WO2011144010A1 - 一种石墨烯基导电材料及其制备方法 - Google Patents

一种石墨烯基导电材料及其制备方法 Download PDF

Info

Publication number
WO2011144010A1
WO2011144010A1 PCT/CN2011/074117 CN2011074117W WO2011144010A1 WO 2011144010 A1 WO2011144010 A1 WO 2011144010A1 CN 2011074117 W CN2011074117 W CN 2011074117W WO 2011144010 A1 WO2011144010 A1 WO 2011144010A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
conductive material
based conductive
metal
preparation
Prior art date
Application number
PCT/CN2011/074117
Other languages
English (en)
French (fr)
Inventor
梁明会
智林杰
Original Assignee
国家纳米科学中心
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国家纳米科学中心 filed Critical 国家纳米科学中心
Priority to JP2013510491A priority Critical patent/JP5540151B2/ja
Priority to US13/698,517 priority patent/US20130059143A1/en
Publication of WO2011144010A1 publication Critical patent/WO2011144010A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C01B32/192—Preparation by exfoliation starting from graphitic oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component

Definitions

  • the present invention relates to a method for preparing a graphene-based conductive material, and a graphene-based conductive material prepared by the method. Background technique
  • Graphene is a two-dimensional sheet having a single atom thickness composed of hexagonal sp 2 carbon atoms, which is a constituent element of graphite.
  • Graphene has been found to have many properties not possessed by graphite, such as room temperature quantum Hall effect, mass transfer resistance, optical properties, thermoelectric transport properties, light transmission, and extremely high Young's modulus. Because graphene has these properties, graphene and graphene-based materials have potential applications in many areas, such as display films, solar cell electrodes, lithium-ion battery electrodes, field effect transistors, and sensors.
  • a graphene material is prepared in large quantities by a method of reducing graphene oxide.
  • Graphene oxide is a product produced by oxidation of graphite, and the elements thereof include carbon, hydrogen and oxygen.
  • the graphite When graphite is oxidized, not only defects but also its original planar structure are destroyed. After the graphene oxide is reduced, the proportion of oxygen decreases, and the graphene sheet structure is restored, and the conductivity is also restored.
  • the graphene products obtained by different methods are greatly different, and these differences are mainly reflected in the structure and composition.
  • the method for reducing graphene oxide mainly includes high temperature heat treatment, hydrazine reduction, sodium borohydride reduction and the like.
  • the composition and structure of graphene obtained by treating graphene oxide by these methods are greatly different. Some heat-containing functional groups are removed by heat treatment, but they bring more defects than oxidation. Some studies have reported that the internal structure of the heat treatment is reformed to form five-membered rings, seven-membered rings and eight-membered rings. The complex carbon structure is structurally different from the pure six-membered ring in graphene. By treatment with hydrazine or sodium borohydride, literature studies have shown that the obtained graphene contains nitrogen or boron, and these nitrogen atoms or boron atoms form a chemical bond with the carbon atoms in the reduced graphene, thus reducing the graphite oxide by the two reducing agents.
  • Alkene-derived graphite The alkene is actually graphene chemically doped with nitrogen or boron, and the two graphenes may be referred to as nitrogen-doped graphene and boron-doped graphene.
  • these reduction methods currently employed have many disadvantages, such as high temperature, which is detrimental to the deposition of graphene on a flexible substrate material, and the ruthenium as a reducing agent is toxic, and sodium borohydride is too expensive.
  • Hydrogen is also a reducing agent, which can be used to reduce graphene oxide, but it requires a very high temperature for hydrogen reduction. For example, it has been reported in the literature to reduce graphene oxide by using 1000 °c hydrogen, which has undergone heat treatment and hydrogen reduction. Very limited.
