CN101702345B - Preparation method for laminated graphene conductive film - Google Patents
Preparation method for laminated graphene conductive film Download PDFInfo
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- CN101702345B CN101702345B CN2009102324911A CN200910232491A CN101702345B CN 101702345 B CN101702345 B CN 101702345B CN 2009102324911 A CN2009102324911 A CN 2009102324911A CN 200910232491 A CN200910232491 A CN 200910232491A CN 101702345 B CN101702345 B CN 101702345B
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Abstract
The present invention discloses a preparation method for laminated graphene conductive film, belonging to the technical field of nano-zided photoelectric material. The present invention in particular relates to a graphene film with wetting reduction oxidation at the temperature of 60-200 DEG C and a preparation method for forming film through lamination several times. The laminated reduction-oxidation graphene film provided by the invention has the following advantages: (1) the utilization rate of raw material is high; (2) the reduction temperature is moderate; (3) the electric conductivity is high; (4) the square resistance is low and controllable; (5) the cost is low. The invention is widely applied to organic photoelectric functional devices such as organic electroluminescent display, organic electric storage and artificial muscle; and the film is expected to become a novel conductive film in place of the ITO and conductive polymer film applied to flexible device.
Description
Technical field
The invention belongs to the nanometer photoelectronic material sciemtifec and technical sphere.Be specifically related to a kind of method of reducing of graphene oxide conductive film and the technology of preparing of the film forming that repeatedly superposes, in conductive film and photoelectric functional device, be widely used.
Technical background
The application widely that conductive film has in a lot of fields is such as the electrode of function elements such as electrical storage, light-emitting diode, artificial-muscle, solar cell.Current, the most common electrode is based on the metal-oxide film of traditional inorganic material, such as ITO, IZO etc.Yet deficient day by day along with rare metal, price is expensive day by day, and its fragility characteristics have further limited their large-scale application in the photoelectric functional devices field, particularly can flexible organic photoelectric function element.So exploitation has cheap, abundant raw materials, high and flexible good conductive film economic interests and strategic importance of stability is great.At present, have flexible material simultaneously and mainly contain conducting polymer and carbon nano-tube with conducting function.Relatively and the inorganic metal conductive film, conventional conductive polymeric material such as PANI, PPy etc. exists conductivity relatively poor relatively.Though conductivity such as novel conductive polymer such as PEDOT:PSS is higher, has the high deficiency of price.Carbon nano-tube has outstanding electric property and excellent mechanical performance, is one of ideal material of preparation compliant conductive film.But carbon nano-tube is low at preparation and not only productive rate in the purge process, and separation difficulty and poor efficiency between metallicity and the semiconductive carbon nano tube, makes the preparation process complexity of film, the cost height.
In recent years, Graphene is because of having high mobility (20000～50000cm
2/ Vs), unique integer quantum hall effect, the research focus that good mechanical performance becomes people, the film of making based on Graphene will become ideal conducting film of new generation.The synthetic method of Graphene mainly contains mechanical stripping method, dilatometry, epitaxy method, heating SiC method, chemical vapour deposition technique, oxidation-reduction method and solvent-thermal method etc., and wherein oxidation-reduction method has the extremely concern of company and research and development institution of efficient height, output is big, cost is low characteristics.Oxidation-reduction method is used Hummers method [Hummers, W.S. usually; Offeman R E.J.Am.Chem.Soc.1958,80,1339.] graphite is transferred to the graphene oxide of nearly insulation, then its reduction is become conductive graphene, reduction can obtain conductive graphene membrane to graphene oxide film.At present, reduction mode mainly contains hydrazine steam or NaBH
4Reduction, high-temperature heat treatment and electrochemical reduction.But they exist, and reduction effect is poor, heat treatment temperature height, immersion liquid and the low deficiency of raw material availability.So developing new method of reducing is a urgent problem for the flexible high conductivity graphene film of efficient production.
Summary of the invention
Technical problem: main purpose of the present invention is to propose a kind of preparation method of lamination Graphene conductive film, and the method for utilizing the multilayer stack to combine with efficient reduction is further optimized the square resistance of film.The film of this method preparation has the conductivity height, and square resistance is low and can regulate and control, and heat treatment temperature is low, the advantage that utilization rate of raw materials height and cost are low.Has potential actual application value at conductive film (particularly compliant conductive film) and photoelectric functional devices field.
