CN102750998B

CN102750998B - Transparent graphene conductive thin film and preparation method thereof

Info

Publication number: CN102750998B
Application number: CN201210235187.4A
Authority: CN
Inventors: 梁奇; 梅佳; 陈冠雄; 吕雪; 孔东亮
Original assignee: Shenzhen Battery Nanotechnology Co Ltd
Current assignee: BTR New Material Group Co Ltd
Priority date: 2012-07-09
Filing date: 2012-07-09
Publication date: 2014-11-19
Anticipated expiration: 2032-07-09
Also published as: CN102750998A

Abstract

The invention discloses a transparent graphene conductive thin film and a preparation method of the film, aiming at improving the acid and alkali resistance of a transparent conductive thin film. The transparent graphene conductive thin film is a graphene thin film with the thickness of 1-50nm and the electrical conductivity of 300-800S/cm, and has the light transmittance of 70-85% for light with the wavelength within the range of 200-1100nm. The preparation method of the transparent graphene conductive thin film comprises the steps of: oxidizing graphite, preparing a graphene oxide water mixed liquid, preparing a graphene oxide thin film, and reducing to obtain the transparent graphene conductive thin film. Compared with the prior art, the transparent graphene conductive thin film which is prepared by a high-temperature reduction or chemical reduction method has the advantages of being good in light transmittance and electrical conductivity, large in preparation area, simple in preparation method and low in cost; and the transparent graphene conductive thin film can be used for replacing the traditional inorganic oxide electrode material indium tin oxide (ITO), thus providing infinite space for the transparent conductive thin film and the related fields.

Description

Transparent graphene conductive film and preparation method thereof

Technical field

The present invention relates to a kind of transparent conductive film and preparation method thereof, particularly a kind of transparent conductive film based on Graphene and preparation method thereof.

Technical background

The current application of transparent conductive film is very wide, such as the transparency electrode of solar cell, and the electro-conductive glass of touch-screen etc.The material that is used for now manufacturing transparent conductive film comparative maturity is tin indium oxide ITO.Yet there is following shortcoming in it: on the earth, the content of indium is very rare, annual underproduce 500 tons, and need from zinc lead ore, extract, cause ITO cost high; Under acid and alkaline environment, the metal ion of ITO tends to be diffused into polymeric layer, causes it very unstable, and limited to the transmitance of light near infrared region.

Summary of the invention

The object of this invention is to provide a kind of transparent graphene conductive film and preparation method thereof, the technical problem that solve is to improve the resistance to acids and bases of transparent conductive film, and reduces costs.

The present invention is by the following technical solutions: a kind of transparent graphene conductive film, and the graphene film that described transparent graphene conductive film is 1 ~ 50nm, conductivity is 300 ~ 800S/cm, to wavelength, at the light transmittance of the light of 200 ~ 1100nm, is 70 ~ 85%.

A kind of preparation method of transparent graphene conductive film, comprise the following steps: one, graphite oxide, press graphite powder, anhydrous nitric acid sodium, the mass ratio 1:0.5:3-6 of strong oxidizer, graphite powder and anhydrous nitric acid sodium are joined in the strongly acidic solution that ice bath temperature is≤0 ℃, the amount of strongly acidic solution adds 20 ~ 50ml by 1g graphite powder, under the mixing speed of 30 ~ 600rpm, stir after 30 ~ 60 minutes and add strong oxidizer, continue to stir 2h, control reaction temperature and be no more than 10 ℃, obtain suspension, add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, add again 30% H ₂o ₂, filtering precipitate, with deionized water washing until in filtrate without acid group, then by prior art vacuum dehydration, obtain water content lower than 30% graphite oxide filter cake, described strong oxidizer is potassium hyperchlorate and/or potassium permanganate, two, prepare graphene oxide water mixed liquid, in pure water, add graphite oxide filter cake, frequency 1-20KHz, power 400-3000w, sonic oscillation 10-30min under room temperature, centrifugal treating, rotating speed is 500-6000rpm, and the time is 1-30min, removes 5 layers of above graphene oxide lamella, obtain graphene oxide water mixed liquid, content is 0.01 ~ 1mg/mL, three, prepare graphene oxide film, graphene oxide liquid mixture is adopted to spraying, spin coating, dip-coating, drips coating method and on substrate, obtains the graphene oxide film that thickness is 1-50nm, four, adopt the method for high temperature reduction or electronation to obtain the transparent graphene conductive film that thickness is 1 ~ 50nm.

