CN103803537A - Preparation method of graphene - Google Patents
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- CN103803537A CN103803537A CN201410030357.4A CN201410030357A CN103803537A CN 103803537 A CN103803537 A CN 103803537A CN 201410030357 A CN201410030357 A CN 201410030357A CN 103803537 A CN103803537 A CN 103803537A
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- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
Abstract
The invention discloses a preparation method of graphene, belonging to the technical field of nanomaterials. The method comprises the steps of adding graphite oxide powder into deionized water, and carrying out ultrasonic oscillation to obtain a graphene oxide dispersion liquid of the graphene oxide in the deionized water; adding green and nontoxic caffeic acid powder into the graphene oxide dispersion liquid to carry out reduction reaction to obtain a graphene solution; finally, filtering through a microporous filter membrane, collecting and carrying out vacuum drying to obtain graphene. By using the method, caffeic acid as a reducing agent widely exists in various plants so as to be green and nontoxic; in addition, the preparation method is simple in process, mild in reaction condition and free of causing environment pollution and generating hazards to human health; moreover, caffeic acid has strong reducing capacity, so that impurity elements or functional groups can not be introduced to a reduzate, the prepared graphene is high in purity and quality, and caffeic acid is suitable for the large-scale industrial production of the graphene and beneficial to the wide application of relevant materials of the graphene.
Description
Technical field
The present invention relates to technical field of nano material, relate in particular to a kind of method of preparing Graphene.
Background technology
Graphene is a kind of individual layer sheet structure novel carbon material being made up of carbon atom, and atom is bi-dimensional cellular shape in the ideal situation to be arranged, and is current known the thinnest material in the world.Graphene, since within 2004, finding first, has caused the very big research interest of vast researcher, has become in recent years one of the ambit such as material, physics and chemistry research hot topic.Due to its unique appearance structure, Graphene has the performances such as very good physics, chemistry, calorifics and mechanics, and it is had broad application prospects in advanced composite material, energy storage, catalysis and sensor field.Meanwhile, the Graphene preparation technology's of large-scale low-cost R and D are the keys that promote above-mentioned application.
At present, the method for preparing for Graphene mainly contains mechanically peel method, epitaxial growth method, arc discharge method, chemical Vapor deposition process, hot reducing method and chemical reduction method etc.Wherein, mechanically peel method, arc discharge method, epitaxial growth method and chemical Vapor deposition process production cost is high and productive rate is lower; therefore be not suitable for the use at large-scale production Graphene; hot reducing method need to carry out under the high temperature more than 1000 ℃ conventionally, and energy consumption is higher and react required complicated condition.By comparison, chemical reduction method is because production cost is lower, and technique is simple, and reaction conditions gentleness is extensively thought and had the great potential that large-scale low-cost is prepared Graphene associated materials.
The ultimate principle of chemical preparation Graphene is, first by strong oxidizer, graphite is oxidized and peeled off, and obtains graphene oxide, then eliminates the oxygen-containing functional group of graphene oxide by reductive agent, and then acquisition grapheme material.At present, the reductive agent extensively adopting comprises hydrazine class, sodium borohydride and Resorcinol etc., can obtain that reducing degree is higher, the Graphene of better performances.But these reductive agents have larger toxicity or have the problems such as inflammable and explosive, therefore can cause environmental pollution and be detrimental to health; Meanwhile, impurity is in use easily introduced in partial reduction agent in product, and then has a strong impact on purity and the quality of the Graphene of preparation.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of green non-poisonous method of preparing Graphene, has compared with large toxicity or has inflammable and explosive problem and the environmental pollution that causes and being detrimental to health to overcome reductive agent; Also overcome that partial reduction agent is in use easily introduced impurity in product and the problem that has a strong impact on Graphene quality simultaneously.
