CN102557013B - Preparation method for reduced graphene oxide - Google Patents
Preparation method for reduced graphene oxide Download PDFInfo
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- CN102557013B CN102557013B CN2010106101794A CN201010610179A CN102557013B CN 102557013 B CN102557013 B CN 102557013B CN 2010106101794 A CN2010106101794 A CN 2010106101794A CN 201010610179 A CN201010610179 A CN 201010610179A CN 102557013 B CN102557013 B CN 102557013B
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Abstract
The invention provides a preparation method for reduced graphene oxide. The method is characterized by comprising the following step of: contacting graphene oxide and a metal or a reductive metallic oxide with an acid. The method has a simple and rapid process, a good reducing effect, can be used for realizing continuous industrial production of reduced graphene oxide, and is a preparation method with low energy consumption and low pollution for reduced graphene oxide.
Description
Technical field
The present invention relates to a kind of preparation method of redox graphene.
Background technology
Graphene is because its high electricity is led, and stability is regarded as substituting the ideal material of ITO.The method for preparing at present Graphene mainly comprise mechanically peel (Science., 2004,306:666), high temperature CVD growth (Nano.Lett., 2009,9:30), epitaxy (J.Phys.Chem.B., 2004,108:19912), the chemistry ultra-sonic dispersion is peeled off (Nat.Nanotechnol., 2008,3:563), graphene oxide reduction (Carbon, 2007,45:1558-1565).The amount of mechanically peel preparation is few, is fit to scientific research, can not satisfy a large amount of industrial requirements far away.CVD, epitaxial growth method can prepare high-quality graphene film, aspect the high-end device application in future good prospect are being arranged.But CVD, epitaxial growth method need high temperature and complicated transfer process, complex process and be the highly energy-consuming process.Chemistry ultra-sonic dispersion stripping means can prepare a certain amount of Graphene, but the productive rate of the method is very low.The solvent of seeking effective dispersed graphite alkene is a bottleneck of its raising productive rate of restriction.By graphene oxide (GO, Grapheneoxide) preparation redox graphene (RGO, Reduced Graphene oxide) is considered to realize the most effective means of suitability for industrialized production, and graphene oxide has good wetting ability, preparation is simple, and productive rate is high.But the method for reducing of graphene oxide also mainly concentrates on the reduction of hydrazine class, high temperature etc. at present.There is high toxicity in these methods, high pollution, high energy consumption, the shortcomings such as low reduction effect.Therefore, realize the suitability for industrialized production of grapheme material, demand seeking less energy-consumption urgently, low pollution, the method for reducing of efficient oxidation Graphene.
Summary of the invention
The object of the invention is to overcome the highly energy-consuming of graphene preparation method in the prior art, the shortcoming of high pollution provides the preparation method of a kind of less energy-consumption, oligosaprobic redox graphene.
The invention provides a kind of preparation method of redox graphene, it is characterized in that, the method comprises graphene oxide and metal or reducing metal oxide compound is contacted with acid.
The present inventor finds, by graphene oxide can directly be prepared the redox graphene nesa coating with metal or reducing metal oxide compound with sour the contact, the method preparation technology is simple, fast, reduction effect is good, can realize the serialization industrial production of redox graphene.
Compared with prior art, the method for reducing of graphene oxide provided by the present invention has following beneficial effect:
The first, less energy-consumption, economy.Preparation process of the present invention is to carry out at a lower temperature, and temperature is no more than 100 ℃, does not pass through the thousands of high temperature of CVD, avoids the high energy consumption process; Simultaneously, making processes of the present invention can realize directly film forming on flexible substrates below 100 ℃, avoids the transfer process of film.Therefore, redox graphene and substrate have good bonding force.
The second, low pollution, environmental protection.The present invention does not use the virose reductive agent of hydrazine hydrate, thereby avoids to people's injury with to the high pollution of environment.The present invention uses metal to reclaim and reuses, and not only can save cost but also environmental protection.