Method of the present invention obtains being warming up to stirring reaction 3h between 30-40 ℃ after suspension, then adds deionized water.

In method of the present invention, graphite powder is natural flake graphite, natural modified graphite, and Delanium, more than one in expanded graphite, its phosphorus content is >=90%, particle diameter D50<10 μ m.

Method middle strong acidity solution of the present invention is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.

In method of the present invention, centrifugal treating is divided and is carried out for three times, removes for the first time the graphite oxide filter cake of peeling off not yet completely, for the second time supernatant liquor is carried out to centrifugation, for the third time by the sediment after centrifugal with carrying out again centrifugation after distilled water diluting.

In method of the present invention, spraying is that substrate is preheating to 50 ~ 80 ℃, with spray gun, graphene oxide liquid mixture is sprayed on substrate, and moisture content obtains graphene oxide film after naturally volatilizing; Described spin coating is to allow substrate rotate with 2000-5000rpm rotating speed, time 5min, graphene oxide liquid mixture is dripped on substrate, make graphene oxide liquid mixture uniform spreading be spread out in substrate surface, directly at 50 ~ 80 ℃ of dry 10min-2h, then naturally cool to room temperature, after being dried, obtain graphene oxide film; Described dip-coating is that substrate is immersed to 5 ~ 60min in graphene oxide liquid mixture, directly, at 50 ~ 80 ℃ of dry 5 ~ 60min, then naturally cools to room temperature; Described painting is that graphene oxide liquid mixture drop is directly dropped on substrate, after graphene oxide liquid mixture is spread out and put on out completely, directly, at 50-80 ℃ of dry 5-60min, then naturally cools to room temperature.

High temperature reduction in method of the present invention, vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen and acetylene gas, in the reacting furnace that is 5 ~ 10L at capacity, flow is 50 ~ 200sccm, with the programming rate of 1-30 ℃/min, is warming up to 200 ~ 1100 ℃, 0 < time≤7h, then naturally cools to room temperature in stove; Electronation, temperature is 70 ~ 90 ℃, graphene oxide film is placed in to reducing agent steam, in the reaction vessel that is 10 ~ 30L at volume, steam flow is 20 ~ 200sccm, time is no less than 1h, and reducing agent is more than one in hydrazine hydrate, hydrogen iodide, concentrated ammonia liquor, Dimethylhydrazine, sodium dithionite, sodium borohydride and potassium borohydride.

Nitrogen, argon gas, helium in method of the present invention, temperature rises to 700 ~ 1100 ℃; Described hydrogen, acetylene, temperature rises to 200 ~ 700 ℃.

A kind of preparation method of transparent graphene conductive film, comprise the following steps: one, graphite oxide, press graphite powder, anhydrous nitric acid sodium, the mass ratio 1:0.5:3-6 of strong oxidizer, graphite powder and anhydrous nitric acid sodium are joined in the strongly acidic solution that ice bath temperature is≤0 ℃, the amount of strongly acidic solution adds 20 ~ 50ml by 1g graphite powder, under the mixing speed of 30 ~ 600rpm, stir after 30 ~ 60 minutes and add strong oxidizer, continue to stir 2h, control reaction temperature and be no more than 10 ℃, obtain suspension, be warming up to stirring reaction 3h between 30-40 ℃, add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, add again 30% H ₂o ₂, filtering precipitate, with deionized water fully wash until in filtrate without acid group, then by prior art vacuum dehydration, obtain water content lower than 30% graphite oxide filter cake, described graphite powder is natural flake graphite, natural modified graphite, and Delanium, more than one in expanded graphite, its phosphorus content is>=90%, particle diameter D50<10 μ m, described strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%, described strong oxidizer is potassium hyperchlorate and/or potassium permanganate, two, graphite oxide reduces, and takes the method for high temperature solid-state reduction or liquid phase chemical reduction, obtains Graphene, described high temperature reduction by graphite oxide filter cake, directly toasts 2 ~ 10h at 50 ~ 80 ℃, is crushed to D ₅₀be 1 ~ 20um, in vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen, acetylene gas, at volume, be in 5 ~ 10L reacting furnace, gas flow is 20 ~ 200sccm, directly high temperature reduction 10s ~ 10min in 900 ~ 1100 ℃, then naturally cools to room temperature in stove, obtains Graphene, described liquid-phase reduction, press graphite oxide filter cake, 80% concentration hydrazine hydrate mass ratio 0.7:1, graphite oxide filter cake and hydrazine hydrate are mixed directly at 70 ~ 90 ℃, rotating speed 30 ~ 100rpm, reaction reductase 12 ~ 10h, obtains graphene solution, then filter and obtain Graphene, with pure water washing and filtering thing 3 ~ 6 times, finally obtain Graphene slurries, by the dry Graphene that obtains of prior art, three, the preparation of graphene film, is mixed with the Graphene mixed liquor of 0.05 ~ 1mg/ml by Graphene, organic solvent, Graphene mixed liquor is adopted to spraying, spin coating, and dip-coating, drips a coating method and obtains the transparent graphene conductive film that thickness is 1 ~ 50nm, described organic solvent is methyl alcohol, ethanol, propyl alcohol, acetone, butanone.

