CN103043654B - Film containing graphene and/or graphene oxide, and preparation method thereof - Google Patents
Film containing graphene and/or graphene oxide, and preparation method thereof Download PDFInfo
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Abstract
The invention provides a film containing graphene and/or graphene oxide, and a preparation method thereof. The method comprises the following steps of (1) dispersing a graphene and/or graphene oxide gel in a solvent to prepare a dispersing solution containing the graphene and/or graphene oxide with a concentration of 0.01-20 mg/mL; (2) making the dispersing solution form a uniform wet film on a substrate by a wire rod coating method, wherein the diameter of the wire used in the wire rod coating method is 0.01-2 mm; and (3) evaporating solvent from the wet film obtained from the step (2). The invention also provides a film containing the graphene and/or graphene oxide with a thickness of 0.6-2,300 nm, and the thickness deviation of the film is smaller than or equal to 37%. The preparation method provided by the invention has the advantages of fast preparation speed and solution economization.
Description
Technical field
The present invention relates to a kind of film that contains Graphene and/or graphene oxide and preparation method thereof.
Background technology
Graphene is the material that a kind of carbon atom of two dimensional surface monoatomic layer thickness Hexagonal array forms, and it has high charge mobility, high mechanical strength, the performance that high surface area etc. are excellent.It is in thin-film solar cells, flat pannel display electrode, and electrical condenser, the aspects such as lithium electricity and coating machine intensity enhancing have a wide range of applications.
At present the preparation method of Graphene or graphene oxide film is mainly contained to drop-coating, spin-coating method, micro-filtration, self-assembly, LB embrane method, spraying method.Drop-coating and micro-filtration method can only be prepared the graphene film compared with small area.Spin coating method is the conventional a kind of method of preparing film in laboratory, prepare fairly simple, but the weak point of the method is to cause tank solution waste, while is due to the cause of spin coating centrifugal force, the film thickness of preparation becomes certain distribution, in addition, also harsher to the requirement of solution.LB film and self-assembling method be the thickness of controlling diaphragm effectively, but the mechanical stability of LB film is poor, and LB film is a kind of metastable structure, to the stability of heat, chemical environment, time and external pressure a little less than; And LB film is special to the structural requirement of membrane-forming molecule, must be amphiphilic, film-forming apparatus is also expensive; Film prepared by self-assembling method is subject to the impact of several factors, such as the chemical constitution of substrate surface, the film that the character of the chemical property of substrate surface and tunic molecule self etc. are all prepared self-assembling method has impact.Spraying method can big area serialization be prepared graphene film, but because the restriction of technology is difficult to the thickness of controlling diaphragm, and thickness deviation (thickness-mean thickness at the minimum place of the thickness of thickness maximum or thickness)/mean thickness calculates) be generally 40-50%.It is a kind of method of preparing ink film being proposed the earliest by Mayer Rod that line rod is filmed.The people such as Dan by the method successfully prepared carbon nano-tube film (ACS Nano 2009,3:835-843).The people such as Hu have successfully prepared nano silver wire film by Mayer rod method, and (ACS Nano 2010,4 (5), 2955-2963).But up to the present also there is not the report that adopts the method to prepare graphene film and graphene composite film.
Summary of the invention
The object of the invention is to overcome the shortcoming of the method for preparing Graphene and/or graphene oxide film of prior art, provide a kind of line rod coating method that utilizes to prepare film that contains Graphene and/or graphene oxide and preparation method thereof, the method have advantages of can make the film that contains Graphene and/or graphene oxide of even thickness and have preparation speed fast, save solution, utilize the prepared film thickness of the method even, and the thickness deviation of the film prepared much smaller than prior art of thickness deviation.
The preparation method who the invention provides a kind of film that contains Graphene and/or graphene oxide, the method comprises the following steps: (1) is dispersed in Graphene and/or graphene oxide colloidal sol in solvent, to be mixed with the dispersion liquid that contains Graphene and/or graphene oxide that Graphene and/or graphene oxide concentration are 0.01-20mg/ml; (2) adopt line rod coating method to make dispersion liquid in substrate, form wet film, the diameter of the line of wherein said line rod coating method line rod used is 0.01-2mm; (3) solvent in the wet film obtaining in volatilization step (2).
The present invention also provides a kind of film that contains Graphene and/or graphene oxide, and the thickness of described film is 0.6-2300 nanometer, and the thickness deviation of film is less than or equal to 37%.
