transform infrared (FTIR) spectrum is shown in Fig. 3 b, and each peak is respectively C-0:1052cm
-1, C-0-C:1283cm
-1, 0-H:1385cm
-1, C=C:1635cm
-1And C=O:1715cm
-1, each characteristic peak intensity is high, explains that surperficial oxy radical content is many, and is consistent with the result that Raman characterizes with XRD.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dissolved in the water; Being configured to mass concentration is the graphite oxide suspension liquid of 7mg/ml, with this suspension liquid ultrasonic under the 40KHZ frequency 10min, be placed on the vibrator then; Under 160rpm/min speed, shake 12h, obtain uniform and stable graphite oxide suspension liquid.
3) preparation of Graphene suspension liquid:
Get the graphene oxide liquid of 50ml 7mg/ml, place the 150ml Erlenmeyer flask, use mass concentration be 10% ammoniacal liquor to regulate pH be 9, add the 1.0g xitix, continue to stir.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 20min.Obtain uniform Graphene suspension liquid.XRD characterizes shown in Fig. 1 curve c, can be 0.372nm in the hope of the interfloor distance of the Graphene of preparation, comes to the same thing with the Graphene interfloor distance of former bibliographical information.Ranman spectrum is shown in Fig. 2 spectral line c, and than the G peak, the D peak obviously strengthens, and explains 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 shown in Fig. 3 spectral line c; Than spectral line b, the peak of various oxy radicals has and significantly weakens even disappear, and explains 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, and is consistent with the structure of Raman spectral characterization.TEM characterizes the Graphene of preparation shown in Fig. 4 curve c, can know the Graphene of seeing individual layer, and transmitance is high, and size is big, is of high quality.
Embodiment 2:
1) preparation of graphite oxide:
Getting 1g (83 order) natural flake graphite and 45ml mass concentration is after 98% sulfuric acid mixes, and adds 1.2g saltpetre, in 10 ℃ water-bath, adds 3g potassium permanganate fast, mixes, and the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 50 ℃, reaction 2h adds 50ml water then; Simultaneously system is warming up to 90 ℃ of reaction 20min; Use the excessive potassium permanganate of 100ml zero(ppm) water and 6ml ydrogen peroxide 50 (30wt%) reduction again, centrifuge washing is that 6,60 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.Similar with embodiment 1 characterization result, through XRD analysis, trying to achieve interfloor distance is 0.853nm, shows that the graphite oxide oxidation effectiveness is good.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in the water; Being configured to concentration is the graphite oxide suspension liquid of 5mg/ml, with this suspension liquid ultrasonic 5min under the 80KHZ frequency, then suspension liquid is placed on the vibrator; Under 180rpm/min speed, shake 8h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
Get the graphene oxide liquid of 50ml 5mg/ml, place the 150ml Erlenmeyer flask, use mass concentration be 20% ammoniacal liquor to regulate pH be 10, add the sodium pyrosulfate (NaHSO3) of 0.8g, keep stirring.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 93 ℃, and the reaction times is 2h.Obtain uniform Graphene suspension liquid.Fourier-transform infrared (FTIR) spectrum is shown in Fig. 3 spectral line d; The peak of various oxy radicals has and significantly weakens even disappear; Explain 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 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 and 40ml mass concentration is after 98% sulfuric acid mixes, and adds 1.5g saltpetre, in 5 ℃ water-bath, adds the 6g potassium perchlorate fast, mixes, and the process that adds potassium perchlorate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 60 ℃, reaction 1.5h adds 80ml water then, simultaneously system is warming up to 95 ℃ of reaction 10min, adds 200ml zero(ppm) water termination reaction again, 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 tangible increase, explains that the graphite oxide oxidation effectiveness is fine.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in the water; Being configured to mass concentration is the graphite oxide suspension liquid of 3mg/ml, with this suspension liquid ultrasonic 5min under the 80KHZ frequency, then suspension liquid is placed on the vibrator; Under 200rpm/min speed, shake 6h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
Get the graphene oxide liquid of 50ml 3mg/ml, place the 150ml Erlenmeyer flask, use mass concentration be 25% ammoniacal liquor to regulate pH be 10, add the sodium sulfite anhy 96 (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 the water-bath that heats in advance, and the control temperature of reaction system is at 96 ℃, and the reaction times is 3h.Through characterizing, the Graphene of preparation is consistent with 2 result with embodiment 1, and through the adding tensio-active agent, the dispersion effect of Graphene in water is better, the quality height, and the lamella size is big, and major part all is a single-layer graphene.
Embodiment 4:
1) preparation of graphite oxide:
Getting 10g (83 order) natural flake graphite and 400ml mass concentration is after 98% sulfuric acid mixes, and adds 15g saltpetre, in 5 ℃ water-bath, adds 60g potassium permanganate fast, mixes, and the process that adds potassium permanganate keeps 0-20 ℃ of system temperature.Then system temperature is elevated to 70 ℃, reaction 1h adds 500ml water then; Simultaneously system is warming up to 95 ℃ of reaction 20min; Use the excessive potassium permanganate of 2L zero(ppm) water and 100ml ydrogen peroxide 50 (30wt%) reduction again, centrifuge washing is that 5,60 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.Characterize the graphite oxide of preparation, similar with the result of embodiment 1, the interfloor distance of trying to achieve graphite oxide is 0.823nm, explains that oxidation effectiveness is fine.