The present invention compared with prior art, adopt the method for high temperature reduction or electronation to prepare transparent graphene conductive film, there is light penetrability good, conductivity is good, prepare area large, preparation method is simple, the advantage that cost is low, transparent graphene conductive film of the present invention is expected to replace traditional inorganic oxide electrode material ITO, for the development of transparent conductive film and association area provides immensity.

Embodiment

Below in conjunction with embodiment, the present invention is described in further detail.Transparent graphene conductive film of the present invention, adopts the graphene film that thickness is 1 ~ 50nm, and conductivity is 300 ~ 800S/cm, to wavelength, at the light transmittance of the light of 200 ~ 1100nm, is 70 ~ 85%.

The preparation method of transparent graphene conductive film of the present invention, adopts graphite oxide, disperses, and prepares graphene oxide film, and reduction, comprises the following steps:

One, graphite oxide, press the mass ratio 1:0.5:3-6 of graphite powder, anhydrous nitric acid sodium, strong oxidizer, graphite powder and anhydrous nitric acid sodium are joined in the strongly acidic solution that ice bath temperature is≤0 ℃, the amount of strongly acidic solution adds 20 ~ 50ml by 1g graphite powder, under the mixing speed of 30 ~ 600rpm, stir after 30 ~ 60 minutes and add strong oxidizer, continue to stir 2h, control reaction temperature and be no more than 10 ℃, obtain suspension.Be warming up to stirring reaction 3h between 30-40 ℃.Then add deionized water, temperature of charge is brought up to 96 ± 1 ℃, react 1h, then add 30% H ₂o ₂, suspension becomes sediment and glassy yellow liquid, filtering precipitate, with deionized water fully wash until in filtrate without acid group, then by prior art vacuum dehydration, obtain water content lower than 30% graphite oxide filter cake.

Graphite powder is natural flake graphite, natural modified graphite, and Delanium, more than one in expanded graphite, its phosphorus content is >=90%, particle diameter D50<10 μ m.

Strongly acidic solution is the concentrated sulfuric acid, red fuming nitric acid (RFNA) or perchloric acid, and concentrated sulfuric acid weight concentration is not less than 70%, and red fuming nitric acid (RFNA) concentration is not less than 65%, and perchloric acid concentration is not less than 60%.

Strong oxidizer is potassium hyperchlorate and/or potassium permanganate.

Two, prepare graphene oxide water mixed liquid, in pure water, add graphite oxide filter cake, frequency 1-20KHz, power 400-3000w, sonic oscillation 10-30min under room temperature, make graphite oxide filter cake be stripped from into the graphene oxide lamella of 1-100 layer, then centrifugal treating, can divide and carry out for three times, remove for the first time the graphite oxide filter cake of peeling off not yet completely, for the second time supernatant liquor is carried out to centrifugation, for the third time by the sediment after centrifugal with carrying out again centrifugation after distilled water diluting, three rotating speeds are 500-6000rpm, centrifugal treating total time is 1-30min, remove 5 layers of above graphene oxide lamella, obtain graphene oxide lamella and be dispersed in the graphene oxide liquid mixture in water, content is 0.01 ~ 1mg/mL.

Three, prepare graphene oxide film, graphene oxide liquid mixture is adopted to spraying, spin coating, dip-coating, drips coating method and on substrate, obtains the graphene oxide film that thickness is 1-50nm.

Spraying is that substrate is preheating to 50 ~ 80 ℃, with spray gun, graphene oxide liquid mixture is sprayed on substrate, and moisture content obtains graphene oxide film after naturally volatilizing.