The preparation method of the film that contains Graphene and/or graphene oxide provided by the invention, by the concentration of Graphene and graphene oxide in control dispersion liquid, and be used in conjunction with the line of special diameter, make the method can make the film that contains Graphene and/or graphene oxide of even thickness and have advantages of that preparation speed is fast, saving solution.Adopt the thickness deviation of the film that contains Graphene and/or graphene oxide that method of the present invention makes to be less than or equal to 37%, and utilizing the scope of the centre plane resistance that prepared by the method for the present invention film that contains Graphene and/or graphene oxide records by four point probe tester is 50-～90000 Ω/sq, the transmittance recording at 550nm place by ultraviolet-visible-near infrared spectrometer is 57.8%～97.1%, utilize the film that contains Graphene and/or graphene oxide prepared by method of the present invention can be applied to the transparent electrode material that preparation contains Graphene, electrode for capacitors, lithium electricity electrode, solar cell and can be used as functional coating etc.
Accompanying drawing explanation
Fig. 1 is that the present invention utilizes Mayer Rod line rod coating method to prepare the principle schematic of the film that contains Graphene and/or graphene oxide;
Fig. 2 is the photo of the laminated film that contains Graphene prepared of the present invention;
Fig. 3 is the atomic force microscopy of the laminated film that contains Graphene prepared of the present invention, wherein a is the atomic force microscope electromicroscopic photograph that the embodiment of the present invention 1 adopts the film that contains Graphene prepared by the dispersion liquid that contains graphene oxide that graphene oxide concentration is 0.1mg/ml, and b is the atomic force microscope electromicroscopic photograph that the embodiment of the present invention 1 adopts the film that contains Graphene prepared by the dispersion liquid that contains graphene oxide that graphene oxide concentration is 1mg/ml;
Fig. 4 is the statistical Butut of the surface resistance of the film that contains Graphene that forms in polyethylene terephthalate (PET) substrate of the embodiment of the present invention 10.
Embodiment
The preparation method who the invention provides a kind of film that contains Graphene and/or graphene oxide, the method comprises the following steps: (1) is dispersed in Graphene and/or graphene oxide colloidal sol in solvent, to be mixed with the dispersion liquid that contains Graphene and/or graphene oxide that Graphene and/or graphene oxide concentration are 0.01-20mg/ml; (2) adopt line rod coating method to make dispersion liquid in substrate, form uniform wet film, the diameter of the line of wherein said line rod coating method line rod used is 0.01-2mm; (3) solvent in the wet film obtaining in volatilization step (2).
According to the present invention, described solvent can be deionized water and/or organic solvent, described organic solvent can be the various organic solvents that can dissolve Graphene and/or graphene oxide colloidal sol and volatile character, can be for example one or more in deionized water, ethanol, methyl alcohol, acetone, ether, dme, ethylene glycol, methylene dichloride, tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone (NMP), DMF (DMF); Preferred described solvent is one or more in N-Methyl pyrrolidone, dme, acetone and ethanol.
According to the present invention, the dispersion liquid that contains Graphene and/or graphene oxide is mixed with to the dispersion liquid that Graphene and/or graphene oxide concentration are 0.01-20mg/mL, be preferably 0.1-20mg/mL, more preferably 0.5-20mg/mL, is further preferably 1-20mg/mL.In the present invention, Graphene and/or graphene oxide concentration refer to the total concn of Graphene and graphene oxide, and in dispersion liquid, containing Graphene and not containing graphene oxide is the concentration of graphene oxide while being 0, the concentration that this concentration is Graphene; In dispersion liquid, containing graphene oxide and not containing Graphene is the concentration of Graphene while being 0, the concentration that this concentration is graphene oxide.
Line rod in line rod coating method, also can be called Mayer Rod line rod; According to the present invention, the diameter that forms the line of line rod is 0.01-2mm, is preferably 0.1-2mm, more preferably 0.6-2mm; The speed that described line rod is pulled through dispersion liquid is 10mm/s-300mm/s, is preferably 150mm/s.
According to the present invention, described substrate can be rigidity or flexible substrates, is preferably one or more in glass, quartz, silicon chip, polyethylene terephthalate (PET), polyimide, Copper Foil and aluminium foil.