  • a catalyst for supporting metal palladium on graphene oxide has been reported in the literature, but such a material containing graphene and a metal utilizes only the catalytic performance of metal palladium therein in an organic reaction, and the literature does not mention whether or not such a material has Conductivity, and the obtained graphene is reduced by ruthenium, so the graphene therein is nitrogen-containing graphene. It has also been reported in the literature that sodium borohydride reduces the complex of graphene oxide and palladium to obtain a material containing graphene and metal palladium, but the graphene therein is boron-containing graphene. Therefore, a solid graphene-based conductive material containing a metal and obtained by hydrogen reduction has not been reported in the prior patents and literature. Summary of the invention
  • the present invention provides a graphene-based conductive material which can be prepared under low temperature conditions and is environmentally friendly and non-polluting, and a preparation method thereof.
  • the inventors of the present invention have found that in the process of reducing graphene oxide, the introduction of a metal can catalyze the reduction process of graphene oxide and can lower the reaction temperature. Based on this finding, the inventors of the present invention have provided a preparation method capable of directly preparing a solid graphene-based conductive material at a low temperature and a solid graphene-based conductive material obtained by the method.
  • the invention provides a method for preparing a graphene-based conductive material, which comprises forming a solid oxide film on a substrate layer by using a graphene oxide sol and a metal salt solution and/or a metal colloid solution, and then the solid film and the base After the material layer is separated or not separated, it is placed in a hydrogen atmosphere at a temperature of -50 ° C to 200 ° C, a hydrogen pressure of 0.01 - 100 MPa or a reducing atmosphere containing hydrogen for 30 seconds - 10000 hours. At this time, a graphene-based conductive material is obtained.
  • the present invention also provides a graphene-based conductive material which is prepared by the above method.
  • the method of the invention has the following beneficial effects:
  • the present invention is the first to prepare a graphene-based conductive material by catalytic hydrogenation reduction of solid graphene oxide.
  • This method reduces the temperature of the hydrogenation reduction reaction by using a catalyst, and reduces the graphene oxide, the skeleton of the graphene oxide by using low-temperature hydrogen.
  • the structure is not destroyed, so it is different from the high-temperature-treated graphene oxide in many defects; and, without introducing a hetero atom, it is different in composition from the graphene obtained by reduction of ruthenium or sodium borohydride.
  • the graphene-based conductive material can be prepared at room temperature on some polymer substrates which cannot withstand high temperature treatment.
  • the graphene obtained by hydrogen reduction of graphene oxide in solution is not solid and does not form a conductive material, and the method of the invention can overcome the cumbersome process of preparing graphene precipitate or particles in solution and processing into a conductive material. Wherever the operation is simple, a graphene-based conductive material can be prepared in a large amount.
  • the present invention employs a method for catalytic hydrogenation reduction of graphene oxide to prepare a graphene-based conductive material, and the present invention provides a completely green reduction route relative to a reduction route using a toxic hydrazine; compared to an expensive sodium borohydride And the reduction route of phenylhydrazine, the hydrogen used in the present invention is a cheap and readily available raw material.
  • the graphene conductive material prepared by the present invention has very good chemical stability and thermal stability, and can be supported on a flexible substrate, and thus can be widely applied to flexible devices such as flexible circuits, flexible transparent window electrodes, and flexibility. Touch screen electrodes, etc.
  • Figure 1 is a graphene-based conductive film on a flexible substrate PET obtained in Example 2 according to the present invention.
  • FIG. 2 is an independently present graphene conductive film obtained according to Example 4 of the present invention.
  • Figure 3 is a graphene conductive film having a pattern on a printing paper obtained in Example 12 according to the present invention. detailed description
  • the invention provides a method for preparing a graphene-based conductive material, which comprises forming a solid oxide film on a substrate layer by using a graphene oxide sol and a metal salt solution and/or a metal colloid solution, and then the solid film and the base After the separation or non-separation, the layer is placed in a hydrogen atmosphere at a temperature of -50 ° C to 200 ° C and a hydrogen pressure of 0.01 to 100 MPa or a reducing atmosphere containing hydrogen for 30 seconds to 10000 hours to obtain a graphene-based conductive material. .
  • the time of the placement is from 5 minutes to 300 hours, more preferably from 2 hours to 5 days.
  • the hydrogen pressure is from 0.2 to 100 MPa.
  • the temperature is from 20 to 120 ° C
  • the hydrogen pressure is from 1 to 15 MPa
  • the reaction time may be from 2 hours to 5 days.
