CN102877109A - Method for preparing grapheme transparent conducting films by electrophoretic deposition - Google Patents
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Abstract
The invention relates to a preparation method of grapheme transparent conducting films, comprising the following steps: taking natural graphite powder as raw materials; ultrasonically stripping in 0.5-1.0% by volume of AMP, 0.4% by volume of water and DMF solution to prepare high-concentration grapheme dispersion liquid; taking the prepared grapheme dispersion liquid as electrolyte; preparing grapheme conducting films by electrophoretic deposition, transferring the grapheme conducting films onto a glass substrate; controlling the electrophoretic deposition voltage and the electrophoretic deposition time to prepare the grapheme conducting films with different thicknesses and improving light transmission and conductivity of the grapheme conducting films through the heat treatment and acid processing technology. The grapheme transparent conducting films prepared by the method has flat surface and less defect; the prepared grapheme transparent conducting films has the light transmittance of 82.1% and the film resistance of 1.0 microhm/sq. Compared with the other preparation method, the method has the advantages of simple operation, easy control and lower coat and is suitable for large-scale preparation.
Description
Technical field
The invention belongs to the carbon material preparation field, be specifically related to a kind of method of utilizing electrophoretic deposition to prepare transparent graphene conductive film.
Background technology
As the important component part of opto-electronic device, transparent conductive film has a wide range of applications in fields such as liquid-crystal display (LCD), organic solar batteries, organic light emitting diodes (LCD).Tin indium oxide (ITO) relies on its high conductivity and light transmission, has become current main transparent conductive film material.Yet because the preparation of ITO is costly and starting material are rare and the continuous rise of price, the fragility of ITO also makes its performance requriements that can't satisfy some new application simultaneously, therefore, needs the equivalent material of exploitation ITO badly.
The electroconductibility that Graphene is good and light transmission make it that good application prospect be arranged aspect transparent conductive film.Compare with the ITO material, Graphene has higher intensity and better toughness, as transparent conductive film, can make can bending fold display device.
At present, the preparation method of transparent graphene conductive film mainly contains: CVD method and based on the method for graphene oxide or graphene dispersing solution.The CVD method can obtain the more perfect high-quality graphene of structure, yet the CVD method still exists the more high defective of equipment requirements.Be the method that raw material prepares transparent conductive film based on graphene oxide or graphene dispersing solution, because the method cost is lower, suitability is stronger etc., can satisfy the application demand of different field.
At present, the method for preparing graphene conductive film based on graphene oxide or graphene dispersing solution mainly contains: electrophoretic deposition, layer assembly method, vacuum filtration method, spin coating method, injection cladding process etc.Compare with other method, that electrophoretic deposition has is easy and simple to handle, be easy to control, cost is lower, be suitable for the advantage such as mass-producing preparation, but the method only has a small amount of report at present.
(Chem. Mater, 2009,21 (16): 3905-3916) adopt electrophoretic deposition to make level and smooth graphene film in conductive substrates such as Lee.The preparation approach comprises two kinds: the firstth, and utilize the aqueous dispersions of the graphene oxide of mechanically peel gained to be raw material, adopt electrophoretic deposition graphene oxide to be deposited on the substrate of glass of indium tin oxide coating, then it is immersed in the aqueous solution of hydrazine hydrate, thereby the graphene oxide reduction that deposits is made graphene film; Another kind then is first with graphene oxide reduction, then will reduce the Graphene electrophoretic deposition of gained to substrate.Yet there is graphene film textural defect more (due to the reduction not exclusively) in the method, waits deficiency.(Adv. Mater, 2009,21 (17): make graphene dispersing solution thereby 1756-1760) adopt the method for chemical stripping in aqueous isopropanol, to peel off synthetic graphite, then add therein Mg (NO such as Cheng
3)
26H
2O is by Mg (NO
3)
26H
2The ionization of O makes Graphene absorption Mg
2+And positively charged, with Mg
2+The absorption graphene suspension is as ionogen, and under electric field action, positively charged graphene film is towards movable cathode and be deposited in an orderly manner cathode surface, thereby obtains graphene film.But still there is charged Mg in this method
2+Be difficult to remove from graphene film, cause the problems such as the film transmittance is relatively poor.
The defective or the deficiency that prepare graphene conductive film for above-mentioned electrophoretic deposition, basic conception of the present invention is: utilize ultrasonic the peeling off of Graphite Powder 99 liquid phase to prepare in the graphene dispersing solution process, introduce 2-amino-2-methyl-1-propanol (AMP) as the additive of preparation graphene dispersing solution.AMP can ionize and be adsorbed in the Graphene surface, and adsorption charge produces electrostatic repulsion and reduces the stacking trend of absorption, thereby improves the concentration of graphene dispersing solution.Simultaneously, because AMP is easy to volatilization, after electrolytic solution electrophoretic deposition gained graphene film drying, foreign matter content is few take this dispersion liquid, and film light transmission and electroconductibility are better.The concrete technology technological line comprises: be raw material with natural graphite powder, take AMP/ water/dimethyl formamide (DMF) system as solvent, adopt the ultrasonic stripping method of liquid phase to prepare the high concentration graphene dispersion liquid.Then take prepared dispersion liquid as electrolytic solution, adopt electrophoretic deposition to prepare graphene film, again the graphene film that makes is transferred to glass or arbitrarily in other substrates.
