CN108314024B - Plasma preparation method of graphene transparent conductive film - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention provides a plasma preparation method of a graphene transparent conductive film. Oxidizing and modifying the outer layer of graphene with the thickness of a double atomic layer or a triple atomic layer by a plasma oxidation technology to obtain an externally-modified graphene material which can be dispersed in a common solvent, and preparing the film by using a wire rod coating method, a spin-coating method and the like and then reducing to obtain the high-conductivity transparent conductive film. According to the method, the outer sides of two or two atomic layers outside the three-atomic-layer graphene are subjected to oxidation modification by using a plasma technology, a sheet layer in the middle of the three-atomic-layer graphene material is not oxidized and still keeps good conductivity, only one side of the two-atomic-layer graphene is oxidized, the oxidation degree is also reduced compared with that of a single layer, meanwhile, the problem that the high-quality graphene material with two or three atomic layers is difficult to process and easy to stack is solved by modifying the oxygen-containing group, the better performance of the graphene is maintained, and the method can be applied to the fields of photoelectric devices, energy storage and the like.
Description
Technical Field
The invention relates to the field of preparation of graphene-based transparent conductive films, and aims to carry out oxidation modification on the outer layers of double-layer or three-layer high-quality graphene by using a plasma oxidation technology to obtain an externally-modified graphene material which can be dispersed in common solvents so as to prepare the transparent conductive film.
Background
Graphene is a fully sp-substituted structure2A quasi-two-dimensional crystalline material composed of hybridized carbon atoms and having a thickness of only a single atomic layer or several single atomic layers is considered as one of the most promising materials for a transparent conductive thin film in terms of chemical stability, flexibility, electrical conductivity, transparency, thermal conductivity, and raw material cost. The graphene with a complete structure is a two-dimensional crystal formed by combining carbon six-membered rings without any unstable bonds, the surface of the graphene is in an inert state, the chemical stability is high, the interaction with a solvent is weak, strong van der waals force exists between sheets, aggregation is easy to generate, and the graphene is difficult to dissolve in water and common organic solvents, so that great difficulty is caused for further research and application of the graphene. In order to fully exert its excellent properties and improve its molding processability, for example, to improve solubility and dispersibility in a matrix, graphene must be functionalized effectively. By introducing specific functional groups, new properties can be endowed to the graphene, and the application field of the graphene is further expanded. Functionalization is the most important means for realizing dispersion, dissolution and molding processing of graphene.
Plasma is an ionized gas substance consisting of atoms with some electrons being deprived and positive and negative electrons generated after the atoms are ionized, and the ionized gas consists of atoms, molecules, atomic groups, ions and electrons and is often used as a means for modifying graphene. The atomic group (free radical) mainly realizes the activation of energy transfer in the chemical reaction process of the surface of an object; the action of electrons on the surface of an object mainly comprises two aspects: on the one hand, the impact action on the surface of the object and, on the other hand, the chemical reaction caused by the impact of a large number of electrons. Nourbakhsh and the like find that oxygen plasma treatment can introduce an amorphous structure into single-layer graphene prepared by a mechanical stripping method, so that the energy band of the graphene is opened to enable the graphene to show the semiconductor characteristic, and meanwhile, the optical performance of the graphene is changed to show an obvious photoluminescence characteristic; surside et al used oxygen plasma to process nanopores in a single-layer graphene film prepared by CVD, and found that the processed film almost 100% prevented the passage of salt, thereby obtaining a high quality desalted film. The low-temperature oxygen plasma treatment introduces a large amount of hydroxyl (C-OH) and carbonyl (C ═ O) into graphene, so that the defect density is increased and the crystal grains are refined. The outer side of the high-quality graphene material with the thickness of the double atomic layer or the triple atomic layer is subjected to oxidation modification by adopting a plasma oxidation technology to obtain the externally-modified graphene material which can be dispersed in common solvents, so that the problems that the graphene material is difficult to process and easy to accumulate are solved, the better performance of the graphene is maintained, and the method can be applied to the fields of photoelectric devices, energy storage and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, a novel preparation method of the graphene-based transparent conductive film is provided, and the problems of difficulty in processing a graphene material, poor conductivity, high oxygen content and great structural damage are solved. The invention provides a plasma preparation method of a graphene transparent conductive film, which is small in damage to a sheet structure of graphene, overcomes the problems that graphene is difficult to process and easy to accumulate, realizes better maintenance of the performance of graphene, and can obtain the graphene transparent conductive film with high conductivity.