Technical scheme: the preparation method of lamination Graphene conductive film of the present invention comprises the preparation of individual layer redox graphene film and the preparation process that superposes repeatedly thereof, comprises that specifically step is as follows:
1) preparation graphene oxide film;
2), wettingly go back original reagent by force and carry out heat treated on the graphene oxide film surface;
3) on the surface of redox graphene conductive film, stack one deck graphene oxide film;
4) graphene oxide film that is applied carry out step 2) reduction of method;
5) repetitive operation step 1) and step 2), realize the plural layers stack.
Mono-layer graphite oxide alkene film thickness provided by the invention is less than 1.4 microns.
Film surface is wetting goes back original reagent by force and is selected from anhydrous hydrazine, hydrazine hydrate, dimethylhydrazine or the diamine any one.
The wetting mode of film surface is selected from painting method, immerse a kind of in the extraction method of back.Between 60-200 ℃, heat treatment time is not less than 4 hours to the heat treatment temperature of wetting film.
The mode of regulation and control redox graphene conductive film square resistance provided by the invention is to realize that with the stacked system of multilayer redox graphene film the regulation and control amplitude of film rectangular resistance is controlled by quantity that is applied film and thickness.
The method of reducing of described stack graphene oxide film is to carry out wetting with the extensive chemical reducing agent to the graphene oxide film surface.Reducing agent mainly comprises anhydrous hydrazine, hydrazine hydrate, dimethylhydrazine and Hydra Ver 2 diamines, and wetting mode mainly contains coating method and immerses the back extraction method.Then to the heat treatment more than 4 hours under 60-200 ℃ of condition of the graphene oxide film after wetting.
Beneficial effect: among the present invention graphene oxide film through the auxiliary reduction of strong reductant profit and mild temperature after, conductivity of electrolyte materials has had and has increased substantially, the conductivity after the reduction reaches 2600S/m, far above other chemical reduction method of the same type.The square resistance of film descends significantly, and is low to 10
2Magnitude is near the square resistance of part inorganic, metal oxide conductive film.In addition, according to the method, expection can obtain the redox graphene conductive film of any square resistance.
Major advantage of the present invention is:
1. conductivity height;
2. square resistance is low and can regulate and control;
3. the reduction temperature gentleness is fit to the compliant conductive film preparation;
4. utilization rate of raw materials height, cost is low.
Description of drawings
Fig. 1. the filtration volume of individual layer redox graphene film and square resistance (side's resistance) graph of a relation.
Fig. 2. the number of plies of multilayer stack redox graphene film and square resistance (side's resistance) relation curve.
Embodiment
In order to understand the content of patent of the present invention better, further specify below by instantiation.But these embodiment do not limit the present invention, and those skilled in the art make some nonessential improvement and adjustment according to the content of foregoing invention, all belong to protection range of the present invention.
Comprise that specifically step is as follows:
1) preparation graphene oxide film;
2), wettingly go back original reagent by force and carry out heat treated on the graphene oxide film surface;
3) on the surface of redox graphene conductive film, stack one deck graphene oxide film;
4) graphene oxide film that is applied carry out step 2) reduction of method;
5) repetitive operation step 1) and step 2), realize the plural layers stack.
Mono-layer graphite oxide alkene film thickness is less than 1.4 microns.Film surface is wetting goes back original reagent by force and is selected from anhydrous hydrazine, hydrazine hydrate, dimethylhydrazine or the diamine any one.The wetting mode of film surface is selected from painting method, immerse a kind of in the extraction method of back.Between 60-200 ℃, heat treatment time is not less than 4 hours to the heat treatment temperature of wetting film.
Embodiment 1: the preparation method of low square resistance redox graphene conductive film.
Graphene oxide preparation: with 2.5g graphite, 1.9g NaNO
3, 11.5g KMnO
4And the dense H of 85ml
2SO
4Mix the first ice bath in back and stirred 1 hour, stirred 2 days under the room temperature then, add the 250ml 5wt%-1-concentrated sulfuric acid and 20ml 30wt%H at last
2O
2Continue to stir 2 days and centrifugal, washed with de-ionized water, so repeat 3 times and obtain graphene oxide.