The size of described substrate can be determined according to the size of the Graphene that will obtain and/or graphene oxide film.Because the present invention adopts line rod coating method, prepare film, therefore can obtain relatively large-area film, can be larger thereby the area of described substrate is corresponding, for example width can be up to 3 meters.
According to the present invention, under preferable case, described dispersion liquid can also contain one or more in small organic molecule, superpolymer, metal oxide, salt.The preparation of this dispersion liquid can comprise: first will contain Graphene and/or graphene oxide colloidal sol and a kind of mixing in small organic molecule, superpolymer, metal oxide, salt, redispersion is mixed with dispersion liquid in solvent.Wherein, described small organic molecule, superpolymer, metal oxide, salt can be for to not containing uniform and stable one or more that are dispersed in the various small organic molecules that cause disadvantageous effect in solvent, superpolymer, metal oxide, salt of Graphene and/or graphene oxide colloidal sol.Described small organic molecule can for contain in the uniform and stable various organic molecules that are dispersed in solvent of Graphene and/or graphene oxide colloidal sol one or more, can be for example one or more in sucrose, glucose, chitosan, be preferably sucrose; Described superpolymer can for contain in the uniform and stable various superpolymer that are dispersed in solvent of Graphene and/or graphene oxide colloidal sol one or more, can be for example one or more in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane, Polythiophene, polypyrrole and polydimethylsiloxane, be preferably one or more in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane and Polythiophene, in dispersion liquid, superpolymer adds the film that can obtain different purposes, optical waveguide film for example, high dielectric coat etc.; Described metal oxide can for contain in the uniform and stable various metal oxides that are dispersed in solvent of Graphene and/or graphene oxide colloidal sol one or more, can be for example stannic oxide, Indium sesquioxide, cobalt sesquioxide, one or more in Manganse Dioxide and titanium dioxide, be preferably stannic oxide, one or more in Manganse Dioxide and titanium dioxide; Described salt can for contain in the uniform and stable various inorganic or organic salt being dispersed in solvent of Graphene and/or graphene oxide colloidal sol one or more, it can be for example Palladous chloride, platinum chloride, ruthenium trichloride, one or more in gold perchloride and Silver Nitrate, be preferably Palladous chloride, one or more in platinum chloride and ruthenium trichloride.
According to the present invention, it can be 1 that the total amount of the small organic molecule in the graphene oxide in described dispersion liquid and/or Graphene and dispersion liquid, superpolymer, metal oxide, salt is counted in mass ratio: 0.1-30 mass ratio, is preferably 1: 1-10.
According to the present invention, the method that contains graphene oxide film and be reduced to graphene film is comprised to various physics and chemical reduction method, be preferably a kind of in high temperature thermal reduction, hydrazine steam reduction, hydrogen iodide steam or catalytic hydrogenation.
According to the present invention, the thickness of described wet film is 1-200 micron, the thickness of the film that the solvent in described volatilization wet film obtains is more preferably 30-2300 nanometer of 0.6-2300 nanometer, and the thickness deviation wherein calculating according to (thickness-mean thickness at the minimum place of the thickness of thickness maximum or thickness)/mean thickness is less than or equal to 37%.Particularly, the present inventor also finds, when the concentration of controlling dispersion liquid is at 1-2mg/ml, the diameter of line rod center line during in 30-2222.3 nanometer, can make the thickness deviation of graphene oxide film be less than 10% at the mean thickness of 0.6-2mm and the film that contains graphene oxide.Adopt graphene oxide that method of the present invention can obtain or length and the width of graphene film not to limit, those skilled in the art can be as required or the large freedom in minor affairs of area of base limit.
According to the present invention, under preferable case, the method is removed substrate after being also included in the solvent of removing in wet film.The method of removing substrate is well known to those skilled in the art, does not repeat them here.
According to a kind of embodiment of the present invention, this preparation method specifically comprises the following steps:
(1) Graphene and/or graphene oxide colloidal sol are dispersed in solvent, use vibrator or agitator or ultrasonic apparatus to mix 1-2 hour, preferably 1 hour, be mixed with the dispersion liquid of stable and uniform;
(2) line rod coating method line rod used is pulled through dispersion liquid with the speed of 10mm/s-300mm/s, and preferably 150mm/s is pulled through dispersion liquid in substrate, forms uniform wet film;
(3) solvent in the wet film obtaining in volatilization step (2), and remove substrate, obtaining thickness is the more preferably film that contains Graphene and/or graphene oxide of 30-2300 nanometer of 0.6-2300 nanometer.