The invention adopts the following technical scheme:
a plasma preparation method of a graphene transparent conductive film comprises the following steps:
(1) iodine chloride, iodine bromide or anhydrous ferric trichloride and graphite are mixed and heated to prepare a second-order or third-order graphite intercalation compound, and the graphite intercalation compound is subjected to chemical reaction in turbulent flow, high temperature or a sub/supercritical fluid, so that high-quality graphene with two atomic layers or three atomic layers is prepared efficiently;
(2) the method comprises the steps of carrying out oxidation modification on the outer side of a high-quality graphene material with the thickness of a diatomic layer or a triatomic layer by adopting a plasma oxidation technology to obtain an externally-modified graphene material which can be dispersed in a common solvent, and reducing the externally-modified graphene material after preparing a film by using a wire rod coating method, a spin-coating method and the like to obtain the high-conductivity transparent conductive film.
In the step (1), the intercalation agent of the second-order or third-order graphite intercalation compound is iodine chloride, iodine bromide or anhydrous ferric trichloride and the like.
The environment of the chemical reaction in the step (1) is turbulent flow generated by high-speed rotation, high-temperature environment with protective atmosphere or sub/supercritical fluid environment.
The chemical reaction type in the step (1) is reaction of iodine bromide and water, pyrolysis of iodine chloride, reaction of ferric trichloride and hydrogen peroxide and the like.
And (3) exciting oxygen into plasma by using a plasma oxidation technology in the step (2), and then etching the outer surface of the bi-atomic layer or tri-atomic layer graphene to perform modification treatment.
In the step (2), the outer side is subjected to oxidation modification, so that oxygen-containing groups are added to the outer surface of the prepared bi-atomic layer or tri-atomic layer graphene under plasma oxidation treatment.
The invention has the following advantages:
(1) the invention provides a strategy for preparing a high-conductivity transparent conductive film by oxidizing and modifying the outer side of double-atomic-layer or three-atomic-layer graphene by using a plasma oxidation technology. The oxygen-containing group on the outer side of the graphene enables the graphene to be dispersed in common solvents, and the problems that the graphene material is difficult to process and easy to accumulate are solved. The three-atomic-layer graphene intermediate sheet layer keeps the intrinsic state of graphene, and the high conductivity of the graphene transparent conductive film is ensured due to the low oxygen content caused by the outside oxidation of the two-atomic-layer graphene.
(2) The method for preparing the graphene material and the transparent conductive film has low requirements on equipment, and is suitable for industrial or laboratory operation.
Drawings
FIG. 1 is a schematic diagram of a bi-atomic layer and a tri-atomic layer graphene film according to the method of the present invention.
FIG. 2 is a TEM image of plasma oxidation treatment of graphene according to the method of the present invention.
FIG. 3 is an infrared image of the plasma oxidation treatment of graphene according to the method of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
(1) 60g of iodine bromide and 100mg of expanded graphite are mixed uniformly, filled with Ar gas as protective gas and sealed in a 100mL glass bottle.
(2) And (3) placing the glass bottle in an oil bath environment at 100 ℃, and heating for 48 hours to prepare the third-order graphite intercalation compound.
(3) The graphite intercalation compound is quickly removed from the vial and filtered.
(4) The intercalation compound is quickly put into a hydrothermal kettle with the volume of 50mL, 10mL of aqueous solution is added into the hydrothermal kettle, and hydrothermal kettle equipment is quickly fixed.
(5) And heating the hydrothermal kettle to 180 ℃, keeping the temperature for 1h, taking out a sample after the reaction is finished, and cleaning the sample to obtain the three-atom-layer high-quality graphene powder aggregate.
(6) And putting the high-quality graphene of the three-atom layer into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve the vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external-modification tri-atomic-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
Fig. 2 is a TEM image of the plasma oxidation treated graphene of the present example.