Graphene oxide film preparation and reduction: the ultrasonic dispersion liquid of graphene oxide of preparation 0.05mg/ml, the centrifugal large stretch of particle of minute quantity of removing in back.Earlier get 50ml respectively, 100ml, the above-mentioned solution of 150ml prepares film by vacuum filtration, and note is made G (50), G (100), G (150), respectively to being transferred to glass substrate behind every part of filtration membrane 4 equal portions.To select HydraVer 2 diamines then be strong reductant and carry out wetting by coating method to the surface of graphene oxide film.Place in the surface plate at last and sealing, heated 18 hours down at 100 ℃.Simultaneously every group of equal thickness sample thin film carried out the reduction of HydraVer 2 diamine steams, reaction temperature and time are the same, in order to the contrast reference.Four point probe test reduction film rectangular resistance shows: square resistance is all above measuring range (10 during the steam reduction
5Ω/), the square resistance of 50ml filter membrane is the twice of 100ml filter membrane square resistance during wetting the reduction, and two kinds of film conductivities are identical, shows all by effectively evenly reduction.With respect to 100ml reduction filter membrane, the square resistance of 150ml reduction filter membrane descends not obvious, shows that its part is reduced.The minimum square resistance of individual layer redox graphene film reaches 450 Ω/.
Embodiment 2: the preparation method of the redox graphene conductive film that square resistance is controlled.
Here select filtering volume is that the graphene oxide film of 0.05mg/ml is a single thin film for 50ml density.Be on the basis of redox graphene film of 50ml at the filtration volume of embodiment 1 preparation, shift the graphene oxide film of stack second layer equal thickness.Adopt the method for reducing among the embodiment 1 that second layer graphene oxide film is reduced then.Similarly method has prepared the three stacked redox graphene conductive films that add.The four point probe test shows: filtering volume among the square resistance of double-deck stack reduction film and the embodiment 1 is the square resistance approximately equal of the redox graphene film of 100ml, show the good and evenly equivalence of reduction of contact between the stack film, conductivity remains unchanged in theory; Three stacked adding, reduced the square resistance of film and are starkly lower than that to filter volume among the embodiment 1 be the square resistance of the redox graphene film of 150ml, reached 300 Ω/.The square resistance and the film thickness product of individual layer and double-deck stack redox graphene film all are constants, three stacked square resistances that add film and the experiment values in the experimental error allowed band according to this constant calculations coincide, so the thickness by the control single thin film and the number of plies realize the regulation and control to film rectangular resistance.
Claims (4)
1. the preparation method of a lamination Graphene conductive film is characterized in that this method comprises the preparation of individual layer redox graphene film and the preparation process that superposes repeatedly thereof, comprises that specifically step is as follows:
1) preparation graphene oxide film;
2), wettingly go back original reagent by force and carry out heat treated on the graphene oxide film surface; Between 60-200 ℃, heat treatment time is not less than 4 hours to the heat treatment temperature of wetting film;
3) on the surface of redox graphene conductive film, stack one deck graphene oxide film;
4) graphene oxide film that is applied carry out step 2) reduction of method;
5) repetitive operation step 1) and step 2), realize the plural layers stack.
2. the preparation method of graphene conductive film according to claim 1 is characterized in that mono-layer graphite oxide alkene film thickness is less than 1.4 microns.
3. the preparation method of graphene conductive film according to claim 1 is characterized in that the wetting original reagent of going back by force of film surface is selected from anhydrous hydrazine, hydrazine hydrate, the dimethylhydrazine any one.
4. the preparation method of graphene conductive film according to claim 1 is characterized in that the wetting mode of film surface is selected from painting method, immerses a kind of in the extraction method of back.
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| CN103310873B (en) * | 2012-03-08 | 2015-08-19 | 中国科学院理化技术研究所 | Transparent conductive graphene membrane and its preparation method and application |
| US20150125758A1 (en) * | 2012-06-29 | 2015-05-07 | Ocean's King Lighting Science & Technology Co., Ltd. | Graphene film, preparation method and application thereof |
| CN102789842B (en) * | 2012-07-27 | 2014-12-31 | 青岛科技大学 | Preparation method of conducting polymer/grapheme composite nanometer material |
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| CN103011149B (en) * | 2012-12-27 | 2014-10-22 | 上海交通大学 | Preparation method and application of multilayer reduced graphene film |
| CN103035666A (en) * | 2012-12-28 | 2013-04-10 | 江苏宇迪光学股份有限公司 | Panel of large-sized flexible flat-panel display and manufacture method thereof |
| CN104313872B (en) * | 2014-10-11 | 2016-06-08 | 江南大学 | A kind of preparation method of graphene/polyaniline covalent bond compliant conductive fabric |
| CN105225766B (en) * | 2015-07-30 | 2017-10-20 | 国家纳米科学中心 | A kind of preparation method of transparent graphene conductive film |
| CN106185901B (en) * | 2016-07-15 | 2019-02-12 | 浙江大学 | A kind of high resiliency graphene film |
| CN110511029A (en) * | 2019-09-10 | 2019-11-29 | 北京中石伟业科技无锡有限公司 | A kind of method that binder free graphene oxide prepares high orientation graphite block body |
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