Spin coating is to allow substrate rotate with 2000-5000rpm rotating speed, time 5min, graphene oxide liquid mixture is dripped on substrate, make graphene oxide liquid mixture uniform spreading be spread out in substrate surface, directly at 50 ~ 80 ℃ of dry 10min-2h, then naturally cool to room temperature, after being dried, obtain graphene oxide film.Regulate the rotating speed of substrate can control the speed of spreading out and putting on and uniformity.

Dip-coating is that substrate is immersed to 5 ~ 60min in graphene oxide liquid mixture, after having soaked, substrate is taken out, and directly, at 50 ~ 80 ℃ of dry 5 ~ 60min, then naturally cools to room temperature, and this mode is applicable to prepare the special graphene oxide film of substrate shape.

Dripping painting is that graphene oxide liquid mixture drop is directly dropped on substrate, after graphene oxide liquid mixture is spread out and put on out completely, directly, at 50-80 ℃ of dry 5-60min, then naturally cools to room temperature.The concentration of this mode mixed liquor is got less.

Substrate, as bearing basement, can be transparency silica glass, transparent organic film, Al ₂o ₃film, smooth sheet metal or smooth nonmetal hard sheet, be of a size of 1 ~ 10 inch of diameter.Sheet metal is gold, silver, aluminium, copper, nickel, and nonmetal is silicon dioxide, plastics, wood chip.

Four, graphene film is prepared in reduction, adopts the method for high temperature reduction or electronation to obtain the graphene film that thickness is 1 ~ 50nm, i.e. transparent graphene conductive film.

High temperature reduction, vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen and acetylene gas, in the reacting furnace that is 5 ~ 10L at capacity, flow is 50 ~ 200sccm, with the programming rate of 1-30 ℃/min, be warming up to 200～1100 ℃, 0 < time≤7h, then naturally cools to room temperature in stove, and the method is exotic material for substrate.When if atmosphere is non-reducing gas, such as nitrogen, argon gas, helium, temperature rises to 700 ~ 1100 ℃, hydrogen atom in oxygen atom in graphene oxide molecular structure and its molecular structure combines, generate steam, carbon atom combination in oxygen atom in graphene oxide molecular structure and its molecular structure, generates carbon dioxide, graphene oxide reduction.If atmosphere is reducibility gas, such as hydrogen, acetylene, temperature rises to 200 ~ 700 ℃, oxy radical meeting and reducibility gas atom combination producing water and carbon dioxide in graphite oxide molecular structure, graphene oxide reduction.

Electronation, temperature is 70 ~ 90 ℃, and graphene oxide film is placed in to reducing agent steam, and in the reaction vessel that is 10 ~ 30L at volume, steam flow is 20 ~ 200sccm, and the time is no less than 1h.Electronation is by reducing agent, the oxygen-containing functional group on graphite oxide molecular structure to be removed, thus redox graphene.

Reducing agent is more than one in hydrazine hydrate, hydrogen iodide, concentrated ammonia liquor, Dimethylhydrazine, sodium dithionite, sodium borohydride and potassium borohydride.

The preparation method of transparent graphene conductive film of the present invention, adopts graphite oxidation, and reduction, prepares graphene film, comprises the following steps:

Strong oxidizer is potassium hyperchlorate and/or potassium permanganate.

Two, graphite oxide reduces, and takes the method for high temperature solid-state reduction or liquid phase chemical reduction, obtains Graphene.

High temperature reduction by graphite oxide filter cake, directly toasts 2 ~ 10h at 50 ~ 80 ℃, is crushed to D ₅₀be 1 ~ 20um, in vacuum environment, or in more than one atmosphere in nitrogen, argon gas, helium, hydrogen, acetylene gas, at volume, be in 5 ~ 10L reacting furnace, gas flow is 20 ~ 200sccm, directly high temperature reduction 10s ~ 10min in 900 ~ 1100 ℃, then naturally cools to room temperature in stove, obtains Graphene.

Liquid-phase reduction, press graphite oxide filter cake, 80% concentration hydrazine hydrate mass ratio 0.7:1, graphite oxide filter cake and hydrazine hydrate are mixed directly at 70 ~ 90 ℃, rotating speed 30 ~ 100rpm, reaction reductase 12 ~ 10h, obtains graphene solution, then filter and obtain Graphene, with pure water washing and filtering thing 3 ~ 6 times, finally obtain Graphene slurries, by the dry Graphene that obtains of prior art.