Summary of the invention
The present invention utilizes a kind of mode of non-covalent physical adsorption to make Graphene charged, then adopts electrophoretic deposition to prepare transparent graphene conductive film.
Specifically the present invention take AMP/ water/DMF system as solvent, adopts the ultrasonic stripping method of liquid phase to prepare the high concentration graphene dispersion liquid take natural graphite powder as raw material.Then take prepared dispersion liquid as electrolytic solution, adopt electrophoretic deposition to prepare graphene film, again the graphene film that makes is transferred on the substrate of glass.
Its concrete process is as follows:
1, the preparation of graphene dispersing solution
Measuring 0.1-0.2 mLAMP and 0.08 mL deionized water joins and is configured to AMP (0.5-1.0 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.2-0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 24-30 h(ultrasonic power 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 90-120 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 7 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 80 V cm
-1Steady electric field, electrophoretic deposition 30-50 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance test of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.
What the present invention was prepared is transparent graphene conductive film.Can control by regulating electrophoretic voltage and depositing time the thickness of transparent graphene conductive film; By being heat-treated with acid treatment, the transparent graphene conductive film after shifting to improve its transmittance and electroconductibility.
Device required for the present invention is simple and cheap, mainly is comprised of two portions: Vltrasonic device, electrophoresis apparatus device.Effect and mutual relationship between two portions are as follows: 1) Vltrasonic device is used for the ultrasonic graphene dispersing solution of peeling off; 2) electrophoresis apparatus device makes graphene film in the electric field action deposit to electrode with Graphene.
The present invention compares with existing technology of preparing and synthetic route, has following advantage and beneficial effect:
1. introduce AMP as the additive of preparation graphene dispersing solution, AMP can ionize and be adsorbed in the Graphene surface, and the Graphene adsorption charge produces electrostatic repulsion and reduces the stacking trend of absorption, thereby can improve the concentration of graphene dispersing solution.Under identical ultrasound condition and ultrasonic time, peel off graphene dispersing solution with direct liquid phase and compare, adding AMP can improve 50% with the concentration of graphene dispersing solution.Simultaneously because AMP is easy to volatilization, be electrolytic solution electrophoretic deposition gained graphene film drying with this dispersion liquid after, foreign matter content is few, film light transmission and electroconductibility are better.
2. the graphene film textural defect that makes of the present invention is few, and degree of oxidation is low, and dispersion system has extraordinary stability.
3. the present invention can be by regulating the thickness of electrophoretic deposition applied voltage and depositing time control graphene conductive film, and prepared graphene film is comparatively complete, and transmittance is better.
4. technique of the present invention is simple, is suitable for the mass-producing preparation.
Embodiment
Embodiment one
1, the preparation of graphene dispersing solution
Measuring 0.2 mLAMP and 0.08 mL deionized water joins and is configured to AMP (1.0 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 24 h(ultrasonic powers, 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 90 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 7 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 80 V cm
-1Steady electric field, electrophoretic deposition 30 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance characterization of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.The evaluation of transmittance index sees Table one.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.The evaluation of sheet resistance index sees Table one.
Embodiment two
1, the preparation of graphene dispersing solution
Measuring 0.1 mLAMP and 0.08 mL deionized water joins and is configured to AMP (0.5 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mixes.Weighing 0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 30 h(ultrasonic powers, 72 W that peel off).After ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 120 min under 4000 rpm rotating speeds.Get centrifuge tube supernatant liquor, set aside for use with clean dropper at last.
2, the preparation of electrophoretic deposition electrode used therein
The used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing.
(1) mechanical polishing of Copper Foil is processed
Use the sand papering Copper Foil, eliminate surface film oxide.Then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect.Polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, cleans with ethanol, then dry for standby.
(2) electroplating processes of Copper Foil
Dispose saturated neutralized verdigris solution, as electrode, neutralized verdigris solution was electroplated 15 minutes under 20 mA constant current modes as ionogen with polished copper sheet, and powering at the negative electrode copper sheet plates layer of copper.Constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface.
3, electrophoretic deposition prepares graphene film
The graphene dispersing solution for preparing is diluted to 5 μ g/mL, and ultrasonic 10 min mix it.Adopt JY 600 type electrophoresis apparatuses as direct supply, between electrode, apply 100 V cm
-1Steady electric field, electrophoretic deposition 50 s.Rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry.