The present invention is for solving the problems of the technologies described above, and a kind of method of preparing Graphene providing comprises:
The preparation process of graphene oxide: graphite oxide powder is added in deionized water, obtain the graphene oxide dispersion liquid of graphene oxide in deionized water by ultrasonic oscillation; Wherein, the usage ratio of graphite oxide powder and deionized water is 0.1 milligram: 1 milliliter～1 milligram: 1 milliliter;
The preparation process of Graphene: add coffic acid powder in graphene oxide dispersion liquid, wherein, the mass ratio of coffic acid powder and graphite oxide powder is 10:1～50:1; The mixture oil bath obtaining is heated to 85 ℃～95 ℃ and continue to stir, obtains graphene solution by 2 hours～24 hours reduction reactions, then with filtering with microporous membrane and collect product, last vacuum-drying product obtains Graphene.
Preferably, before the method, also comprise the preparation process of graphite oxide:
The vitriol oil that is 98% by natural graphite and mass concentration at room temperature evenly mixes, at ice bath temperature, add in batches potassium permanganate and continue and stir, by the mixture heating in water bath to 35 obtaining ℃ and stir, react and add deionized water after 2 hours, then adding mass concentration is 30% hydrogen peroxide, the solution obtaining is cleaned repeatedly with hydrochloric acid and deionized water, and last vacuum-drying obtains graphite oxide powder; Wherein, the usage ratio of the vitriol oil and natural graphite is 25 milliliters: 1 gram, the mass ratio of potassium permanganate and natural graphite is 3.5:1～5.5:1, and the usage ratio of deionized water and natural graphite is 100 milliliters: 1 gram, the usage ratio of hydrogen peroxide and natural graphite is 8 milliliters: 1 gram.
Preferably, ice bath temperature refers to 0 ℃.
Preferably, add in batches potassium permanganate to comprise: in 1 hour～2 hours, point 6 homogeneous add potassium permanganate, and every timed interval adding for twice is 10min～20min.
Preferably, stirring comprises: adopt magnetic agitation.
Preferably, the solution obtaining is repeatedly cleaned further and is comprised with hydrochloric acid and deionized water:
First adopting volume fraction is that 10% dilute hydrochloric acid carries out 15min centrifuge washing, then adopts deionized water to carry out 15min centrifuge washing; Wherein, centrifugal rotational speed is 8000 revs/min.
Preferably, ultrasonic oscillation comprises: by graphite oxide powder and deionized water mixture supersound process 2 hours under 300W power.
Preferably, millipore filtration comprises: aperture is the polyvinylidene fluoride microporous filtering film of 0.22 μ m.
Preferably, lasting stirring comprises: adopt magnetic force to continue to stir.
Preferably, vacuum-drying comprises: in vacuum drying oven, at 35 ℃, be dried 24 hours.
The method of what the embodiment of the present invention provided prepare Graphene, adopts the coffic acid that is extensively present in various plants as reductive agent, and green non-poisonous, preparation technology is simple, and reaction conditions gentleness can not cause environmental pollution and be detrimental to health; And because coffic acid has strong reducing power, can not introduce impurity element or functional group in reduzate, Graphene purity and the quality of preparation are high, the large-scale industrial that is suitable for Graphene is produced, and is conducive to the widespread use of Graphene associated materials.
Accompanying drawing explanation
Graphene transmission electron microscope (TEM) figure that Fig. 1 obtains for the embodiment of the present invention three.
Graphene oxide and Graphene X-ray diffraction (XRD) spectrogram that Fig. 2 obtains for embodiment tri-.
The graphene oxide that Fig. 3 obtains for the embodiment of the present invention three and X-ray electronic energy (XPS) spectrogram of Graphene.
Ultraviolet-visible light (UV-vis) spectrogram of the Graphene that Fig. 4 obtains for the present embodiment five, the Graphene that embodiment tetra-obtains, Graphene that embodiment tri-obtains.
Thermogravimetric (TGA) performance chart of the Graphene that the Graphene that Fig. 5 obtains for the present embodiment five, the Graphene that embodiment tetra-obtains and embodiment tri-obtain.