Preparation in accordance with the present invention, wherein, under preferable case, the method is also included in step (2) before, first in substrate, form the film of a kind of superpolymer and/or metal oxide, the method of the film of formed superpolymer and/or metal oxide is prepared according to the preparation method of the film that contains Graphene and/or graphene oxide of the present invention, difference is that Graphene and/or graphene oxide are dispersed in solvent and replace with superpolymer and/or metal oxide are dispersed in solvent, and this preparation method specifically comprises the following steps:
(1) superpolymer and/or metal oxide are dispersed in solvent, use vibrator or agitator or ultrasonic apparatus to mix 1-2 hour, preferably 1 hour, be mixed with the dispersion liquid of stable and uniform;
(2) line rod coating method line rod used is pulled through dispersion liquid with the speed of 10mm/s-300mm/s, and preferably 150mm/s is pulled through dispersion liquid in substrate, forms uniform wet film;
(3) solvent in the wet film obtaining in volatilization step (2), obtain the film that contains superpolymer and/or metal oxide, and then the film that formation contains Graphene and/or graphene oxide on the film of the superpolymer forming and/or metal oxide, the method of the film that formation contains Graphene and/or graphene oxide is prepared according to the preparation method of the film that contains Graphene and/or graphene oxide of the present invention, and remove substrate, obtain the mixed film that contains Graphene and/or graphene oxide and superpolymer and/or metal oxide.
The present invention also provides a kind of film that contains Graphene and/or graphene oxide of being prepared by aforesaid method, and the thickness of described film is preferably 0.6-2300 nanometer, is further preferably 30-2300 nanometer, and the thickness deviation of film is less than or equal to 37%.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Below will describe the present invention by embodiment.In following examples, described in contain Graphene and/or graphene oxide film thickness by atomic force microscope (Nanoman IIdimention3100), record; Surface resistance parameter records according to GB/T1551-2009 by four point probe resistance meter (the two electrical measurement four point probe testers of RTS-9 type, Guangzhou four point probe scientific & technical corporation); Transmittance parameter records by ultraviolet-visible-near infrared spectrometer (Lambda950UV/VIS/NIR, perkin elmer Instrument Ltd.).
Contain Graphene and/or graphene oxide colloidal sol by the method preparation in preparation example 1 and preparation example 2.
Preparation example 1
Natural graphite powder (1 part of quality) is processed 3 hours with the vitriol oil (30 parts of quality) and potassium permanganate (3 parts of quality) under condition of ice bath, be warmed up to 35 ℃ of left and right, keep 30 minutes, the water that adds 45 parts of quality 95 ℃ of temperature, react after 15 minutes, add 30 % by weight hydrogen peroxide of 3.5 parts of quality and the water of 26.5 parts of quality, obtain jonquilleous suspension.By suspension filtered, use the hydrochloric acid washing leaching cake 3 times of 3 % by weight, by the filter cake obtaining 60 ℃ of oven dry, gained filter cake is scattered in water, obtain graphene oxide colloidal sol, by this colloidal sol centrifugation, again disperse, after repeatedly processing, (generally processing more than 3 times) obtains purer graphene oxide colloidal sol (wherein the content of graphene oxide is 20mg/ml % by weight), for the preparation of the film that contains graphene oxide.
Preparation example 2
Thermal expansion Graphite Powder 99 or micro crystal graphite or natural graphite (1 part of quality) are joined in N-Methyl pyrrolidone solvent (1000 parts) to ultrasonic 30min in the ultrasonic apparatus of 300w power.Use whizzer by the dispersion liquid obtaining centrifugal 60min under the rotating speed of 500 revs/min.Discard the thick graphite flake layer in bottom, obtain the colloidal sol of upper strata grey.The colloidal sol of this upper strata grey is centrifugal under the speed conditions of 5000 revs/min, and bottom obtains the Graphene colloidal sol (wherein the content of Graphene is 1mg/ml % by weight) of black, for the preparation of the film that contains Graphene.
Embodiment 1
The graphene oxide colloidal sol of preparation example 1 preparation is dispersed in to the alcohol dispersion liquid that is mixed with graphene oxide concentration graphene oxide as shown in table 1 below in ethanol, uses vibrator concussion to mix 1h, obtain homodisperse stable dispersion liquid.Get the one end at the bottom of 0.5ml drops in the silicon wafer-based of 5cm * 5cm, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is as shown in table 1 below, at silicon wafer-based basal surface, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide film, and the graphene oxide film that uses atomic force microscope to prepare preparation method of the present invention characterizes, and the mean thickness of this graphene oxide film provides at table 1.