Three, the preparation of graphene film, is mixed with the Graphene mixed liquor of 0.05 ~ 1mg/ml by Graphene, organic solvent, Graphene mixed liquor is adopted to spraying, spin coating, dip-coating, drips coating method and obtains the graphene film that thickness is 1 ~ 50nm, i.e. transparent graphene conductive film.

Spraying is that substrate is preheating to 50 ~ 80 ℃, with spray gun, Graphene mixed liquor is sprayed on substrate, and solvent obtains graphene oxide film after naturally volatilizing.

Spin coating is to allow substrate rotate with 2000-5000rpm rotating speed, Graphene mixed liquor is dripped on substrate, make Graphene mixed liquor uniform spreading be spread out in substrate surface, directly at 50 ~ 80 ℃ of dry 10 ~ 30min, then naturally cool to room temperature, after being dried, obtain graphene film.Regulate the rotating speed of substrate can control the speed of spreading out and putting on and uniformity.

Dip-coating is that substrate is immersed to 5 ~ 60min in Graphene mixed liquor, after having soaked, substrate is taken out, and directly, at 50 ~ 80 ℃ of dry 5 ~ 60min, then naturally cools to room temperature, and this mode is applicable to prepare the special graphene film of substrate shape.

Dripping painting is that Graphene mixed liquor drop is directly dropped on substrate, after Graphene mixed liquor is spread out and put on out completely, directly, at 50 ~ 80 ℃ of dry 5 ~ 60min, then naturally cools to room temperature.The concentration of this mode mixed liquor is got less.

Organic solvent is alcohols, ketone or 1-METHYLPYRROLIDONE NMP.Alcohols is methyl alcohol, ethanol, the propyl alcohol of molecular weight, and ketone is acetone, butanone.

Substrate, as bearing basement, can be transparency silica glass, transparent organic film, Al ₂o ₃film, smooth sheet metal or smooth nonmetal hard sheet, be of a size of 1 ~ 10 inch of diameter.

Transparent graphene conductive film prepared by the inventive method, by the di D3100 of U.S. Veeco company atomic force microscope, surveying film thickness is 1 ~ 50nm, with U.S. Midwest company's T P28-SZT-2000 four point probe conductivity measurement, recording conductivity is 300 ~ 800 S/cm, and with the U.S. F10-RT-UV of FILMETRICS company type light transmittance detector, recording wavelength is 70-85% at the light transmittance of 200 ~ 1100nm.

The transparent graphene conductive film that the present invention is prepared, under the wavelength of 500nm, light permeable rate is more than 70%, conductance is greater than 500S/cm, can be used as electrode of solar battery, touch-screen conductive film, be expected to replace traditional inorganic oxide electrode material ITO, for the development of transparent conductive film and association area provides immensity.

Embodiment 1,

One, under room temperature, the concentrated sulfuric acid solution 200ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake.

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 1mg/mL.

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 4000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light brown film of coating, thickness 3nm.

Four, the program control high temperature furnace of above-mentioned film being put into capacity 5L, passes into argon gas, flow 200sccm, and heating rate is 30 ℃/min, temperature is controlled at 1000 ℃ after rising, reaction 30min.Naturally cooling rear taking-up obtains graphene film.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 80%, and conductance is 600S/cm.

Embodiment 2,

One, under room temperature, the concentrated sulfuric acid solution 300ml that is 70% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 0.5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 60g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake.

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 20KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL.

Three, adopt the mode of spin coating that above-mentioned solution is applied in quartz substrate, spin speed is 5000rpm.Rotational time 5min is dried 2h standby in baking oven at 70 ℃.The film making is the uniform light brown film of coating, thickness 4nm.

Four, the program control high temperature furnace of above-mentioned film being put into capacity 10L, passes into nitrogen, flow 300sccm, and heating rate is 30 ℃/min, temperature is controlled at 1000 ℃ after rising, reaction 30min.Naturally cooling rear taking-up obtains graphene film.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 71%, and conductance is 500S/cm.

Embodiment 3,

One, under room temperature, the concentrated sulfuric acid solution 250ml that is 80% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 50g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake.

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 10KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.1mg/mL.

Three, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2 μ L, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dries 2h, naturally cooling standby.The film making is the uniform light brown film of coating, thickness 5nm.