The 3rd, fast restore, easily serialization production.The graphene oxide film can be at 0.5-10min reduction preparation redox graphene nesa coating among the present invention.Adopt the metallic reducing manufacture craft simple, reduction fast.Be conducive to realize industrial continuous Roll-to-Roll production process.
The 4th, efficient reduction, the redox graphene film conductivity of the present invention's preparation can be good, and light transmission is 40-95% at 550nm wavelength place, the square resistance of film is 10-10000 Ω/, for redox graphene is providing good prospect aspect the window mould material of photoelectric device.
Description of drawings
(a) of Fig. 1 is the photo that embodiment 1 graphene oxide is dispersed in water, and (b) of Fig. 1 is the photo that the redox graphene of embodiment 2 preparations is dispersed in water;
Fig. 2 be the graphene oxide of embodiment 1 preparation and embodiment 2 preparations thermogravimetric analysis (TGA) and the differential thermal analysis (DTA) of redox graphene scheme;
Fig. 3 (A) is total spectrogram of the Multifunctional imaging Electron Energy Disperse Spectroscopy (XPS) of the graphene oxide of embodiment 1 preparation and the redox graphene that embodiment 2 prepares, (B) being the match spectrogram of graphene oxide C1s, (C) is the match spectrogram of the redox graphene C1s of embodiment 1 preparation;
Fig. 4 is the graphene oxide of embodiment 1 preparation and the X-ray diffractogram of the redox graphene that embodiment 2 prepares;
(a) of Fig. 5 is the transmission electron microscope picture of the redox graphene of embodiment 2 preparations, and (b) of Fig. 5 is the electron diffraction photo of the redox graphene of embodiment 2 preparations;
Fig. 6 is the redox graphene nesa coating of embodiment 11 preparations.
Embodiment
The invention provides a kind of preparation method of redox graphene, it is characterized in that, the method comprises graphene oxide and metal or reducing metal oxide compound is contacted with acid.
In the present invention, described graphene oxide can be variety of way known in the field with metal or reducing metal oxide compound with the mode that acid contacts.After for example graphene oxide being prepared into the graphene oxide water-sol, apply the graphene oxide water-sol at substrate, 60-100 ℃ of oven dry, obtain the graphene oxide film, at graphene oxide film plated surface layer of metal or reducing metal oxide compound, obtain the graphene oxide film that metal or reducing metal oxide compound cover, the graphene oxide film to metal or the covering of reducing metal oxide compound that gets is contacted with acid, after removing metal level, drying.
In the present invention, the method for above-mentioned drying can be the whole bag of tricks known in the field.The present invention is preferably 60-100 ℃ of oven dry, and it is membranaceous obtaining redox graphene.The thickness of membranaceous redox graphene is generally the 5-1200 nanometer.The light transmission of this redox graphene nesa coating is 40-95% at 550nm wavelength place, and square resistance is 10-10000 Ω/.
In the present invention, the preparation method of the described graphene oxide water-sol can prepare for the whole bag of tricks known in the field.The concentration of the graphene oxide in the described graphene oxide water-sol can in very large range change.The present invention is preferably 0.1-20mg/mL.
In the present invention, the consumption of described graphene oxide, metal or reducing metal oxide compound can in very large range change.Generally speaking, can be equivalent to the graphene oxide of 1 weight part for take the weight of described graphene oxide as benchmark, the consumption of described metal or reducing metal oxide compound is the 1-100 weight part; The consumption that is preferably described metal or reducing metal oxide compound is the 1.5-70 weight part.
In addition, in the present invention, acid plays katalysis and does in order to removing metal with excess metal where necessary, and the existence of acid do not have disadvantageous effect to the redox graphene that generates, and therefore, the consumption of acid can be greatly excessive.Generally speaking, as long as satisfied graphene oxide with respect to 1 weight part, the consumption of acid gets final product greater than 1 weight part, and under the preferable case, the consumption of acid is the 1-10000 weight part, and more preferably the consumption of acid is the 1-1000 weight part.
Above-mentioned acid can be various acid known in the field.For example can be protonic acid.Be preferably in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the acetic acid one or more.The concentration of acid can be 5-100 quality %; The concentration that is preferably acid is 30-100 quality %.
