CN103710685B - A kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate - Google Patents
A kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate Download PDFInfo
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- CN103710685B CN103710685B CN201310723398.7A CN201310723398A CN103710685B CN 103710685 B CN103710685 B CN 103710685B CN 201310723398 A CN201310723398 A CN 201310723398A CN 103710685 B CN103710685 B CN 103710685B
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Abstract
The present invention relates to a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate, preparation water-ethanol-graphene oxide dispersion, flexible base board is carried out cleaning and drying in baking oven under ultrasonic, then utilizing on hot-plate is heated to close to flexible base board softening temperature, water-ethanol-graphene oxide dispersion being joined is connected with in the airbrush of air pump, be ejected on flexible base board, obtain graphene oxide film, graphene oxide film is reduced, prepares transparent graphene conductive film.Compared with prior art, the present invention have efficient, feasible, be suitable for the advantage such as big area, extensive preparation.
Description
Technical field
The invention belongs to function film technical field, especially relate to a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate.
Background technology
Each carbon atom in Graphene is with sp
2mode (σ key) and other 3 carbon atoms of hybridized orbital are connected, and extremely strong C-C key causes graphene sheet layer to have excellent mechanical property.A remaining p electronic orbit, perpendicular to graphene planes, forms the π key of delocalization with the carbon atom of surrounding, causes electronics can move freely in crystal, imparts the electrical property that Graphene is good.Because interatomic reactive force is very strong, at normal temperatures, even if around carbon atom telescopes, the interference that the electronics in Graphene is subject to is also very little.Not easily scattering occurs when electronics transmits in Graphene, mobility can reach 2 × 10
5cm
2/ (Vs).Its surface resistance is about 31 Ω/sq, and specific conductivity can reach 10
6s/m is the material of room temperature conductivity the best.Compared with traditional ITO, Graphene has the following advantages: (1) has higher conductivity, and (2) have good snappiness, (3) resource comparatively horn of plenty.Therefore, graphene-based transparent conductive film develops rapidly in recent years, and is applied to the fields such as touch-screen, Organic Light Emitting Diode, organic photovoltaic devices and organic transistor.
The preparation method of graphene-based transparent conductive film is mainly divided into two large classes: Physical and chemical method.Wherein Physical is mainly divided into CVD and liquid phase physics stripping method.In general, CVD is compared to liquid phase physics stripping method and chemical method, and prepared graphene-based transparent conductive film has higher electroconductibility and transmittance.But also there is outstanding limitation, be mainly manifested in manufacturing cost higher, preparation technology is comparatively complicated.It is lower that the limitation that liquid phase physics stripping method is comparatively given prominence to is mainly manifested in production efficiency.And chemical method is compared to Physical, its advantage is mainly manifested in following method: (1) production cost is lower; (2) preparation technology is comparatively simple; (3) preparation efficiency is higher.Therefore, chemical method prepares the important directions studied after graphene-based transparent conductive film will be.The method of current chemical preparation transparent graphene conductive film mainly contains: vacuum filtration, LB method, spin-coating method, self-assembly and spraying method.And spraying method is compared to the advantage of additive method: (1) spraying can be carried out on curved substrate; (2) preparation process is easy, and production efficiency is higher; (3) be applicable to can be used for big area film forming; (4) spray equipment is easy to carry and moves.
Spraying method refers to, sprays in the substrate of preheating, obtain the process of graphene film after solvent evaporates with the airbrush of specialty by graphene dispersing solution.The effect of fog gun is atomised dispersion, forms small droplets.Preheating substrate is that solvent can evaporate rapidly, avoids the reunion of graphene film in order to ensure after on droplet deposition to substrate, the graphene-based transparent conductive film of final formation.2010, graphene oxide solution and hydrazine hydrate solution mixed by Pham etc., and graphene oxide and hydrazine hydrate mixing solutions being ejected into Heating temperature in advance by the mode of spraying is that the graphene film that area is 4 inches prepared by the substrate of 240 DEG C.Test shows, when the transmittance (λ=550nm) of prepared TCFs is 84%, square resistance is 2.2k Ω/sq.2013, Iskandar
[copper nano-wire net has been prepared Deng by spraying, the graphene oxide film that utilized spin coating to prepare, chemical treatment 24h under hydrazine hydrate atmosphere, 400 DEG C of thermal treatment 1h, prepare transparent graphene conductive film, the two combines by the method eventually through transfer, has prepared Graphene/copper nano-wire film.Test result shows that gained TCFs is in the wavelength region of λ=550nm, and transmittance is 80%, and square resistance is 34 ± 2.6 Ω/sq.