Embodiment
In order to make technical problem to be solved by this invention, technical scheme and beneficial effect clearer, clear, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment mono-
A kind of method of preparing Graphene that the embodiment of the present invention provides comprises the following steps:
The preparation process of S20, graphene oxide: graphite oxide powder is added in deionized water, obtain the graphene oxide dispersion liquid of graphene oxide in deionized water by ultrasonic oscillation; Wherein, the usage ratio of graphite oxide powder and deionized water is 0.1mg:1ml～1mg:1ml, in every ml deionized water, adds 0.1 milligram～1 milligram graphite oxide powder.
The preparation process of S30, Graphene: add coffic acid powder in graphene oxide dispersion liquid, wherein, the mass ratio of coffic acid powder and graphite oxide powder is 10:1～50:1; The mixture oil bath obtaining is heated to 85 ℃～95 ℃ and continue to stir, obtains graphene solution by 2 hours～24 hours reduction reactions, then with filtering with microporous membrane and collect product, last vacuum-drying product obtains Graphene.
Wherein, oil bath refers to take oil as medium, heated oil, and mixture is put into beaker, with oil heating beaker.
As a kind of preferred embodiment, ultrasonic oscillation comprises: by graphite oxide powder and deionized water mixture supersound process 2 hours under 300W power.
As another kind of preferred embodiment, millipore filtration comprises: aperture is the polyvinylidene fluoride microporous filtering film of 0.22 μ m.
As another kind of preferred embodiment, lasting stirring comprises: adopt magnetic force to continue to stir.
As another kind of preferred embodiment, vacuum-drying comprises: in vacuum drying oven, at 35 ℃, be dried 24 hours.
The method of preparing Graphene provided by the invention, the beneficial effect compared with prior art having:
1) compare with chemical Vapor deposition process etc. with hot reducing method, mechanically peel method, arc discharge method, epitaxial growth method, low based on caffeinic chemical reduction method energy consumption and matching requirements, process is simple and productive rate is high, is applicable to carrying out the extensive preparation of Graphene.
2) compare with traditional preparation method based on redox graphenes such as hydrazine class, sodium borohydride and Resorcinol, coffic acid is a kind of green non-poisonous reductive agent, is extensively present in various plants.
3) due to the constructional feature of coffic acid uniqueness (thering is vicinal hydroxyl groups and height conjugation vinylformic acid side chain on phenyl ring), therefore have than green non-poisonous reductive agents such as gallic acid, tea-polyphenol and methyl alcohol and there is stronger reducing power, in final product, realize higher C/O ratio and reduction effect.
4) (need under alkaline environment, carry out during as reductive agent as sugar and Dopamine HCL than particular surroundings demand in use of partial reduction agent, natural cellulose needs ionic liquid during as reductive agent), adopt coffic acid during as reductive agent without adding any stablizer or dispersion agent, preparation process technique is simple, reaction conditions gentleness.
5) during than employing metallic reducing agent, easily in final product, introduce impurity element, coffic acid is elementary composition simple, can in reduction process, not introduce other impurity element or functional group, can guarantee product purity and quality level.
Embodiment bis-
A kind of method of preparing Graphene that the preferred embodiment of the present invention provides comprises the following steps:
The preparation process of S10, graphite oxide.
Specifically, the vitriol oil that is 98% by natural graphite and mass concentration at room temperature evenly mixes, and wherein the usage ratio of the vitriol oil and natural graphite is 25ml:1g, and every 1 gram of natural graphite adds 25 milliliters of vitriol oils; At ice bath temperature, add in batches potassium permanganate and continue and stir, wherein, ice bath temperature refers to 0 ℃, and the mass ratio of potassium permanganate and natural graphite is 3.5:1～5.5:1, preferably 3.5:1; By the mixture heating in water bath to 35 obtaining ℃ and stir, react and add deionized water after 2 hours, wherein the usage ratio of deionized water and natural graphite is 100ml:1g, every 1 gram of natural graphite adds 100 ml deionized water; Then adding mass concentration is 30% hydrogen peroxide, and wherein the ratio of hydrogen peroxide and natural graphite is 8ml:1g, and every 1 gram of natural graphite adds 8 milliliters of hydrogen peroxide; The solution obtaining is cleaned repeatedly with hydrochloric acid and deionized water, and last vacuum-drying obtains graphite oxide powder.