The temperature and time that described graphene oxide contacts with metal or reducing metal oxide compound can be all temps known in those skilled in the art and time.Particularly, the temperature that graphene oxide contacts with metal or reducing metal oxide compound is 15-100 ℃, and the time of contact is 0.01-12 hour; In order to make more convenient operation, being preferably the temperature that graphene oxide contacts with metal or reducing metal oxide compound is 20-40 ℃, and the time of contact is 0.1-6 hour.
In the present invention, described metal can be for following the protonic acid reaction or having low-melting active metal (fusing point is less than 500 ℃) easily.The metal that satisfies above-mentioned condition can be enumerated as lithium, sodium, potassium, indium, tin, one or more in aluminium, magnesium, zinc and the nickel.In addition, the form of described metal of the present invention does not have special requirement, can be the metal of variform, for example can be metal powder, metal slurry or metal paste.
Reducing metal oxide compound of the present invention can be various metal oxides with reductibility known in the field.For example, can be in tin protoxide, iron protoxide and the Red copper oxide one or more; Be preferably tin protochloride and/or Red copper oxide.
Described substrate comprises the substrate that all kinds of organic transparent materials are made, and is preferably in flexible polyethylene terephthalate (PET), flexible polyvinyl chloride (PVC), flexible polymethylmethacrylate (PMMA), glass and the quartz one or more.
Described method at graphene oxide film plated surface layer of metal layer can be the whole bag of tricks known in the field.In for example ion sputtering, hot evaporation, magnetron sputtering and the silk screen printing one or more.
The present invention is described further below in conjunction with embodiment.
The concentration that the natural flaky graphite of 1g is added 20g is in the vitriol oil of 95 % by weight, under 0 ℃ ice bath, stir and spend the night, then the potassium permanganate that adds 0.15g in the mixture that obtains adds the potassium permanganate of 3g again and controls temperature below 20 ℃ after stirring 30min; And then rising temperature to 35 ℃, and keep this temperature 30min, then add the water of 45mL in this mixture, the rising temperature is kept this temperature 15min to 90-95 ℃; The concentration that adds again afterwards 30mL is the hydrogen peroxide of 30 % by weight, the water that adds again 26mL behind the stirring 30min, filtered while hot, be the salt acid elution 3 times of 3 % by weight with the concentration of 50mL, the gained filter cake is put into the water supersound process 1h of 400mL, with the dispersion liquid centrifugal graphene oxide particle do not peeled off fully of removing under the condition of 3000r/min that obtains, obtain the graphene oxide dispersion liquid of black; With the dispersion liquid centrifugal graphene oxide subparticle of removing a small amount of reunion under the condition of 10000r/min that obtains after the centrifugation, obtain jelly, add the water-dispersion of about 1000mL in this jelly, namely obtain the graphene oxide water-sol of 1mg/ml, the photo of this graphene oxide water-sol is shown in (a) among Fig. 1, and the GO curve among Fig. 2 is seen in thermogravimetric analysis.
Embodiment 2
After in the 1mg/mL graphene oxide water-sol 100mL of embodiment 1 preparation, adding metallic tin powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 1g (8.4mmol) mixing, divide 2 times and add concentrated hydrochloric acid (massfraction is 37%) 4mL (weight with respect to acid is 1.48g), stir 4h, treat that solution all becomes black, filter, with the salt pickling of 1mol/L (30mL * 3 time), wash (50mL * 5 time) with deionized water, filter, obtain redox graphene.This redox graphene is joined in the 5mL water, and the photo of gained mixture is shown in (b) among Fig. 1, and the RGO curve among Fig. 2 is seen in thermogravimetric analysis.