2) preparation of graphene oxide suspension liquid:
Oxidation graphite solid is dispersed in the water; Being configured to concentration is the graphite oxide suspension liquid of 2mg/ml, with this suspension liquid ultrasonic 5min under the 80KHZ frequency, then suspension liquid is placed on the vibrator; Under 200rpm/min speed, shake 6h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
Get the graphene oxide liquid of 50ml 2mg/ml, place the 150ml Erlenmeyer flask, use mass concentration be 28% ammoniacal liquor to regulate pH be 9, add the 0.2g oxammonium hydrochloride, keep stirring.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 1h.Through characterizing, the Graphene of preparation is similar with 2 result with embodiment 1, and Graphene is dispersed in the water uniformly, and quality is high, and the lamella size is big, and the number of plies is few.
Embodiment 5:
1) preparation of graphite oxide:
Getting 10g (83 order) natural flake graphite and 150ml concentration is after 67% nitric acid mixes, and adds 15g saltpetre, adds the 20g Vanadium Pentoxide in FLAKES under the water bath condition fast, mixes, and the process that adds Vanadium Pentoxide in FLAKES keeps system temperature at 0-20 ℃.Then system temperature is elevated to 70 ℃, reaction 1h adds 400ml water then, simultaneously system is warming up to 95 ℃ of reaction 10min, uses 2L zero(ppm) water again, and centrifuge washing is that 6,50 ℃ of vacuum-dryings obtain oxidation graphite solid to pH.Through 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 the water; Being configured to concentration is the graphite oxide suspension liquid of 3mg/ml, with this suspension liquid ultrasonic 10min under the 40KHZ frequency, then suspension liquid is placed on the vibrator; Under 160rpm/min speed, shake 12h, obtain uniform and stable graphite oxide suspension liquid;
3) preparation of Graphene suspension liquid:
Get the graphene oxide liquid of 50ml 2mg/ml, place the 150ml Erlenmeyer flask, use mass concentration be 28% ammoniacal liquor to regulate pH be 9, the 0.4g oxammonium hydrochloride adds mass concentration and is 10% Triton X100 aqueous solution 2g, keeps stirring.Erlenmeyer flask is placed the water-bath that heats in advance, and the control temperature of reaction system is at 90 ℃, and the reaction times is 1h.Through characterizing, the Graphene of preparation is similar with 2 result with embodiment 1, and Graphene is dispersed in the water uniformly, and quality is high, and the lamella size is big, and the number of plies is few.
Claims (8)
1. an a kind of redox prepares the method for Graphene, and its concrete steps are following:
1) preparation of graphite oxide:
Hummer legal system through modification is equipped with graphite oxide; By the mass ratio of the volume of strong acid and graphite is after 15ml/g-50ml/g gets natural flake graphite and strong acid solution and mixes, to add saltpetre then, and wherein saltpetre and graphite mass ratio are 1-2: 1; Be 0-20 ℃ at bath temperature and add strong oxidizer down, wherein the mass ratio of strong oxidizer and graphite is 2-6: 1, be warming up to 40-70 ℃ of reaction 1-3h down; Ratio by the volume of zero(ppm) water and graphite is 30ml/g-80ml/g; Add zero(ppm) water,, stop oxidizing reaction at 75-95 ℃ of reaction 10-30min; Filtration or centrifuge washing graphite oxide system pH are between the 5-7, obtain oxidation graphite solid 40-80 ℃ of following vacuum-drying;
2) preparation of graphene oxide:
The oxidation graphite solid that step 1) is prepared is dispersed in the water; Forming mass concentration is the graphite oxide suspension liquid of 2-7.0mg/ml, with this suspension liquid ultra-sonic dispersion, on vibrator, shakes then and peels off; The realization individual layer is peeled off, and obtains uniform and stable graphene oxide suspension liquid;
3) preparation of Graphene suspension liquid:
With step 2) adding alkali in the graphene oxide suspension liquid that makes, to regulate pH be between the 9-10; Mass ratio by graphene oxide in reductive agent and the graphene oxide suspension liquid is 2-10 then: 1; Reductive agent is joined in the graphene oxide suspension liquid; The mass ratio that adds graphene oxide again is 0-2: 1 tensio-active agent is 90-96 ℃ of reaction 20min-3h down in temperature, obtains uniform and stable Graphene dispersion liquid.
2. method according to claim 1 is characterized in that: described strong acid mass concentration is that 98% sulfuric acid, 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 the Vanadium Pentoxide in FLAKES.
4. according to claim 1 or 3 described methods; It is characterized in that: the termination oxidizing reaction described in the step 1) is: if the strong oxidizer that adds is a potassium permanganate; Add zero(ppm) water earlier and add ydrogen peroxide 50 termination oxidizing reaction then; The volume that wherein adds zero(ppm) water is 50ml/g-200ml/g with the ratio of graphite, and the mass concentration of ydrogen peroxide 50 is 30%, and adding the volume of ydrogen peroxide 50 and the mass ratio of potassium permanganate is 1ml/g-3ml/g; If the strong oxidizer that adds is potassium perchlorate or Vanadium Pentoxide in FLAKES, add zero(ppm) water and stop oxidizing reaction, the volume that wherein adds zero(ppm) water is 50ml/g-200ml/g with the ratio of graphite.
5. the method that requires according to right 1 is characterized in that: step 2) in ultrasonic frequency be 40-80KHz, ultrasonic time is 5-10 minute; Vibrator speed is 160-200rpm, and the concussion splitting time is 6-12h.
6. the method that requires according to right 1 is characterized in that: the reductive agent described in the step 3) is at least a kind of in xitix, sodium sulfite anhy 96 or the oxammonium hydrochloride.
7. the method that requires according to right 1, it is characterized in that: the used alkali of pH of the adjusting graphene oxide solution described in the step 3) is that mass concentration is the ammoniacal liquor of 10-28%.
8. the method that requires according to right 1, it is characterized in that: the tensio-active agent described in the step 3) is polyoxyethylene laurel ether or Triton X100.
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