Four, the program control high temperature furnace of above-mentioned film being put into capacity 8L, passes into hydrogen, flow 200sccm, and heating rate is 30 ℃/min, temperature is controlled at 1000 ℃ after rising, reaction 10min.Naturally cooling rear taking-up obtains graphene film.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 74%, and conductance is 480S/cm.

Embodiment 4,

One, under room temperature, the concentrated sulfuric acid solution 230ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake.

Two, the oxidized graphite flake layer of pulverizing after grinding is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL.

Four, the program control high temperature furnace of above-mentioned film being put into capacity 10L, passes into argon gas, flow 200sccm, and heating rate is 30 ℃/min, temperature is controlled at 1000 ℃ after rising, reaction 30min.Naturally cooling rear taking-up obtains graphene film.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 510S/cm.

Embodiment 5,

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.01mg/mL.

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light brown film of coating, thickness 5nm.

Four, above-mentioned film being put into the reacting furnace of capacity 10L, was under the condition below 1Pa in vacuum degree, and programming rate is 20 ℃/min, 1000 ℃ of reactions 3 hours.Naturally cooling rear taking-up obtains graphene film.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 505 S/cm, and conductance is 510 S/cm.

Embodiment 6,

Two, the oxidized graphite flake layer of pulverizing after grinding is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture.Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min.The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.05mg/mL.

Three, adopt the mode of spraying that above-mentioned mixed liquor is applied on quartz substrate, discharge rate is 5ml, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light brown film of coating, thickness 3nm.

Four, the graphene oxide film above-mentioned reaction being obtained, be placed in volumetric concentration and be 5% hydrazine hydrate (or hydrogen iodide) steam, in the reaction vessel of capacity 10L, temperature is that 80 ℃ of steam flows are 50sccm, reaction time is 1h, and taking-up obtains graphene film after drying.Light brown film becomes light grey semitransparent thin film.Under the wavelength of 500nm, recording light penetrability is 72%, and conductance is 515S/cm.

Embodiment 7,

One, under room temperature, the concentrated sulfuric acid solution 200ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um.

Two, the program control high temperature furnace of 3g left and right graphite oxide powder being put into capacity 5L left and right, passes into argon gas, flow 200sccm, and heating rate is 2000 ℃/min, temperature rises to 1000 ℃, reaction 30s.Naturally cooling rear taking-up obtains graphene powder.

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL.

Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 4000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light grey semitransparent thin film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 80%, and conductance is 600S/cm.

Embodiment 8,

One, under room temperature, the concentrated sulfuric acid solution 300ml that is 70% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 0.5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 60g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um.

Two, the program control high temperature furnace of 3g left and right graphite oxide powder being put into capacity 10L left and right, passes into argon gas, flow 400sccm, and heating rate is 2000 ℃/min, temperature rises to 1000 ℃, reaction 30s.Naturally cooling rear taking-up obtains graphene powder.

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor.Its medium frequency 20KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL.

Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 4000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light grey semitransparent thin film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 71%, and conductance is 500S/cm.

Embodiment 9,

One, under room temperature, the concentrated sulfuric acid solution 250ml that is 80% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 50g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um.

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor.Its medium frequency 10KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.05mg/mL.

Four, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2mL, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dries 2h, naturally cooling standby.The film making is the uniform light grey semitransparent thin film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 74%, and conductance is 580S/cm.

Embodiment 10,

Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 70 ℃, rotating speed 50rpm, reaction reduction 10 h, obtain graphene solution, then filter and obtain Graphene, use pure water washing and filtering thing 3 ~ 6 times, finally add pure water to obtain graphene solution, concentration is 0.5mol/ml.

Three, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2mL, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dries 2h, naturally cooling standby.The film making is the uniform light grey semitransparent thin film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 800S/cm.

Embodiment 11,

Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 90 ℃, rotating speed 60rpm, reaction reductase 12 h, obtain graphene solution, then filter and obtain Graphene, use pure water washing and filtering thing 3 ~ 6 times, finally add pure water to obtain graphene solution, concentration is 1mol/ml.

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light grey film of coating, thickness 5nm.Under the wavelength of 500nm, recording light penetrability is 70%, and conductance is 505S/cm, and conductance is 710S/cm.

Embodiment 12,

One, under room temperature, the concentrated sulfuric acid solution 230ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, add 10g natural flake graphite and 5g sodium nitrate, mixing speed is controlled at 600rpm, stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension.Be warming up to 35 ℃ of stirring reaction 3h.Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um.