Product after reducing as can be known according to Fig. 1 is water insoluble, has illustrated that redox graphene generates.Can find out that according to Fig. 2 thermogravimetric analysis figure graphene oxide has obvious weightlessness, and the Sn-RGO after the reduction is significantly not weightless.Illustrate that the product that obtains is redox graphene.Can find out C according to Fig. 3 XPS collection of illustrative plates (A): the mol ratio of O brings up to 12.93 by graphene oxide 2.33, and the most oxygen-containing functional group in graphene oxide surface has been removed in reduction.(C) compare with (B) can find out reduction after, the C-O on the graphene oxide, C (O) O group obviously weakens, C=O group, the basic disappearance.According to Fig. 4 XRD figure spectrum, can find out GO interlamellar spacing d=0.66nm, product S n-RGO interlamellar spacing d=0.37nm and graphite layers after the reduction are close apart from 0.34nm, can find out that the product degree of graphitization after the reduction improves.According to Fig. 5 (b) diffractogram, can find out the Sn-RGO after the reduction, have the diffraction of graphite plane.The product that comprehensive various sign obtains is redox graphene.
Embodiment 3
The method of employing embodiment 1 prepares the graphene oxide water-sol of 20mg/mL, add in this graphene oxide water-sol of 5mL after metallic tin powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 1g mixes, divide 2 times and add concentrated hydrochloric acid (massfraction is 37%) 4mL, stir 4h, treat that solution all becomes black, filter, with the salt pickling of 1mol/L (30mL * 3 time), wash (50mL * 5 time) with deionized water, filter, obtain redox graphene.According to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 4
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g (8.4mmol) is replaced by aluminium powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 0.16g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by strong phosphoric acid (massfraction is 85%) 1mL (weight with respect to acid is 0.85g), obtains redox graphene.According to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by magnesium powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 0.21g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by Glacial acetic acid 2g, obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 6
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by zinc powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 0.55g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by oxalic acid 2g, obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 7
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by nickel powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 0.5g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by concentrated hydrochloric acid (massfraction is 37%) 10mL (weight with respect to acid is 3.7g), obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 8
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by tin protochloride (Chemical Reagent Co., Ltd., Sinopharm Group) 2g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by concentrated hydrochloric acid (massfraction is 37%) 2mL (weight with respect to acid is 0.74g), obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 9
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by Red copper oxide (Chemical Reagent Co., Ltd., Sinopharm Group) 2.4g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by concentrated hydrochloric acid (massfraction is 37%) 2mL (weight with respect to acid is 0.74g), obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and the product that XPS analysis obtains as can be known is redox graphene.
Method according to embodiment 2 prepares redox graphene, different is that metallic tin powder 1g is replaced by titanous chloride (Chemical Reagent Co., Ltd., Sinopharm Group) 2.6g, concentrated hydrochloric acid (massfraction is 37%) 4mL is replaced by concentrated hydrochloric acid (massfraction is 37%) 2mL (weight with respect to acid is 0.74g), obtains the mixture of redox graphene and titanium dioxide.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis, the product that obtains as can be known are redox graphene.
Embodiment 11
(2cm * 2cm) drips the graphene oxide water-sol of 0.5mL embodiment 1 preparation on PET (polyphenyl dioctyl phthalate glycol ester) substrate, (Chinese Academy of Sciences electron institute produces to use the spin coating instrument, model: kW-4A) in spin coating under the 5000r/min speed after 60 seconds, 80 ℃ of oven dry.Use magnetic control sputtering device (ULVACInc., model ACS-400-C4), at graphene oxide film plated surface one deck tin metal layer, the thickness of metal level is about 15nm, and (weight of metal level is 4.4 * 10
-5G).The plated graphene oxide film that obtains is immersed in the 10mL hydrochloric acid soln, and (concentration is 4mol/L, weight with respect to acid is 1.46g) in, take out behind the 3min, put into deionized water and wash, oven dry obtains flexible redox graphene nesa coating.Simultaneously, can also prepare multilayer film by repeating said process in order to obtain more excellent printing opacity conductivity.
With Scanning Probe Microscopy instrument (Digital Instruments, Dimension 3100) detect the thickness of redox graphene film, two electrical measurement four point probe testers (Guangzhou four point probe science and technology, RTS-9 type) detect the square resistance of this flexibility redox graphene nesa coating.(transmittance of this flexibility redox graphene nesa coating Lambda950UV/VIS/NIR) detects to ultraviolet/visible spectrophotometer in perkin elmer instrument (Shanghai) Co., Ltd..The results are shown in Table 1.