  • the hydrogen pressure when it is a hydrogen atmosphere, the hydrogen pressure is a gauge pressure; and when it is a hydrogen-containing reducing atmosphere such as a mixed gas atmosphere of hydrogen and nitrogen and/or an inert gas, the hydrogen pressure is a hydrogen partial pressure.
  • the graphene-based conductive material can be conveniently prepared at a relatively low temperature, for example, room temperature, by the production method of the present invention.
  • the metal atom in the graphene-based conductive material and the carbon in the graphene can be controlled by controlling the amount of the graphene oxide and the metal salt solution and/or the metal colloid solution.
  • the ratio of atoms is 0.0001-0.13.
  • the colloidal particle diameter in the metal colloidal solution is 0.7-lOnm
  • the concentration of the graphene oxide sol is 0.5-2 g/liter
  • the concentration of the metal salt solution is 1-3 g/liter
  • the metal colloid The concentration is 3-7 g / liter.
  • the catalytic hydrogenation reaction can be achieved by introducing a small amount of a metal salt solution and/or a metal colloidal solution, so that when a noble metal or a salt thereof is used as a catalyst or a catalyst precursor, the amount of the noble metal can be saved.
  • the metal salt when a metal salt is used as a catalyst in the preparation process, the metal salt First, it is reduced to metal particles in the reduction reaction, and then the metal particles are catalytically hydrogenated to reduce the reduction reaction of graphene oxide.
  • the metal in the metal salt solution and/or metal colloidal solution is one or more of palladium, platinum, rhodium, ruthenium, osmium, iridium and nickel, and the metal salt is selected from the group consisting of nitrate, hydrochloride, and sulfuric acid.
  • the solvent in the metal salt solution is water or a carbon atom a solvent of one or more of a lower alcohol of 1-4, acetone and dimethylformamide, wherein the solvent of the graphene oxide sol is one of water, a lower alcohol having 1 to 4 carbon atoms, and acetone.
  • the method for forming a solid film on a substrate layer by using a graphene oxide sol and a metal salt solution and/or a metal colloid solution includes spin coating, drop coating, spray coating, ink jet printing, and Heating one or more of the solution forming methods.
  • the material of the substrate layer is one selected from the group consisting of a glass plate, a quartz plate, a silicon wafer, a silicon carbide sheet, a fibrous flexible material, a natural flexible ore material, and a polymer polymer film.
  • the polymer polymer film is a transparent film made of polybutylene terephthalate, polyethylene, polypropylene, polystyrene or polyvinyl chloride, and the fiber-containing flexible material is printing paper,
  • the natural flexible ore material is mica flakes.
  • different graphenes can be obtained by controlling the conditions under which the reduction reaction of graphene oxide is reduced by catalytic hydrogenation, such as reaction time, thickness and size of solid matter, and the like.
  • Base conductive material such as reaction time, thickness and size of solid matter, and the like.
  • the graphene conductive material obtained after the reduction has a thickness of 1-100 nm, and the thus obtained graphene-based conductive layer
  • the light transmittance of the material is excellent;
  • the film thickness of the mixture of the graphene oxide hydrosol and the metal salt solution and/or the metal colloid solution is 100 nm-lmm, thus obtained
  • the graphene-based conductive material is excellent in electrical conductivity.
  • the graphene oxide can be prepared by various methods known in the art, including Staudenmaier, Brodie and Hummers, Method, Staudenmaier, Fami, Concentrated Sulfuric Acid and A mixture of fuming nitric acid as solvent and oxidant, potassium chlorate as oxidant, graphite as raw material to prepare graphite oxide, Bradie method using fuming nitric acid as solvent and oxidant, potassium chlorate as oxidant to prepare graphite oxide from graphite, and Hummers method using concentrated sulfuric acid as solvent Oxidizing agents, sodium nitrate and potassium permanganate are used as oxidizing agents, or other methods based on these methods can be used.