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor.Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min.The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min.The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.5mg/mL.

Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, time 5min, and in baking oven, 70 ℃ of oven dry 2h are standby.The film making is the uniform light grey film of coating, thickness 3nm.Under the wavelength of 500nm, recording light penetrability is 72%, and conductance is 615S/cm.

Claims

1. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 200ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake;

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 1mg/mL;

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 4000rpm, and time 5min is dried 2h for 70 ℃ in baking oven, and the film making is the uniform light brown film of coating, thickness 3nm;

Four, the program control high temperature furnace of above-mentioned film being put into capacity 5L, passes into argon gas, flow 200sccm, and heating rate is 30 ℃/min, after temperature rises, is controlled at 1000 ℃, reaction 30min obtains graphene film after naturally cooling.

2. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 300ml that is 70% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 0.5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 60g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake;

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 20KHz, power 350W, the sonic oscillation time is 15min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL;

Three, adopt the mode of spin coating that above-mentioned solution is applied in quartz substrate, spin speed is 5000rpm; Rotational time 5min is dried 2h at 70 ℃ in baking oven, and the film making is the uniform light brown film of coating, thickness 4nm;

Four, the program control high temperature furnace of above-mentioned film being put into capacity 10L, passes into nitrogen, flow 300sccm, and heating rate is 30 ℃/min, after temperature rises, is controlled at 1000 ℃, reaction 30min obtains graphene film after naturally cooling.

3. a preparation method for transparent graphene conductive film, comprises the following steps: embodiment 3,

One, under room temperature, the concentrated sulfuric acid solution 250ml that is 80% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 50g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake;

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 10KHz, power 350W, the sonic oscillation time is 15min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.1mg/mL;

Three, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2 μ L, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dry 2h, naturally cooling, the film making is the uniform light brown film of coating, thickness 5nm;

Four, the program control high temperature furnace of above-mentioned film being put into capacity 8L, passes into hydrogen, flow 200sccm, and heating rate is 30 ℃/min, after temperature rises, is controlled at 1000 ℃, reaction 10min obtains graphene film after naturally cooling.

4. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 230ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake;

Two, the oxidized graphite flake layer of pulverizing after grinding is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.3mg/mL;

Four, the program control high temperature furnace of above-mentioned film being put into capacity 10L, passes into argon gas, flow 200sccm, and heating rate is 30 ℃/min, after temperature rises, is controlled at 1000 ℃, reaction 30min obtains graphene film after naturally cooling.

5. a preparation method for transparent graphene conductive film, comprises the following steps:

Two, graphite oxide filter cake is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.01mg/mL;

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, and time 5min is dried 2h for 70 ℃ in baking oven, and the film making is the uniform light brown film of coating, thickness 5nm;

Four, above-mentioned film being put into the reacting furnace of capacity 10L, is under the condition below 1Pa in vacuum degree, and programming rate is 20 ℃/min, 1000 ℃ of reactions 3 hours, obtains graphene film after naturally cooling.

6. a preparation method for transparent graphene conductive film, comprises the following steps:

Two, the oxidized graphite flake layer of pulverizing after grinding is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain graphene oxide liquid mixture; Its medium frequency 1KHz, power 350W, the sonic oscillation time is 15min; The graphene oxide of ultrasonic dispersion is carried out to centrifugation, first remove the oxidized graphite flake layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 3000rpm and 3min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 5000rpm and 5min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, be configured to the graphene oxide liquid mixture that concentration is 0.05mg/mL;

Three, adopt the mode of spraying that above-mentioned mixed liquor is applied on quartz substrate, discharge rate is 5ml, in baking oven, dries 2h for 70 ℃, and the film making is the uniform light brown film of coating, thickness 3nm;

Four, the graphene oxide film above-mentioned reaction being obtained, be placed in volumetric concentration and be 5% hydrazine hydrate or hydrogen iodide steam, in the reaction vessel of capacity 10L, temperature is that 80 ℃ of steam flows are 50sccm, reaction time is 1h, takes out to dry and obtain graphene film.

7. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 200ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um;

Two, the program control high temperature furnace of 3g graphite oxide powder being put into capacity 5L, passes into argon gas, flow 200sccm, and heating rate is 2000 ℃/min, and temperature rises to 1000 ℃, and reaction 30s, obtains graphene powder after naturally cooling;

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor; Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min; The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL;

Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 4000rpm, and time 5min is dried 2h for 70 ℃ in baking oven, and the film making is the uniform light grey semitransparent thin film of coating, thickness 3nm.

8. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 300ml that is 70% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 0.5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 60g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um;

Two, the program control high temperature furnace of 3g graphite oxide powder being put into capacity 10L, passes into argon gas, flow 400sccm, and heating rate is 2000 ℃/min, and temperature rises to 1000 ℃, and reaction 30s, obtains graphene powder after naturally cooling;

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor; Its medium frequency 20KHz, power 400W, the sonic oscillation time is 10min; The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.1mg/mL;

9. a preparation method for transparent graphene conductive film, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 250ml that is 80% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 50g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um;

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor; Its medium frequency 10KHz, power 400W, the sonic oscillation time is 10min; The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.05mg/mL;

Four, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2mL, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dry 2h, naturally cooling, the film making is the uniform light grey semitransparent thin film of coating, thickness 5nm.

10. a preparation method for transparent graphene conductive film, comprises the following steps:

Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 70 ℃, rotating speed 50rpm, reaction reduction 10h, obtain graphene solution, then filter and obtain Graphene, use pure water washing and filtering thing 3～6 times, finally add pure water to obtain graphene solution, concentration is 0.5mol/ml;

Three, the mode adopt to drip being coated with at the bottom of silicon wafer-based, is dripped above-mentioned mixing drop a painting amount and is controlled at 2mL, after drop is spread out completely in substrate, directly in baking oven, at 70 ℃, dry 2h, naturally cooling, the film making is the uniform light grey semitransparent thin film of coating, thickness 5nm.

The preparation method of 11. 1 kinds of transparent graphene conductive films, comprises the following steps:

Two, press oxidized graphite flake layer, 80% concentration hydrazine hydrate mass ratio 0.7:1,3g oxidized graphite flake layer and hydrazine hydrate are mixed directly at 90 ℃, rotating speed 60rpm, reaction reductase 12 h, obtain graphene solution, then filter and obtain Graphene, use pure water washing and filtering thing 3～6 times, finally add pure water to obtain graphene solution, concentration is 1mol/ml;

Three, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, and time 5min is dried 2h for 70 ℃ in baking oven, and the film making is the uniform light grey film of coating, thickness 5nm.

The preparation method of 12. 1 kinds of transparent graphene conductive films, comprises the following steps:

One, under room temperature, the concentrated sulfuric acid solution 230ml that is 98% by concentration is placed in container, and ice bath is controlled temperature at 0 ℃, adds 10g natural flake graphite and 5g sodium nitrate, and mixing speed 600rpm stirs 30min, more slowly adds wherein 30g strong oxidizer KMnO ₄, continue to stir 2h, control reaction temperature being no more than 10 ℃, obtain suspension; Be warming up to 35 ℃ of stirring reaction 3h; Add deionized water, temperature of charge is brought up to 96 ± 1 ℃, reaction 1h, is 30% H with deionized water by adding volumetric concentration after reactant solution dilution ₂o ₂, filtering precipitate while hot, with deionized water washing sediment in filtrate without SO ₄ ²-, vacuum dehydration obtains graphite oxide filter cake, and crushed after being dried is ground to granularity and is less than 50um;

Three, graphene powder is disperseed in water, utilize the weak ultrasonic oxidized graphite flake layer of peeling off, obtain Graphene mixed liquor; Its medium frequency 1KHz, power 400W, the sonic oscillation time is 10min; The Graphene of ultrasonic dispersion is carried out to centrifugation, first remove the graphene sheet layer of peeling off not yet completely, centrifugal rotational speed and time are respectively 4000rpm and 1min; Then supernatant liquor is carried out to centrifugation, centrifugal rotational speed and time are respectively 6000rpm and 3min; Finally that the precipitation after centrifugal is centrifugal with carrying out after distilled water diluting again, centrifugal rotational speed is 3000rpm, and the time is 3min; The precipitation of centrifugal treating gained is disperseed with distilled water again, and being configured to concentration is the Graphene mixed liquor of 0.5mg/mL;

Four, adopt the mode of spin coating that above-mentioned mixed liquor is applied on quartz substrate, spin speed is 5000rpm, and time 5min is dried 2h for 70 ℃ in baking oven, and the film making is the uniform light grey film of coating, thickness 3nm.