Table 1
| Apply the number of plies | Conducting film thickness/nm | Transmittance/% | Square resistance/(Ω/) |
| 1 | 5 | 91 | 10000 |
| 5 | 25 | 86 | 1200 |
| 10 | 50 | 71 | 400 |
| 20 | 100 | 62 | 25 |
| 25 | 120 | 45 | 12 |
Embodiment 12
Method according to embodiment 11 prepares flexible redox graphene nesa coating, different is that the PET substrate is replaced by the PMMA substrate, and (weight of metal level is 1.6 * 10 by the tin protoxide layer at graphene oxide film plated surface one deck tin metal layer by magnetron sputtering
-5G) replace, hydrochloric acid soln is replaced by 10mL phosphoric acid solution (concentration is 4mol/L, is 3.92g with respect to the weight of acid), obtains flexible redox graphene nesa coating.Simultaneously, can also prepare multilayer film by repeating said process in order to obtain more excellent printing opacity conductivity.
With Scanning Probe Microscopy instrument (Digital Instruments, Dimension 3100) detect the thickness of redox graphene film, two electrical measurement four point probe testers (Guangzhou four point probe science and technology, RTS-9 type) detect the square resistance of this flexibility redox graphene nesa coating.(transmittance of this flexibility redox graphene nesa coating Lambda950UV/VIS/NIR) detects to ultraviolet/visible spectrophotometer in perkin elmer instrument (Shanghai) Co., Ltd..The results are shown in Table 2.
Table 2
| Apply the number of plies | Conducting film thickness/nm | Transmittance/% | Square resistance/(Ω/) |
| 1 | 5 | 95 | 9900 |
| 5 | 25 | 87 | 1100 |
| 10 | 50 | 72 | 390 |
| 20 | 100 | 62 | 25 |
| 25 | 120 | 43 | 11 |
Embodiment 13
Method according to embodiment 11 prepares flexible redox graphene nesa coating, PET substrate that different is is replaced by the PMMA substrate, by magnetron sputtering at graphene oxide film plated surface one deck tin metal layer by (weight of metal level is 4.3 * 10 at graphene oxide film plated surface layer of metal zinc by the ion sputtering method
-5G) replace, hydrochloric acid soln is replaced by the hydrochloric acid soln of 10mL (concentration is 4mol/L, is 1.46g with respect to the weight of acid), obtains flexible redox graphene nesa coating.Simultaneously, can also prepare multilayer film by repeating said process in order to obtain more excellent printing opacity conductivity.
With Scanning Probe Microscopy instrument (Digital Instruments, Dimension 3100) detect the thickness of redox graphene film, two electrical measurement four point probe testers (Guangzhou four point probe science and technology, the RTS-9 type) detects the square resistance of this flexibility redox graphene nesa coating.(transmittance of this flexibility redox graphene nesa coating Lambda950UV/VIS/NIR) detects to ultraviolet/visible spectrophotometer in perkin elmer instrument (Shanghai) Co., Ltd..The results are shown in Table 3.
Table 3
| Apply the number of plies | Conducting film thickness/nm | Transmittance/% | Square resistance/(Ω/) |
| 1 | 5 | 91 | 9800 |
| 5 | 25 | 88 | 1100 |
| 10 | 50 | 70 | 450 |
| 20 | 100 | 66 | 30 |
| 25 | 120 | 50 | 15 |
Embodiment 14
Method according to embodiment 11 prepares flexible redox graphene nesa coating, and different is that (weight of metal level is 4.4 * 10 at graphene oxide film plating one deck tin cream by all crossing silk screen printing at graphene oxide film plated surface one deck tin metal layer by magnetron sputtering
-5G) replace, hydrochloric acid soln is replaced by the hydrochloric acid soln of 10mL (concentration is 4mol/L, is 1.46g with respect to the weight of acid), obtains flexible redox graphene nesa coating.Simultaneously, can also prepare multilayer film by repeating said process in order to obtain more excellent printing opacity conductivity.