Fig. 3 is an infrared image of the graphene subjected to the plasma oxidation treatment in the embodiment.
Example 2
(1) 30g of iodine bromide and 50mg of expanded graphite are uniformly mixed, filled with protective gas Ar gas, sealed in a 50mL glass bottle, placed in an oil bath environment at 100 ℃ and heated for 12 hours to prepare the third-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly removed from the vial and filtered.
(3) The intercalation compound is rapidly placed into a supercritical water apparatus having a volume of 50 mL.
(4) 2mL of aqueous solution is added into the supercritical water device, and the equipment is quickly fixed.
(5) And heating the high supercritical water device to 180 ℃, increasing the pressure to 22.1Mpa, keeping for 1h, taking out the sample after the reaction is finished, and cleaning the sample to obtain the graphene powder aggregate.
(6) And putting the high-quality graphene of the three-atom layer into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve the vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external-modification tri-atomic-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
Example 3
(1) 0.3g of anhydrous FeCl3Mixing with 0.05g of expanded graphite, and vacuum sealingAnd closing, heating to 380 ℃ within 1 hour, and maintaining for 12 hours to prepare the third-order graphite intercalation compound.
(2) Dissolving the graphite intercalation compound in a dilute hydrochloric acid solution, and carrying out suction filtration and drying for later use.
(3) Rapidly placing graphite intercalation compound into 50mL supercritical CO2In the device.
(4) To supercritical CO25mL of hydrogen peroxide solution with the mass fraction of 30% is added into the device, and the device is quickly fixed.
(5) Mixing high supercritical CO2Heating the device to 38 ℃, increasing the pressure to 75atm, keeping for 1h, taking out the sample after the reaction is finished, and cleaning the sample to obtain the graphene powder aggregate.
(6) And putting the high-quality graphene of the three-atom layer into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve the vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external-modification tri-atomic-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
Example 4
(1) 0.3g of anhydrous FeCl3Mixing with 0.05g of expanded graphite, sealing in vacuum, heating to 380 ℃ within 1 hour, and maintaining for 12 hours to prepare a third-order graphite intercalation compound.
(2) Dissolving the graphite intercalation compound in a dilute hydrochloric acid solution, and carrying out suction filtration and drying for later use.
(3) The intercalation compound is dispersed in the organic solvent N-methylpyrrolidone, to prepare a 5mg/mL suspension.
(4) 10mL of a 30% by mass aqueous hydrogen peroxide solution was added and the high-speed centrifuge was immediately operated at 7000 rpm for 0.5 hour.
(5) And after the reaction is finished, cleaning the sample to obtain the three-atomic-layer graphene powder aggregate.
(6) And putting the high-quality graphene of the three-atom layer into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve the vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external-modification tri-atomic-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
Example 5
(1) 30g of iodine bromide and 50mg of expanded graphite are uniformly mixed, filled with protective gas Ar gas, sealed in a 50mL glass bottle, placed in an oil bath environment at 100 ℃ and heated for 12 hours to prepare the third-order graphite intercalation compound.
(2) The graphite intercalation compound is quickly removed from the vial and filtered.
(3) All graphite intercalation compounds are quickly put into a quartz boat, and the quartz boat is put into an argon protective atmosphere.
(4) The quartz boat was heated to 800 ℃.
(5) And after the reaction is finished, taking out the sample, and cleaning the sample to obtain the graphene powder aggregate.
(6) And putting the high-quality graphene of the three-atom layer into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve the vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external-modification tri-atomic-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
Example 6
(1) 30g of iodine chloride and 50mg of high-temperature oriented pyrolytic graphite are uniformly mixed, filled with protective gas Ar gas and sealed in a 50mL glass bottle.
(2) And placing the mixture in an oil bath environment at 160 ℃, and heating for 48 hours to prepare the second-order graphite intercalation compound.
(3) The graphite intercalation compound is quickly removed from the vial and filtered.
(4) All graphite intercalation compounds are quickly put into a quartz boat, and the quartz boat is put into an argon protective atmosphere.
(5) And heating the quartz boat to 800 ℃, maintaining for 5min, taking out the sample after the reaction is finished, and cleaning the sample to obtain the double-layer graphene powder aggregate.