Prepare graphene film on flexible substrates both at home and abroad at present, mainly contain two kinds of methods, one carries out hydrophilic treatment to flexible base board, carries out film forming utilizing the means such as spin coating, self-assembly.Two is by film preparation on hard substrate, by transfer mode the most at last graphene oxide film transfer on flexible base board.This process not only very complicated, and in transfer process, the integrity of film is damaged.Because flexible base board is mostly macromolecule material, can not be high temperature resistant, more hydrophobic.As it is, be difficult to directly prepare graphene-based transparent conductive film on flexible substrates.
Summary of the invention
Object of the present invention is exactly provide a kind of efficient, feasible, spraying method directly preparing transparent graphene conductive film on a flexible substrate of being suitable for big area, extensive preparation to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
Directly prepare a spraying method for transparent graphene conductive film on a flexible substrate, it is characterized in that, the method adopts following steps:
(1) prepare water-ethanol-graphene oxide dispersion, the concentration of controlled oxidization Graphene is at 0.1 ~ 2mg/ml, and the volume ratio of water and ethanol is 1: 1 ~ 1: 10, and sonic oscillation obtains water-ethanol-graphene oxide dispersion that is dispersed and good stability;
(2) flexible base board is carried out cleaning and drying in baking oven under ultrasonic, ensure flexible base board surface clean, dustless;
(3) flexible base board is heated on hot plate close to flexible base board softening temperature;
(4) water-ethanol-graphene oxide dispersion is joined be connected with in the airbrush of air pump, be ejected on flexible base board, obtain graphene oxide film;
(5) graphene oxide film is reduced, prepare transparent graphene conductive film.
Described flexible base board is that transparent material makes the flexible base board obtained.
Preferred PC or the PET transparent material of described flexible base board makes the flexible base board obtained.Described flexible base board softening temperature is 20-200 DEG C.
Described flexible base board softening temperature is preferably 80-120 DEG C.
Airbrush is when spraying water-ethanol-graphene oxide dispersion, and the distance of distance flexible base board is 5 ~ 20cm.
Airbrush is when spraying water-ethanol-graphene oxide dispersion, and the injection air pressure of employing is 20 ~ 80psi.
Compared with prior art, the invention provides a kind of efficient, feasible, method of being suitable for big area, preparing transparent graphene conductive film on a large scale, provide certain air pressure by air pump, graphene oxide solution is sprayed by airbrush.Utilize hot-plate to improve substrate for film deposition surface temperature, be beneficial to solvent flashing better.Spraying ratio juris sprays in the substrate of preheating with the airbrush of specialty by graphene dispersing solution, obtains the process of graphene film after solvent evaporates.The effect of fog gun is atomised dispersion, forms small droplets.Preheating substrate is that solvent can evaporate rapidly, avoids the reunion of graphene film in order to ensure after on droplet deposition to substrate, the graphene-based transparent conductive film of final formation.Boiling point due to ethanol is 78 DEG C, lower than the boiling point of water.And the surface tension of ethanol is less, on the material of macromolecule material, wettability is better.But graphene oxide is owing to making its surface with carboxyl and hydroxyl in oxidising process, make it comparatively hydrophilic, and dispersiveness is in ethanol poor.Based on this, in the present invention, we have successfully prepared water-ethanol-graphene oxide dispersion.This dispersion liquid effectively can reduce solvent boiling point, can realize the wettability to some polymer flexible base boards simultaneously, and can well disperse graphene oxide.By the method for spraying, above-mentioned solution is injected on pre-heated substrate, directly on the flexible base board without any process, has successfully prepared graphene oxide film, finally, through suitable chemical reduction, prepared transparent graphene conductive film.This patent is efficient, simply directly prepared transparent graphene conductive film on flexible substrates, and prepared by extensive, big area that this technology can be used for transparent graphene conductive film, have the following advantages:
(1) by preparing water-ethanol-graphene oxide dispersion, the boiling point of ejection of solvent volatilization is reduced.
