CN102557013A - Preparation method for reduced graphene oxide - Google Patents
Preparation method for reduced graphene oxide Download PDFInfo
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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 the ideal material that can substitute ITO.The method for preparing at present Graphene mainly comprise mechanically peel (Science., 2004,306:666), the high temperature CVD (Nano.Lett. that grows; 2009,9:30), epitaxy (J.Phys.Chem.B., 2004; 108:19912), chemical ultra-sonic dispersion peel off (Nat.Nanotechnol., 2008,3:563); The 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 this method is very low.Seeking effectively to disperse the solvent of Graphene 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 effectively 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, 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 objective 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 present invention provides a kind of preparation method of redox graphene, it is characterized in that, this method comprises graphene oxide and metal or reducing metal oxide compound are contacted with acid.
Contriver of the present invention finds; Through graphene oxide can directly be prepared the redox graphene nesa coating with metal or reducing metal oxide compound with sour the contact, preparation technology is simple for this method, 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 80, thereby avoids to people's injury with to the high pollution of environment.The present invention uses metal can reclaim repeated use, not only can practice thrift cost but also environmental protection.
The 3rd, fast restore, serialization production easily.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.Help realizing 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% in the 550nm wavelength; 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 that embodiment 1 graphene oxide is dispersed in the photo in the water, and (b) of Fig. 1 is that the redox graphene of embodiment 2 preparations is dispersed in the photo in the water;
Fig. 2 be embodiment 1 preparation graphene oxide and embodiment 2 preparations the thermogravimetric analysis (TGA) and the DTA (DTA) of redox graphene scheme;
Fig. 3 (A) is total spectrogram of the multi-functional image-forming electron energy spectrometer (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 present invention provides the present invention that a kind of preparation method of redox graphene is provided, and it is characterized in that, this method comprises graphene oxide and metal or reducing metal oxide compound are contacted with acid.
In the present invention, said 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, on substrate, apply the graphene oxide water-sol, 60-100 ℃ of oven dry; Obtain the graphene oxide film; At graphene oxide film surperficial plating 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, above-mentioned exsiccant method 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% in the 550nm wavelength, and square resistance is 10-10000 Ω/.
In the present invention, the preparation method of the said graphene oxide water-sol can prepare for the whole bag of tricks known in the field.The concentration of the graphene oxide in the said 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 said graphene oxide, metal or reducing metal oxide compound can in very large range change.Generally speaking, can be benchmark for weight with said graphene oxide, be equivalent to the graphene oxide of 1 weight part, the consumption of said metal or reducing metal oxide compound is the 1-100 weight part; The consumption that is preferably said 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 excessive greatly.Generally speaking, as long as satisfy the 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 said 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, said 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 said 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 paste.
Reducing metal oxide compound of the present invention can be various MOXs 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.
Said substrate comprises the substrate that all kinds of organic transparent materials are processed, and is preferably in flexible polyethylene terephthalate (PET), flexible polyvinyl chloride (PVC), flexible polymethylmethacrylate (PMMA), glass and the quartz one or more.
Said method at graphene oxide film surface plating layer of metal layer can be the whole bag of tricks known in the field.In for example ion sputtering, hot vapor deposition, magnetron sputtering and the silk screen printing one or more.
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment 1
The concentration that the natural flaky graphite of 1g is added 20g is in the vitriol oil of 95 weight %; Stirred overnight under 0 ℃ ice bath; The potassium permanganate that in the mixture that obtains, adds 0.15g then stirs the potassium permanganate that adds 3g behind the 30min again and controlled temperature below 20 ℃; And then elevated temperature to 35 ℃, and keep this temperature 30min, and in this mixture, adding the water of 45mL then, elevated temperature is kept this temperature 15min to 90-95 ℃; The concentration that adds 30mL afterwards again is the ydrogen peroxide 50 of 30 weight %; The water that adds 26mL behind the stirring 30min again; Filtered while hot, the concentration of using 50mL are the salt acid elution 3 times of 3 weight %, the gained filter cake are put into the water supersound process 1h of 400mL; With the dispersion liquid that obtains centrifugal graphene oxide particle of not peeled off fully of removing under the condition of 3000r/min, obtain the graphene oxide dispersion liquid of black; With the dispersion liquid that obtains after the spinning centrifugal graphene oxide subparticle of removing a small amount of reunion under the condition of 10000r/min; Obtain jelly; In this jelly, add the water-dispersion of about 1000mL; Promptly 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,, wash (50mL * 5 time) with deionized water with the salt pickling of 1mol/L (30mL * 3 time); 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.