Table 1
The thickness deviation that contains graphene oxide film that from table 1 prepared by preparation in accordance with the present invention is within the scope of 2.0%-37%, much smaller than the thickness deviation of prior art 40%-50%.From the result of table 1, it can also be seen that, when the concentration of controlling dispersion liquid is at 1-2mg/ml, the diameter of line rod center line during in 30-2222.3 nanometer, can make the thickness deviation of graphene oxide film be less than 10% at the mean thickness of 0.6-2mm and the film that contains graphene oxide.
Fig. 3 is atomic force microscope electromicroscopic photograph, a is that embodiment 1 graphene oxide dispersion liquid concentration is 0.1mg/ml, under line rod linear diameter 0.2mm condition, be coated in the film that contains graphene oxide on silicon chip, b is that embodiment 1 graphene oxide dispersion liquid concentration is 1mg/ml, under line rod linear diameter 0.2mm condition, be coated in the film that contains graphene oxide on silicon chip, from figure, a can find out that the thickness of film is 0.9-1.5nm, and the mean thickness of film is 1.1nm, and thickness deviation is 37%; From figure, b can find out that the thickness of film is 10.2-15.3nm, and the mean thickness of film is 12.3nm, and thickness deviation is 17.1%.Figure a and figure b show that the film that contains graphene oxide prepared by preparation method of the present invention is more even.
Embodiment 2
The Graphene colloidal sol obtaining in preparation example 2 is dispersed in to the N-Methyl pyrrolidone dispersion liquid that is mixed with Graphene concentration Graphene as shown in table 2 below in N-Methyl pyrrolidone, uses the ultrasonic 1h of ultrasonic apparatus, obtain homodisperse stable dispersion liquid.Get the one end at the bottom of 1ml drops in the silicon wafer-based of 10cm * 10cm, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is as shown in table 2 below, at silicon wafer-based basal surface, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and removes substrate, obtains the film that contains Graphene, and the film that contains Graphene that uses atomic force microscope to prepare preparation method of the present invention characterizes, and the mean thickness of graphene film provides at table 2.
Table 2
The thickness deviation that contains graphene film that from table 2 prepared by preparation in accordance with the present invention is within the scope of 5.5%-36.0%, much smaller than the thickness deviation of prior art 40%-50%.
The film that contains Graphene that the thickness that uses four point probe resistance meter to prepare preparation method of the present invention is 0.6nm characterizes, the centre plane resistance that records film is 1000 Ω/sq, and by ultraviolet-visible-near infrared spectrometer, recording the transmittance of this graphene film at 550nm place is 97.1%.
Embodiment 3
The graphene oxide colloidal sol of preparation in preparation example 1 and sucrose be take to ratio blending dispersion that mass ratio is 1: 1 and in ethanol, be mixed with graphene oxide that graphene oxide concentration is 1mg/mL and the alcohol dispersion liquid of sucrose, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml and drop in a section of quartz plate, use line rod to be pulled through solution with the speed of 150mm/s, on quartz plate surface, form the uniform wet film of one deck.Wet film removes solvent in flowing air volatilization, obtains the laminated film of graphene oxide-sucrose.Then graphene oxide-sucrose laminated film is placed in to high temperature reaction stove, at H
2under the mixed atmosphere of Ar, 1100 ℃ of reaction annealing vapor away solvent, and remove substrate, obtain Graphene-sucrose laminated film, Graphene-sucrose the laminated film that uses atomic force microscope to prepare preparation method of the present invention characterizes, and obtaining mean thickness is Graphene-sucrose laminated film that 6.8nm, thickness deviation are 9%.Graphene-sucrose the laminated film that contains that uses four point probe resistance meter to prepare preparation method of the present invention characterizes, the centre plane resistance that records this film is 1173 Ω/sq, and by ultraviolet-visible-near infrared spectrometer, recording the transmittance of this Graphene-sucrose laminated film at 550nm place is 83%.