With Scanning Probe Microscopy instrument (Digital Instruments, Dimension 3100) detect the thickness of redox graphene film, two electrical measurement four point probe testers (Guangzhou four point probe science and technology, the RTS-9 type) detects the square resistance of this flexibility redox graphene nesa coating.(transmittance of this flexibility redox graphene nesa coating Lambda950UV/VIS/NIR) detects to ultraviolet/visible spectrophotometer in perkin elmer instrument (Shanghai) Co., Ltd..The results are shown in Table 4.
Table 4
| Apply the number of plies | Conductive layer thickness/nm | Transmittance/% | Square resistance/(Ω/) |
| 1 | 5 | 92 | 9500 |
| 5 | 25 | 87 | 1050 |
| 10 | 50 | 71 | 460 |
| 20 | 100 | 62 | 27 |
| 25 | 120 | 40 | 10 |
Result from table 1 to table 4 can find out, can under cold condition, realize directly preparing on the flexible substrates redox graphene film by method of the present invention.This film demonstrates good light transmission and electroconductibility.
Claims (9)
1. the preparation method of a redox graphene is characterized in that, described redox graphene is membranaceous, and the method comprises graphene oxide and metal or reducing metal oxide compound are contacted with acid; Wherein, the mode that described graphene oxide and metal or reducing metal oxide compound contacts with acid is after graphene oxide is prepared into the graphene oxide water-sol, apply the graphene oxide water-sol at substrate, 60-100 ℃ of oven dry, obtain the graphene oxide film, at graphene oxide film plated surface layer of metal or reducing metal oxide compound, obtain the graphene oxide film that metal or reducing metal oxide compound cover, the graphene oxide film that the metal that obtains or reducing metal oxide compound are covered contacts with sour, after removing metal level or reducing metal oxide compound, drying; Described metal is one or more in lithium, sodium, potassium, indium, tin, aluminium, magnesium, zinc and the nickel; Described metal oxide is one or more in tin protoxide, iron protoxide and the Red copper oxide.
2. method according to claim 1, wherein, take the weight of described graphene oxide as benchmark, with respect to the graphene oxide of 1 weight part, the consumption of described metal or reducing metal oxide compound is the 1-100 weight part.
3. method according to claim 2, wherein, take the weight of described graphene oxide as benchmark, with respect to the graphene oxide of 1 weight part, the consumption of described metal or reducing metal oxide compound is the 1.5-70 weight part.
4. method according to claim 1, wherein, described acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the acetic acid.
5. according to claim 1 or 4 described methods, wherein, temperature described and that acid contacts is 15-100 ℃, and the time of contact is 0.01-12 hour.
6. method according to claim 5, wherein, temperature described and that acid contacts is 20-40 ℃, the time of contact is 0.1-6 hour.
7. method according to claim 1, wherein, the concentration of the graphene oxide in the described graphene oxide water-sol is 0.1-20mg/mL.
8. method according to claim 1, wherein, the light transmission of the film of redox graphene is 40-95% at 550nm wavelength place.
9. method according to claim 8, wherein, the square resistance of the film of redox graphene is 10-10000 Ω/.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
| CN101830458A (en) * | 2010-05-06 | 2010-09-15 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009049375A1 (en) * | 2007-10-19 | 2009-04-23 | University Of Wollongong | Process for the preparation of graphene |
-
2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549864A (en) * | 2009-04-30 | 2009-10-07 | 上海大学 | Method for simply and innoxiously preparing single-layer graphene |
| CN101830458A (en) * | 2010-05-06 | 2010-09-15 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
Non-Patent Citations (2)
| Title |
|---|
| Facile Synthesis of Graphene Nanosheets via Fe Reduction of Exfoliated Graphite Oxide;Zhuang-Jun Fan et al.;《ACS Nano》;20101207;第5卷(第1期);191-198 * |
| Zhuang-Jun Fan et al..Facile Synthesis of Graphene Nanosheets via Fe Reduction of Exfoliated Graphite Oxide.《ACS Nano》.2010,第5卷(第1期),191-198. |
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