It should be noted that, the usage ratio of the above-mentioned vitriol oil, potassium permanganate, deionized water and hydrogen peroxide and natural graphite is to be 98% in the mass concentration of the vitriol oil of giving an example, the mass concentration of hydrogen peroxide is a kind of preferred embodiment under 30% prerequisite, and in practical application, the mass concentration of the vitriol oil and the mass concentration of hydrogen peroxide can be configured as required, in the time that the mass concentration of the vitriol oil or the mass concentration of hydrogen peroxide change, the usage ratio of the vitriol oil, potassium permanganate, deionized water and hydrogen peroxide and natural graphite also will be adjusted thereupon.In addition, the preparation method of graphite oxide also can adopt other modes to carry out completely, the mode that is not limited to describe in this step.
As another kind of preferred embodiment, add in batches potassium permanganate to comprise: in 1 hour～2 hours, point 6 homogeneous add potassium permanganate, and every timed interval adding for twice is 10min～20min.
As another kind of preferred embodiment, stirring comprises: adopt magnetic agitation.
As another kind of preferred embodiment, the solution obtaining is repeatedly cleaned further and comprised with hydrochloric acid and deionized water: first adopting volume fraction is that 10% dilute hydrochloric acid carries out 15min centrifuge washing; Then adopt deionized water to carry out 15min centrifuge washing; Wherein, centrifugal rotational speed is 8000 revs/min.
As another kind of preferred embodiment, vacuum-drying comprises: in vacuum drying oven, at 35 ℃, be dried 24 hours.
The preparation process of S20, graphene oxide.
Specifically, the graphite oxide powder that step S10 is obtained adds in deionized water, and wherein the usage ratio of graphite oxide powder and deionized water is 0.1mg:1ml～1mg:1ml; Obtain the graphene oxide dispersion liquid of graphene oxide in deionized water by ultrasonic oscillation.
The preparation process of S30, Graphene.
Specifically, in the graphene oxide dispersion liquid obtaining, add coffic acid powder at step S20, wherein the mass ratio of coffic acid powder and graphite oxide powder is 10:1～50:1, preferably 50:1; The mixture oil bath obtaining is heated to 85 ℃～95 ℃ and continue to stir, obtains graphene solution by 2 hours～24 hours reduction reactions, then with filtering with microporous membrane and collect product, last vacuum-drying obtains Graphene.
The method of preparing Graphene provided by the invention; take natural graphite as starting material; obtain graphene oxide powder by strong oxidizer; under ultrasonic oscillation effect, obtain the dispersion liquid of graphene oxide in deionized water; utilize green non-poisonous reductive agent coffic acid to realize the reduction of graphene oxide; finally obtain Graphene by filtration, collection and vacuum-drying, the large-scale industrial that is suitable for Graphene is produced, and is conducive to the widespread use of Graphene associated materials.
Embodiment tri-
The vitriol oil that is 98% by natural graphite and mass concentration at room temperature evenly mixes, and wherein the usage ratio of the vitriol oil and natural graphite is 25ml:1g; In 2 hours, divide at ice bath temperature (0 ℃), to add potassium permanganate for 6 times and continue and stir, every timed interval adding for twice is 20min, and the mass ratio of potassium permanganate and natural graphite is 3.5:1.By the mixture heating in water bath to 35 ℃ obtaining, and stir by magnetic stirring apparatus.React and add deionized water after 2 hours, wherein the usage ratio of deionized water and natural graphite is 100ml:1g, then adding mass concentration is 30% hydrogen peroxide, and wherein the usage ratio of hydrogen peroxide and natural graphite is 8ml:1g, and the solution obtaining is cleaned repeatedly with hydrochloric acid and deionized water.In cleaning process, first adopting volume fraction is that 10% dilute hydrochloric acid carries out 15min centrifuge washing, with method operation 4 times, then adopts deionized water to carry out 15min centrifuge washing, and with method operation 4 times, wherein centrifugal rotational speed is 8000 revs/min.Finally sample is placed in vacuum drying oven, at 35 ℃, is dried 24 hours, obtain graphite oxide powder.Obtained graphite oxide powder is added in deionized water, wherein the usage ratio of graphite oxide powder and deionized water is 0.1mg:1ml, graphite oxide powder and deionized water mixture are carried out to 2 hours supersound process under 300W power, carry out graphite oxide and peel off, obtain the dispersion liquid of graphene oxide in deionized water.In obtained graphene oxide dispersion liquid, add coffic acid powder, wherein the mass ratio of coffic acid powder and graphite oxide powder is 50:1, by the mixture oil bath obtaining be heated to 95 ℃ and by magnetic stirring apparatus continue stir, after reduction reaction, obtained graphene solution by 24 hours, then filter and collect product with the polyvinylidene fluoride microporous filtering film that aperture is 0.22 μ m, finally sample is placed in vacuum drying oven to the dry Graphene that obtains for 24 hours at 35 ℃.