(6) And (3) putting the double-layer graphene into a cavity of a small vacuum oxygen plasma cleaning machine, and vacuumizing the working chamber by using a vacuum pump to achieve a vacuum degree of 0.02-0.03mbar and maintaining the vacuum degree for 0.5 hour.
(7) The working gas is oxygen, the power is about 300W, and the working gas is maintained for 0.5 h.
(8) And ultrasonically dispersing the product in ethanol to obtain the external modified double-layer graphene solution.
(9) And preparing the transparent conductive film by adopting a wire rod coating method.
(10) And immersing the transparent conductive film into a hydriodic acid solution for reduction, and taking out after half an hour.
(11) And (4) repeatedly cleaning the transparent conductive film by using ethanol, and drying.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (5)
1. A plasma preparation method of a graphene transparent conductive film comprises the following steps:
(1) iodine chloride, iodine bromide or anhydrous ferric trichloride are mixed with graphite and heated to prepare a second-order or third-order graphite intercalation compound, and the graphite intercalation compound is subjected to chemical reaction in turbulent flow, high temperature or a sub/supercritical fluid, so that high-quality graphene with two atomic layers or three atomic layers is efficiently prepared;
(2) the method comprises the steps of carrying out oxidation modification on the outer side of a high-quality graphene material with the thickness of a diatomic layer or a triatomic layer by adopting a plasma oxidation technology to obtain an externally-modified graphene material which can be dispersed in a common solvent, and reducing the externally-modified graphene material after preparing a film by using a wire rod coating method and a spin-coating method to obtain the high-conductivity transparent conductive film.
2. The production method according to claim 1, wherein the environment in which the chemical reaction is performed in step (1) is a turbulent flow generated by high-speed rotation, a high-temperature environment having a protective atmosphere, or a sub/supercritical fluid environment.
3. The preparation method according to claim 1, wherein the chemical reaction in step (1) is a reaction between iodine bromide and water, a pyrolysis of iodine chloride, or a reaction between iron trichloride and hydrogen peroxide.
4. The preparation method according to claim 1, wherein the plasma oxidation technology in the step (2) excites oxygen into plasma, and then the external surface of the bi-atomic layer or tri-atomic layer graphene is etched for modification treatment.
5. The preparation method according to claim 1, wherein the outer side is oxidatively modified in step (2) such that an oxygen-containing group is attached to the outer surface of the prepared bi-atomic layer or tri-atomic layer graphene under plasma oxidation treatment.
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| CN109266187B (en) * | 2018-08-10 | 2021-02-05 | 恒力盛泰（厦门）石墨烯科技有限公司 | Heat dissipation coating containing isocyanate modified graphene and preparation method thereof |
| CN110482539B (en) | 2019-09-06 | 2021-09-21 | 常州富烯科技股份有限公司 | Mixed slurry of strong and weak graphene oxide, preparation method of mixed slurry, composite film of strong and weak graphene oxide and preparation method of composite film |
| CN112510204B (en) * | 2021-02-05 | 2021-04-20 | 宁波埃氪新材料科技有限公司 | Carbon nanotube graphene composite conductive agent and preparation method thereof |
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| CN107857258A (en) * | 2017-11-27 | 2018-03-30 | 盐城师范学院 | A kind of method of full carbon face oxidation adjusting function graphite alkene functional group species |
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| CN105000552A (en) * | 2015-07-24 | 2015-10-28 | 浙江大学 | Preparation method for graphene oxide |
| CN105225766A (en) * | 2015-07-30 | 2016-01-06 | 国家纳米科学中心 | A kind of preparation method of transparent graphene conductive film |
| CN106198674A (en) * | 2016-08-25 | 2016-12-07 | 无锡盈芯半导体科技有限公司 | A kind of mesoporous Graphene preparation technology and based on mesoporous graphene field effect transistor biosensor |
| CN107345818A (en) * | 2017-06-29 | 2017-11-14 | 上海集成电路研发中心有限公司 | A kind of preparation method of graphene-based sensor |
| CN107857258A (en) * | 2017-11-27 | 2018-03-30 | 盐城师范学院 | A kind of method of full carbon face oxidation adjusting function graphite alkene functional group species |
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