4, the transfer of graphene film
(1) the anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface.
The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level.
(3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min, to remove residual etching liquid ion at every turn.Then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries.
The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn.The PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass.
5, the processing of graphene conductive film
(1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃.
(2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%.
6, the performance characterization of graphene film
(1) transmittance of graphene film test
Adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film.The evaluation of transmittance index sees Table one.
(2) sheet resistance of graphene film test
Adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm.The evaluation of sheet resistance index sees Table one.
The evaluation of transparent graphene conductive film in table one example
| ? Embodiment | Transmittance | Resistance |
| Example one | 82.1% | 1.0 MΩ/sq |
| Example two | 81.3% | 1.2 MΩ/sq |
Claims (1)
1. an electrophoretic deposition prepares the method for transparent graphene conductive film, it is characterized in that comprising following process:
The preparation of graphene dispersing solution: measure 0.1-0.2 mLAMP and 0.08 mL deionized water and join and be configured to AMP (0.5-1.0 vol.%)/water (0.4 vol.%)/DMF solution among 20 mLDMF and mix, weighing 0.2-0.4 g Graphite Powder 99 adds in this mixing solutions, then with its ultrasonic 24-30 h(ultrasonic power 72 W that peel off), after ultrasonic the finishing, suspension is changed in the centrifuge tube, then use 800 type whizzers centrifugal 90-120 min under 4000 rpm rotating speeds, get centrifuge tube supernatant liquor, set aside for use with clean dropper at last;
The preparation of electrophoretic deposition electrode used therein: the used anode of electrophoretic deposition is the Copper Foil (copper thickness 0.1 mm) after mechanical polishing is processed, and the used negative electrode of electrophoretic deposition is the Copper Foil of elder generation after the re-plating processing is processed in mechanical polishing; (1) mechanical polishing of Copper Foil is processed: use the sand papering Copper Foil, eliminate surface film oxide, then use P-1 type polishing machine to carry out further mechanical polishing, reach at last mirror effect, polished Copper Foil is cut into the lengthy motion picture of 1.8 cm * 3.5 cm, clean with ethanol, then dry for standby; (2) electroplating processes of Copper Foil: dispose saturated neutralized verdigris solution, with polished copper sheet as electrode, neutralized verdigris solution is as ionogen, under 20 mA constant current modes, electroplated 15 minutes, power at the negative electrode copper sheet and to plate layer of copper, constantly washing after the electroplating processes copper sheet with deionized water dries stand-by to remove the ionogen on surface;
Electrophoretic deposition prepares graphene film: the graphene dispersing solution for preparing is diluted to 7 μ g/mL, and ultrasonic 10 min mix it, adopt JY 600 type electrophoresis apparatuses as direct supply, apply 80 V cm between electrode
-1Steady electric field, electrophoretic deposition 30 s, rapid taking-up anode copper sheet after deposition is finished is 90 ℃ of lower oven dry;
The transfer of graphene film: (1) anode copper sheet after oven dry deposits the methyl-phenoxide solution (concentration 1%) of the one side coating last layer PMMA of graphene film, at room temperature allows it naturally dry, and namely forms the PMMA film of layer of transparent on the graphene film surface; The copper sheet that (2) will simultaneously apply PMMA is immersed in the ferric chloride aqueous solutions of 3 g/mL, and after soaking about 12 hours, copper is fully by the iron trichloride etching, and Graphene/PMMA film swims on the liquid level; (3) Graphene/PMMA film is taken out, place deionized water to soak three times, soak 10 min at every turn, to remove residual etching liquid ion, then Graphene/PMMA film is transferred on the slide glass that cleans up, naturally dries; The slide glass that (4) will adhere to Graphene/PMMA film soaks in acetone three times, soaks 12 h at every turn, and the PMMA film is dissolved in acetone, removes from the Graphene surface, obtains being attached to the graphene film on the slide glass;
The processing of graphene conductive film: (1) thermal treatment: in air, graphene film thermal treatment 2 h to obtaining under 250 ℃; (2) acid treatment: to the film after the thermal treatment with rare nitric acid dousing 2 h of 50%;
The performance test of graphene film: the transmittance of (1) graphene film: adopt U-3010 type ultraviolet-visible spectrophotometer, take blank slide glass as reference, in 400-900 nm wavelength region, measure the transmittance of graphene film, and with at the transmittance at the wavelength X=550 nm places transmittance as graphene film, this graphene conductive film transmittance is at 80-82%; (2) sheet resistance of graphene film: adopt the sheet resistance of graphene film on the SB100A/2 type four point probe tester test slide base material, the distance between the probe is 3 mm, and this graphene conductive film resistance is at 1.0-1.2 M Ω/sq.
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