Embodiment 4
Polymethylmethacrylate (PMMA) is dispersed in and in dme, is mixed with the solution that concentration is 10 % by weight, get 1ml and drop in one end of PET, use line rod to be pulled through solution with the speed of 150mm/s, at pet sheet face, form the uniform wet film of one deck, by oven dry, remove solvent, obtain the film of polymethylmethacrylate.The graphene oxide colloidal sol of preparation in preparation example 1 is dispersed in and in ethanol, is mixed with the alcohol dispersion liquid that graphene oxide concentration is the graphene oxide of 0.1mg/ml, use vibrator concussion to mix 1h, obtain homodisperse stable dispersion liquid, get 2ml and drop in one end of the PET that scribbles PMMA, use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, dry, and remove substrate, obtain containing graphene oxide/PMMA laminated film, graphene oxide/PMMA the laminated film that uses atomic force microscope to prepare preparation method of the present invention characterizes, the mean thickness of graphene oxide/PMMA laminated film is 198.6nm, thickness deviation is 7.3%.By ultraviolet-visible-near infrared spectrometer, recording the transmittance of this graphene oxide/PMMA laminated film at 550nm place is 60%.
Embodiment 5
The graphene oxide of preparation in preparation example 1 and epoxy resin be take to ratio blending dispersion that mass ratio is 1: 10 and in acetone, be mixed with graphene oxide that graphene oxide concentration is 1mg/ml and the acetone dispersion liquor of epoxy resin, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop at one section of quartz plate, use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 2mm, on quartz plate surface, form the uniform wet film of one deck, wet film is removed solvent in flowing air volatilization, and remove substrate, the laminated film of graphene oxide-epoxy resin that use atomic force microscope is prepared preparation method of the present invention characterizes, the laminated film mean thickness of the graphene oxide-epoxy resin obtaining is 2 microns, and thickness deviation is 3.5%.The transmittance of the laminated film that records this graphene oxide-epoxy resin by ultraviolet-visible-near infrared spectrometer at 550nm place is 60%.
Embodiment 6
The Graphene of preparation in preparation example 1 and Polythiophene be take to ratio blending dispersion that mass ratio is 1: 1 and in N-Methyl pyrrolidone, be mixed with Graphene that Graphene concentration is 0.2mg/ml and the N-Methyl pyrrolidone dispersion liquid of Polythiophene, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop at one section of quartz plate, use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.1mm, on quartz plate surface, form the uniform wet film of one deck, wet film is by drying or removing solvent in flowing air volatilization, and remove substrate, the laminated film of Graphene-Polythiophene that use atomic force microscope is prepared preparation method of the present invention characterizes, the mean thickness of the laminated film of the Graphene-Polythiophene obtaining is 2nm, and thickness deviation is 13.0%.Graphene-the polythiophene film that uses four point probe resistance meter to prepare preparation method of the present invention characterizes, and the centre plane resistance that draws film is 2000 Ω/sq.By ultraviolet-visible-near infrared spectrometer, recording the transmittance of this Graphene-polythiophene film at 550nm place is 95.2%.
Embodiment 7
The Graphene of preparation in preparation example 2 and ITO colloidal sol be take to ratio blending dispersion that mass ratio is 1: 30 and in water, be mixed with the dispersion liquid of the water of Graphene that Graphene concentration is 0.1mg/ml and ITO, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the PET of 10cm * 10cm substrate, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 1mm, at pet sheet face, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and the Graphene-ITO laminated film that uses atomic force microscope to prepare preparation method of the present invention characterizes, and the mean thickness of the Graphene-ITO laminated film obtaining is 300nm, and thickness deviation is 27.5%.The centre plane resistance that records Graphene-ITO laminated film by four point probe tester is 100/sq, and by ultraviolet-visible-near infrared spectrometer, recording the transmittance of this Graphene-ITO laminated film at 550nm place is 85%.
Embodiment 8
The graphene oxide colloidal sol of preparation in preparation example 1 and stannic oxide be take to ratio blending dispersion that mass ratio is 1: 2 and in water, be mixed with graphene oxide that graphene oxide concentration is 1mg/ml and the aqueous dispersions of stannic oxide, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the Copper Foil substrate of 10cm * 10cm, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 2mm, at copper foil surface, form the uniform wet film of one deck, dry wet film, and remove substrate, obtain graphene oxide-stannic oxide laminated film.By this graphene oxide-stannic oxide laminated film as for high temperature reduction in atmosphere of hydrogen, obtain Graphene-stannic oxide laminated film, Graphene-stannic oxide the laminated film that uses atomic force microscope to prepare preparation method of the present invention characterizes, the mean thickness of the Graphene-stannic oxide laminated film obtaining is 600nm, and thickness deviation is 6.8%.Graphene-stannic oxide the laminated film that uses four point probe resistance meter to prepare preparation method of the present invention characterizes, the centre plane resistance that draws film is 50 Ω/sq, and by ultraviolet-visible-near infrared spectrometer, recording the transmittance of this Graphene-stannic oxide laminated film at 550nm place is 57.8%.