Can know that according to Fig. 1 the product after the reduction is water insoluble, explain that redox graphene generates.Can find out that according to Fig. 2 thermogravimetric analysis figure graphene oxide has tangible weightlessness, and the Sn-RGO after the reduction is significantly not weightless.Explain that the product that obtains is a 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 a redox graphene.
Embodiment 3
Adopt the method for embodiment 1 to prepare the graphene oxide water-sol of 20mg/mL, in this graphene oxide water-sol of 5mL, add after metallic tin powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 1g mixes, divides adding concentrated hydrochloric acid (massfraction is 37%) 4mL 2 times; 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 can know that the product that obtains is a 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 SPA (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 can know that the product that obtains is a 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 min. 99.5 2g, obtains redox graphene.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis can know that the product that obtains is a redox graphene.
Embodiment 6
Method according to embodiment 2 prepares redox graphene, and different is that metallic tin powder 1g is replaced by zinc powder (Tianjin Kermel Chemical Reagent Co., Ltd.) 0.55g, and 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 can know that the product that obtains is a 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 can know that the product that obtains is a 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 can know that the product that obtains is a 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 XPS analysis can know that the product that obtains is a redox graphene.
Embodiment 10
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 oxide.According to according to thermogravimetric analysis, the XRD figure spectrum, diffraction, and XPS analysis can know that the product that obtains is a 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 appearance; 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 surface plating one deck tin layer, metal layer thickness 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 (concentration is 4mol/L, is 1.46g with respect to the weight of acid), takes out behind the 3min, put into deionized water and wash, oven dry obtains flexible redox graphene nesa coating.Simultaneously, can also prepare multilayer film through the repetition 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 result sees 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, and 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 surface plating one deck tin layer through 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 through the repetition 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 result sees 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; Different is that the PET substrate is replaced by the PMMA substrate, and (weight of metal level is 4.3 * 10 by plating layer of metal zinc through the ion sputtering method on graphene oxide film surface at graphene oxide film surface plating one deck tin layer through 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 through the repetition 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 result sees 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 crossing silk screen printing all at graphene oxide film surface plating one deck tin layer through 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 through the repetition 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 result sees 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 |
Can find out from the result of table 1 to table 4, can under coldcondition, realize directly preparing on the flexible substrates redox graphene film through method of the present invention.This film demonstrates good light transmission and electroconductibility.
Claims (12)
1. the preparation method of a redox graphene is characterized in that, this method comprises graphene oxide and metal or reducing metal oxide compound are contacted with acid.
2. method according to claim 1, wherein, the mode that said graphene oxide and metal or reducing metal oxide compound contacts with acid is after graphene oxide is prepared into the graphene oxide water-sol; On substrate, apply the graphene oxide water-sol; 60-100 ℃ of oven dry obtains the graphene oxide film, at graphene oxide film surface plating layer of metal or reducing metal oxide compound; Obtain the graphene oxide film that metal or reducing metal oxide compound cover; With cover or the graphene oxide film of reducing metal oxide compound contacts with sour to metal, remove metal level after, drying.
3. method according to claim 1 wherein, is a benchmark with the weight of said graphene oxide, and with respect to the graphene oxide of 1 weight part, the consumption of said metal or reducing metal oxide compound is the 1-100 weight part.
4. method according to claim 3 wherein, is a benchmark with the weight of said graphene oxide, with respect to the graphene oxide of 1 weight part, and the consumption 1.5-70 weight part of said metal or reducing metal oxide compound.
5. method according to claim 1, wherein, said acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and the acetic acid.
6. according to claim 1 or 5 described methods, wherein, the said temperature that contacts with acid is 15-100 ℃, and the time of contact is 0.01-12 hour.
7. method according to claim 6, wherein, the said temperature that contacts with acid is 20-40 ℃, the time of contact is 0.1-6 hour.
8. method according to claim 1, wherein, said metal is one or more in lithium, sodium, potassium, indium, tin, aluminium, magnesium, zinc and the nickel.
9. method according to claim 1, wherein, said MOX is one or more in tin protoxide, iron protoxide and the Red copper oxide.
10. method according to claim 1, wherein, the concentration of the graphene oxide in the said graphene oxide water-sol is 0.1-20mg/mL.
11. method according to claim 2, wherein, redox graphene is membranaceous, and the light transmission of said film is 40-95% in the 550nm wavelength.
12. method according to claim 11, wherein, the square resistance of said film is 10-10000 Ω/.
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