(2) by preparing water-ethanol-graphene oxide dispersion, improve the wettability of graphene oxide solution to flexible transparent substrate.
(3) any process is not carried out to flexible base board, directly successfully preparing graphene oxide film on flexible base board surface by the method for spraying.
(4) direct spraying water-ethanol-graphene oxide dispersion method is compared to traditional transfer method, substrate surface hydrophilic treatment etc., saves time, efficiently, succinctly.
(5) the method processing ease, spray equipment is easy to mobile, has outstanding advantage compared to additive method preparing on large area film.
Accompanying drawing explanation
Fig. 1 is graphene oxide concentration is transparent conductive film AFM picture prepared by 1/8000mg/ml;
Fig. 2 is graphene oxide concentration is transparent conductive film AFM picture prepared by 1/2000mg/ml;
Fig. 3 is graphene oxide concentration is transparent conductive film AFM picture prepared by 1/1000mg/ml;
Fig. 4 is graphene oxide concentration is transparent conductive film AFM picture prepared by 1/400mg/ml;
Fig. 5 is graphene oxide concentration is transparent conductive film AFM picture prepared by 1/250mg/ml;
Fig. 6 is graphene oxide consumption is transparent conductive film AFM picture prepared by 1ml;
Fig. 7 is graphene oxide consumption is transparent conductive film AFM picture prepared by 2ml;
Fig. 8 is graphene oxide consumption is transparent conductive film AFM picture prepared by 3ml;
Fig. 9 is graphene oxide consumption is transparent conductive film AFM picture prepared by 4ml.
In Fig. 1-5, graphene oxide solution consumption is in 1ml, Fig. 6-9, and the concentration of graphene oxide is 1/1200mg/ml.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
By changing concentration, sheet mica is prepared the transparent graphene conductive film of Cover treatment degree
Get 1mg/ml graphene oxide solution 5ml, add 25ml ethanol wherein.In ultrasonic a moment, get 2ml homogeneous solution and join in airbrush watering can.Clean ultrasonic for mica substrate, with post-drying, put on warm table and be warmed up to 100 DEG C.Now utilize the airbrush being associated with air pump to be injected in by above-mentioned solution on the flexible mica substrate that area is 1.8 × 1.3cm, jet length is about 5cm, and air pump air pressure is 35psi.The consumption of graphene oxide is 1ml, by changing graphene oxide concentration, being followed successively by 1/8000mg/ml, 1/2000mg/ml, 1/1000mg/ml, 1/400mg/ml, 1/250mg/ml and we have studied the impact (as Figure 1-5) of graphene oxide concentration on transparent graphene conductive film microtexture.Result shows, utilize this spraying method the graphene oxide lamella that sprays out be uniformly dispersed, and fold is less.But along with the increase of concentration, its coverage increases gradually, and film fold is also increasing gradually.
Embodiment 2
Flexible pet substrate prepares transparent graphene conductive film
Get 1mg/ml graphene oxide solution 1ml, add 5ml ethanol wherein.In ultrasonic a moment, get 2ml homogeneous solution and join in airbrush watering can.Clean ultrasonic for pet substrate, with post-drying, put in heating too and be warmed up to 80 DEG C.Now utilize the airbrush being associated with air pump to be injected in by above-mentioned solution on the flexible pet substrate that area is 5 × 5cm, jet length is about 10cm, and air pump air pressure is 35psi.Final prepared graphene oxide film is immersed in HI acid, reduces, finally successfully prepared transparent graphene conductive film to it.
Embodiment 3
By changing graphene oxide consumption, sheet mica is prepared the transparent graphene conductive film of Cover treatment degree
Get 1mg/ml graphene oxide solution 5ml, add 25ml ethanol wherein.In ultrasonic a moment, get 2ml homogeneous solution and join in airbrush watering can.Clean ultrasonic for mica substrate, with post-drying, put on warm table and be warmed up to 100 DEG C.Now utilize the airbrush being associated with air pump to be injected in by above-mentioned solution on the flexible mica substrate that area is 1.8 × 1.3cm, jet length is about 5cm, and air pump air pressure is 35psi.Graphene oxide concentration is 1/1200mg/ml, by changing the consumption of graphene oxide, be respectively 1ml, 2ml, 3ml, 4ml, we have studied the impact (as Figure 6-9) of graphene oxide consumption on transparent graphene conductive film microtexture.Result shows, utilize this spraying method the graphene oxide lamella that sprays out be uniformly dispersed, and fold is less.But along with the increase of consumption, its coverage increases gradually, and film fold is also increasing gradually.