Be illustrated in figure 1 Graphene transmission electron microscope (TEM) figure that the present embodiment three obtains.Can be observed by TEM figure, the Graphene obtaining is thin and transparent, and edge is fold slightly, meets the general pattern characteristic of Graphene.
As shown in Figure 2, the graphene oxide (a) obtaining for the present embodiment three for initial natural graphite, (b) and Graphene X-ray diffraction (XRD) spectrogram that (c) the present embodiment three obtains.From XRD spectra, (002) diffractive features peak position of the XRD of natural graphite is in 2 θ=26.6 °, and corresponding interlamellar spacing is 0.335nm; The characteristic peak that is positioned at 26.6 ° in the XRD spectra of graphene oxide disappears, and locates to form (001) diffractive features peak in 2 θ=10.02 °, and corresponding interlamellar spacing increases to 0.880nm; And the Graphene of preparing by the present embodiment (001) diffractive features peak disappears, locate to form a wider diffractive features peak simultaneously in 2 θ=24.79 °, respective layer spacing is 0.359nm, interlamellar spacing than natural graphite is bigger, but much smaller than the interlamellar spacing of graphene oxide, this has confirmed that coffic acid reduction has realized the reduction of graphene oxide and peeled off.
Figure 3 shows that (a) graphene oxide that embodiment tri-obtains and (b) X-ray electronic energy (XPS) spectrogram of Graphene.By the matching of C1s spectrogram, can parse 4 characteristic peaks corresponding different functional groups respectively, that is: 284.6(carbon-carbon double bond/singly-bound: C=C/C-C), 286.5 (hydroxyls: C-OH), 287.6 (carbonyls: C=O) and 289.1eV (carboxyl: O=C-OH).Can obviously be found out by Fig. 3, by embodiments of the invention three, each oxygen-containing functional group characteristic peak intensity of Graphene has reduction in various degree, and this confirms, in the process of chemical reduction, the fracture of carbon-oxygen bond to have occurred.By calculating, find that the Graphene C/O ratio preparing is 7.15, be significantly higher than the C/O of graphene oxide than 2.46, fully confirm the high quality reduction of coffic acid to graphene oxide.
Embodiment tetra-
The difference of the present embodiment and above-described embodiment three is only: the reduction reaction time is 12 hours.Other technologies feature is identical, no longer repeats here.
Embodiment five
The difference of the present embodiment and above-described embodiment three is only: the reduction reaction time is 2 hours.
Ultraviolet-visible light (UV-vis) spectrogram of the Graphene that the Graphene (a) obtaining for the present embodiment five for graphene oxide, (b) as shown in Figure 4,, the Graphene that (c) obtains for embodiment tetra-, (d) obtain for embodiment tri-.As can be seen from the figure, along with the increase of reduction reaction time, absorption peak is by the 230nm red shift gradually of graphene oxide, after the coffic acid reduction reaction of 2 hours (embodiment five), 12 hours (embodiment tetra-) and 24 hours (embodiment tri-), the position of UV-vis absorption peak moves to respectively 262nm, 265nm and 270nm.This explanation is along with the prolongation of reduction reaction time, and the recovery that the Two-dimensional electron conjugated structure in graphene-structured progressively obtains, has confirmed the reduction of coffic acid to graphene oxide.