Embodiment 9
The graphene oxide colloidal sol of preparation in preparation example 1 and Manganse Dioxide be take to ratio blending dispersion that mass ratio is 1: 3 and in ethanol, be mixed with graphene oxide that graphene oxide concentration is 1mg/ml and the alcohol dispersion liquid of Manganse Dioxide, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the nickel foil substrate of 10cm * 10cm, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 1mm, on nickel foil surface, form the uniform wet film of one deck, dry wet film, and remove substrate, obtain graphene oxide-Manganse Dioxide laminated film.By this graphene oxide-Manganse Dioxide laminated film as for high temperature reduction in atmosphere of hydrogen, obtain Graphene-Manganse Dioxide laminated film, Graphene-Manganse Dioxide the laminated film that uses atomic force microscope to prepare preparation method of the present invention characterizes, the mean thickness of the Graphene-Manganse Dioxide laminated film obtaining is 400nm, and thickness deviation is 8%.Graphene-Manganse Dioxide the laminated film that uses four point probe resistance meter to prepare preparation method of the present invention characterizes, the centre plane resistance that records film is 100 Ω/sq, and by ultraviolet-visible-near infrared spectrometer, recording the transmittance of this Graphene-Manganse Dioxide laminated film at 550nm place is 58.0%.
Embodiment 10
By graphene oxide colloidal sol and PdCl in preparation example 1
2the ratio blending dispersion that the mass ratio of take is 1: 0.1 is mixed with graphene oxide and the PdCl that graphene oxide concentration is 1mg/ml in ethanol
2alcohol dispersion liquid, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the PET of 10cm * 10cm substrate, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, at pet sheet face, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-PdCl
2laminated film.By this graphene oxide-PdCl
2laminated film is as in atmosphere of hydrogen, and reduction 6h, obtains Graphene-PdCl
2laminated film, the Graphene-PdCl that uses atomic force microscope to prepare preparation method of the present invention
2laminated film characterizes, and dries the Graphene-PdCl obtaining
2the mean thickness of laminated film is 10.8nm, and thickness deviation is 35.8%.By four point probe tester, record Graphene-PdCl prepared by preparation method of the present invention
2the centre plane resistance of laminated film is 1670 Ω/sq, by ultraviolet-visible-near infrared spectrometer, records this Graphene-PdCl
2the transmittance of laminated film at 550nm place is 65%.
Fig. 4 is Graphene-PdCl that embodiment 10 obtains
2the statistical Butut of the centre plane resistance of equally distributed 100 points of laminated film, as can be seen from the figure Graphene-PdCl
2the standard deviation of laminated film centre plane resistance is 3.7%, shows Graphene-PdCl prepared by preparation method of the present invention
2laminated film resistance ratio is more even.
Embodiment 11
By graphene oxide colloidal sol and PtCl in preparation example 1
2the ratio blending dispersion that the mass ratio of take is 1: 0.5 is mixed with graphene oxide and the PtCl that graphene oxide concentration is 0.5mg/ml in ethanol
2alcohol dispersion liquid, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the PET of 10cm * 10cm substrate, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.2mm, at pet sheet face, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-PtCl
2laminated film.By this graphene oxide-PtCl
2laminated film is as in atmosphere of hydrogen, and 80 ℃ of reduction 6h, obtain Graphene-PtCl
2laminated film, the Graphene-PtCl that uses atomic force microscope to prepare preparation method of the present invention
2laminated film characterizes, and dries the Graphene-PtCl obtaining
2the mean thickness of laminated film is 2.8nm, and thickness deviation is 35%.By four point probe tester, record Graphene-PtCl prepared by preparation method of the present invention
2the centre plane resistance of composite membrane is 90000 Ω/sq, by ultraviolet-visible-near infrared spectrometer, records this Graphene-PtCl
2the transmittance of laminated film at 550nm place is 90%.