Embodiment 4
Transparent graphene conductive film prepared by flexible PC substrate
Get 1mg/ml graphene oxide solution 5ml, add 25ml ethanol wherein.In ultrasonic a moment, get 2ml homogeneous solution and join in airbrush watering can.Clean ultrasonic for PC substrate, with post-drying, put on warm table and be warmed up to 100 DEG C.Now utilize the airbrush being associated with air pump to be injected in by above-mentioned solution on the flexible PC substrate that area is 5 × 5cm, jet length is about 10cm, and air pump air pressure is 35psi.Graphene oxide consumption is 2ml, and concentration is 0.17mg/ml.Finally, graphene oxide film (as Fig. 3 so) has successfully been prepared.Prepared graphene oxide film utilizes 0.5mlHI acid stifling, reduces to it.Now substrate P C substrate temperature is 100 DEG C, and final prepared graphene film square resistance is 16.4k Ω, and transmittance is 64.1%.
Claims (6)
1. directly prepare a spraying method for transparent graphene conductive film on a flexible substrate, it is characterized in that, the method adopts following steps:
(1) prepare water-ethanol-graphene oxide dispersion, the concentration of controlled oxidization Graphene is at 0.1 ~ 2mg/ml, and the volume ratio of water and ethanol is 1:1 ~ 1:10, and sonic oscillation obtains water-ethanol-graphene oxide dispersion that is dispersed and good stability;
(2) flexible base board is carried out cleaning and drying in baking oven under ultrasonic, ensure flexible base board surface clean, dustless;
(3) be heated on hot plate by flexible base board close to flexible base board softening temperature, described flexible base board softening temperature is 20-200 DEG C;
(4) water-ethanol-graphene oxide dispersion is joined be connected with in the airbrush of air pump, be ejected on flexible base board, obtain graphene oxide film;
(5) graphene oxide film is reduced, prepare transparent graphene conductive film.
2. a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate according to claim 1, it is characterized in that, described flexible base board is that transparent material makes the flexible base board obtained.
3. a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate according to claim 2, it is characterized in that, preferred PC or the PET transparent material of described flexible base board makes the flexible base board obtained.
4. a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate according to claim 1, it is characterized in that, described flexible base board softening temperature is preferably 80-120 DEG C.
5. a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate according to claim 1, is characterized in that, airbrush is when spraying water-ethanol-graphene oxide dispersion, and the distance of distance flexible base board is 5 ~ 20cm.
6. a kind of spraying method directly preparing transparent graphene conductive film on a flexible substrate according to claim 1, it is characterized in that, airbrush is when spraying water-ethanol-graphene oxide dispersion, and the injection air pressure of employing is 20 ~ 80psi.
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| CN105761774A (en) * | 2014-12-19 | 2016-07-13 | 北京生美鸿业科技有限公司 | Novel electrode material applicable to intelligent liquid crystal dimming film and preparation method thereof |
| CN105084858B (en) * | 2015-08-07 | 2018-05-18 | 常州富烯科技股份有限公司 | A kind of preparation method of graphene film |
| CN105582751B (en) * | 2015-12-17 | 2018-05-22 | 常州碳星科技有限公司 | Filter core and its preparation method and application |
| CN105951302B (en) * | 2016-06-08 | 2020-10-27 | 海南大学 | Method for preparing oil-water separation nanofiber membrane |
| CN108242452B (en) * | 2016-12-27 | 2020-12-04 | 青岛翼晨镭硕科技有限公司 | Photonic integrated device and manufacturing method thereof |
| CN107887076A (en) * | 2017-10-27 | 2018-04-06 | 成都天航智虹知识产权运营管理有限公司 | A kind of preparation method of graphene conductive film |
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