Thermogravimetric (TGA) performance chart of the Graphene that the Graphene (a) obtaining for the present embodiment five for graphene oxide, (b) as shown in Figure 5,, the Graphene that (c) obtains for embodiment tetra-, (d) obtain for embodiment tri-.As shown in the figure, 100 ℃ of left and right, the weightless ratio of graphene oxide is approximately 10%, and this is to be caused by the evaporation of the inner contained humidity of graphene oxide.When temperature further raises, in graphene oxide, a large amount of oxygen-containing functional groups starts progressively to decompose, and weightless ratio is increasing.By comparison, the Graphene of preparing by the present invention is more stable under temperature action, and along with the increase in reaction times, the stability of Graphene is become better and better simultaneously, and this has confirmed the reduction of coffic acid to graphene oxide.
Embodiment six
The difference of the present embodiment and above-described embodiment three is only: the mass ratio of potassium permanganate and natural graphite is 5.5:1, and dilute hydrochloric acid enters with the number of times of deionized water centrifuge washing to be 8 times.
Embodiment seven
The difference of the present embodiment and above-described embodiment three is only: the usage ratio of graphite oxide powder and deionized water is 1mg:1ml, and in 1 hour, point 6 homogeneous add potassium permanganate, and every timed interval adding for twice is 10min.
Embodiment eight
The difference of the present embodiment and above-described embodiment three is only: the mass ratio of coffic acid powder and graphite oxide powder is 10:1, and mixture oil bath is heated to 85 ℃.
The method of what the embodiment of the present invention provided prepare Graphene, adopts the coffic acid that is extensively present in various plants as reductive agent, and green non-poisonous, preparation technology is simple, and reaction conditions gentleness can not cause environmental pollution and be detrimental to health; And because coffic acid has strong reducing power, can in reduzate, not introduce impurity element or functional group, Graphene purity and the quality of preparation are high.Can promote quickly extensive green non-poisonous production and the industrial application of this high-quality nano material of Graphene by this method, have the potential prospect of utilizing in the energy, catalysis and sensor field, and can produce huge economic benefits.
With reference to the accompanying drawings of the preferred embodiments of the present invention, not thereby limit to interest field of the present invention above.Those skilled in the art do not depart from the scope and spirit of the present invention interior done any modification, are equal to and replace and improve, all should be within interest field of the present invention.
Claims (10)
1. a method of preparing Graphene, is characterized in that, the method comprises:
The preparation process of graphene oxide: graphite oxide powder is added in deionized water, obtain the graphene oxide dispersion liquid of graphene oxide in deionized water by ultrasonic oscillation; Wherein, the usage ratio of graphite oxide powder and deionized water is 0.1 milligram: 1 milliliter～1 milligram: 1 milliliter;
The preparation process of Graphene: add coffic acid powder in described graphene oxide dispersion liquid, wherein, the mass ratio of coffic acid powder and graphite oxide powder is 10:1～50:1; The mixture oil bath obtaining is heated to 85 ℃～95 ℃ and continue to stir, obtains graphene solution by 2 hours～24 hours reduction reactions, then with filtering with microporous membrane and collect product, product obtains Graphene described in last vacuum-drying.
2. the method for preparing Graphene according to claim 1, is characterized in that, also comprises the preparation process of graphite oxide before the method:
The vitriol oil that is 98% by natural graphite and mass concentration at room temperature evenly mixes, at ice bath temperature, add in batches potassium permanganate and continue and stir, by the mixture heating in water bath to 35 obtaining ℃ and stir, react and add deionized water after 2 hours, then adding mass concentration is 30% hydrogen peroxide, the solution obtaining is cleaned repeatedly with hydrochloric acid and deionized water, and last vacuum-drying obtains graphite oxide powder; Wherein, the usage ratio of the vitriol oil and natural graphite is 25 milliliters: 1 gram, the mass ratio of potassium permanganate and natural graphite is 3.5:1～5.5:1, and the usage ratio of deionized water and natural graphite is 100 milliliters: 1 gram, the usage ratio of hydrogen peroxide and natural graphite is 8 milliliters: 1 gram.