Embodiment 12
By graphene oxide colloidal sol and RuCl in preparation example 1
3the ratio blending dispersion that the mass ratio of take is 1: 1 is mixed with graphene oxide and the RuCl that graphene oxide concentration is 3mg/ml in ethanol
3alcohol dispersion liquid, the even 1h of mechanically mixing, obtains homodisperse stable dispersion liquid.Get 1ml dispersant liquid drop in one end of the polyimide substrate of 10cm * 10cm, then use line rod to be pulled through dispersion liquid with the speed of 150mm/s, wherein, the diameter of line rod center line is 0.1mm, at polyimide surface, forms the uniform wet film of one deck.Wet film vapors away solvent in flowing air, and removes substrate, obtains graphene oxide-RuCl
3laminated film.By graphene oxide-RuCl
3laminated film is as in atmosphere of hydrogen, and 160 ℃ of reduction 6h, dry, and obtain Graphene-RuCl
3laminated film, the Graphene-RuCl that uses atomic force microscope to prepare preparation method of the present invention
3laminated film characterizes, the Graphene-RuCl obtaining
3the mean thickness of laminated film is 12.2nm, and thickness deviation is 15%.The centre plane resistance of testing this film by four point probe tester is 400 Ω/sq, by ultraviolet-visible-near infrared spectrometer, records this Graphene-RuCl
3the transmittance of laminated film at 550nm place is 60.0%.
Claims (12)
1. a preparation method who contains the film of Graphene and/or graphene oxide, the method comprises the following steps:
(1) Graphene and/or graphene oxide colloidal sol are dispersed in and in solvent, are mixed with the dispersion liquid that contains Graphene and/or graphene oxide that the concentration of Graphene and/or graphene oxide is 1-2mg/ml;
(2) adopt line rod coating method to make dispersion liquid in substrate, form uniform wet film, the diameter of the line of wherein said line rod coating method line rod used is 0.6-2mm;
(3) solvent in the wet film obtaining in volatilization step (2);
And when the thickness of the film that contains Graphene and/or graphene oxide is 30-2222.3 nanometer, make the thickness deviation of film be less than or equal to 10%.
2. preparation method according to claim 1, wherein, described solvent is deionized water and/or organic solvent.
3. preparation method according to claim 2, wherein, described solvent is one or more in N-Methyl pyrrolidone, dme, acetone and ethanol.
4. preparation method according to claim 1, wherein, the pulling rate of described line rod coating method center line rod is 10mm/s-300mm/s.
5. preparation method according to claim 1, wherein, described substrate is rigidity or flexible substrates.
6. preparation method according to claim 5, wherein, described substrate is one or more in glass, quartz, silicon chip, polyethylene terephthalate, polyimide, Copper Foil and aluminium foil.
7. preparation method according to claim 1, wherein, described dispersion liquid also contains one or more in small organic molecule, superpolymer, metal oxide and salt.
8. according to the preparation method described in claim 1 or 7, wherein, the total amount of the small organic molecule in the Graphene in described dispersion liquid and/or graphene oxide and dispersion liquid, superpolymer, metal oxide and salt is counted 1:0.1-30 in mass ratio.
9. preparation method according to claim 8, wherein, described small organic molecule is one or more in sucrose, glucose and chitosan, described superpolymer is one or more in polymethylmethacrylate, 2-glycidyl ethers dihydroxyphenyl propane, Polythiophene, polypyrrole and polydimethylsiloxane, described metal oxide is one or more in stannic oxide, Indium sesquioxide, cobalt sesquioxide, Manganse Dioxide and titanium dioxide, and described salt is one or more in Palladous chloride, platinum chloride, ruthenium trichloride, gold perchloride and Silver Nitrate.
10. preparation method according to claim 1, wherein, the method is also included in step (2) before, first in substrate, form the film of a kind of superpolymer and/or metal oxide, and then form the film that contains Graphene and/or graphene oxide on the film of the superpolymer forming and/or metal oxide.
11. according to the preparation method described in claim 1 or 10, wherein, the described dispersion liquid that contains Graphene and/or graphene oxide is the dispersion liquid that contains graphene oxide, and the method also comprises reduces the thermal reduction of step (3) products therefrom employing high temperature, hydrazine steam reduction, hydrogen iodide steam or catalytic hydrogenation.
12. films that in claim 1-11 prepared by the preparation method described in any one.
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