3. the method for preparing Graphene according to claim 2, is characterized in that, described ice bath temperature refers to 0 ℃.
4. the method for preparing Graphene according to claim 2, is characterized in that, the described potassium permanganate that adds in batches comprises: in 1 hour～2 hours, point 6 homogeneous add potassium permanganate, and every timed interval adding for twice is 10min～20min.
5. the method for preparing Graphene according to claim 2, is characterized in that, described stirring comprises: adopt magnetic agitation.
6. the method for preparing Graphene according to claim 2, is characterized in that, described the solution obtaining is repeatedly cleaned further and comprised with hydrochloric acid and deionized water:
First adopting volume fraction is that 10% dilute hydrochloric acid carries out 15min centrifuge washing, then adopts deionized water to carry out 15min centrifuge washing; Wherein, centrifugal rotational speed is 8000 revs/min.
7. the method for preparing Graphene according to claim 1, is characterized in that, described ultrasonic oscillation comprises: by graphite oxide powder and deionized water mixture supersound process 2 hours under 300W power.
8. the method for preparing Graphene according to claim 1, is characterized in that, described millipore filtration comprises: aperture is the polyvinylidene fluoride microporous filtering film of 0.22 μ m.
9. the method for preparing Graphene according to claim 1, is characterized in that, described lasting stirring comprises: adopt magnetic force to continue to stir.
10. the method for preparing Graphene according to claim 1, is characterized in that, described vacuum-drying comprises: in vacuum drying oven, at 35 ℃, be dried 24 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
| CN102534643A (en) * | 2012-01-16 | 2012-07-04 | 清华大学深圳研究生院 | Method for regenerating waste battery carbon rods into graphene |
| CN102530931A (en) * | 2011-12-14 | 2012-07-04 | 天津大学 | Graphene-based nano composite material and preparation method thereof |
| CN102634106A (en) * | 2012-04-12 | 2012-08-15 | 上海交通大学 | Preparation method of graphene oxide nanobelt/polar rubber composite material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530927A (en) * | 2010-12-24 | 2012-07-04 | 中国科学院兰州化学物理研究所 | Graphene preparation method |
| CN102275908B (en) * | 2011-07-07 | 2013-03-13 | 中南大学 | Preparation method of graphene material |
| CN103466602A (en) * | 2012-06-06 | 2013-12-25 | 东丽先端材料研究开发（中国）有限公司 | Preparation method of graphene powder, and application of graphene powder in lithium ion battery |
| CN103803537A (en) * | 2014-01-22 | 2014-05-21 | 深圳市智慧低碳技术有限公司 | Preparation method of graphene |
-
2014
- 2014-01-22 CN CN201410030357.4A patent/CN103803537A/en active Pending
- 2014-12-26 WO PCT/CN2014/095109 patent/WO2015109916A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
| CN102530931A (en) * | 2011-12-14 | 2012-07-04 | 天津大学 | Graphene-based nano composite material and preparation method thereof |
| CN102534643A (en) * | 2012-01-16 | 2012-07-04 | 清华大学深圳研究生院 | Method for regenerating waste battery carbon rods into graphene |
| CN102634106A (en) * | 2012-04-12 | 2012-08-15 | 上海交通大学 | Preparation method of graphene oxide nanobelt/polar rubber composite material |
Non-Patent Citations (1)
| Title |
|---|
| JAEHO PARK 等: "Deoxidation of Graphene using Caffeic Acid", 《INTERNATIONAL JOURNAL OF EMERGING TECHNOLOGY AND ADVANCED ENGINEERING》, vol. 3, no. 12, 31 December 2013 (2013-12-31), pages 468 - 470 * |
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| CN110117002A (en) * | 2018-02-06 | 2019-08-13 | 山东欧铂新材料有限公司 | A kind of high dispersive lacks the preparation method of layer graphene |
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