  • the graphene oxide of the present invention can be prepared by the following steps, but is not limited to the following method to obtain graphene oxide:
  • scaly graphite is oxidized in concentrated sulfuric acid, potassium permanganate mixed oxidant and treated with hydrogen peroxide;
  • the graphene oxide of the present invention is prepared as follows: About 1 g of natural flaky graphite is added to 20-100 g of concentrated sulfuric acid, and stirred under an ice bath at 0 ° C overnight. Then adding 0.05-0.5 g of potassium permanganate to the obtained mixture, in order to prevent the temperature from rising, stirring for 10-100 min, then adding 1-10 g of potassium permanganate and controlling the temperature below 20 ° C; Raise the temperature to 20-50 V again and keep this temperature for 10-100 min.
  • the mixture becomes viscous; then add 20-100 ml of water to the mixture and raise the temperature to 90- 95 V, maintain this temperature for 15-60 min; then add 30-60 ml of 20-50% by weight of hydrogen peroxide, stir for 10-100 min, then add 10-100 ml of water, filter while hot, use 20 - 100 ml of a concentration of 1-10% by weight of hydrochloric acid, the resulting filter cake is sonicated in 400-1000 ml of water for 0.5-2 hours, and the resulting dispersion is centrifuged to remove the graphene oxide particles which are not completely peeled off.
  • the dispersion obtained after the separation of the heart is centrifuged to remove a small amount of agglomerated fine particles of graphene oxide to obtain a jelly, and about 500-2000 ml of water (or a mixture of ethanol and water, methanol and water) is added to the gel.
  • the mixed solution methanol or a volume ratio of ethanol to water in the range of 0.1 to 10) or dimethylformamide is dispersed to obtain a colloidal solution of graphene oxide.
  • the invention also provides a graphene-based conductive material prepared by the above method To.
  • a graphene-based conductive material according to the present invention wherein the material comprises a conductive layer comprising a metal and graphene, the conductive layer having a resistivity of 0.01 Q/s to 50 kQ/sq, and a light transmittance 0-96%, thickness 1 nm-1 mm.
  • the light transmittance is 0-90% and the thickness is 5 nm-l mm.
  • the conductive layer has a resistivity of 100 Q/s -50 kQ/sq, a light transmittance of 50-90%, and a thickness of l-100 nm
  • the conductive material can simultaneously Has good conductivity and light transmission.
  • the resistivity of the conductive layer is ⁇ . ⁇ - ⁇ /sq and the thickness is 100 nm - 1 mm
  • the conductive material has excellent electrical conductivity and can be used as a conductive material in the circuit instead of the metal.
  • the unit symbol ⁇ /sq represents ohm/cm 2 , that is, the resistance in the present invention is a sheet resistance.
  • the content of graphene in the conductive layer is 60 to 99.999 wt%, and the content of the metal is 0.001 to 40 wt% based on the total amount of the conductive layer.
  • Water and impurities may also be contained in the conductive material of the present invention.
  • the content of graphene in the conductive layer is 64 to 98% by weight based on the total amount of the conductive layer, and the content of the metal is 1 to 15% by weight, the total content of water and impurities is 0 to 35% by weight.
  • the metal is one or more selected from the group consisting of palladium, platinum, rhodium, ruthenium, osmium, iridium and nickel.
  • the graphene-based conductive material of the present invention further includes a substrate layer to which the conductive layer is attached.
  • the material of the substrate layer is one selected from the group consisting of a glass plate, a quartz plate, a silicon wafer, a silicon carbide sheet, a fibrous flexible material, a natural flexible ore material, and a polymer polymer film.
  • the polymer polymer film is a transparent film made of poly(ethylene terephthalate), polyethylene, polypropylene, polystyrene or polyvinyl chloride, and the fibrous material is printing paper.
  • the natural flexible ore is a mica flake.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • a solid substance of graphene oxide and palladium chloride on the glass piece is obtained, and the solid substance is placed in an autoclave under a hydrogen atmosphere at a hydrogen pressure of 1 MPa and a temperature of 25 ° C for 12 h to obtain a thickness of the conductive layer of 2 a graphene conductive material of ⁇ .
  • the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene is 0.020
  • the content of graphene is 83.1% by weight
  • the content of metal palladium is 15% by weight
  • water and impurities The content was 1.9% by weight.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide is 0.002, the content of graphene is 95.5% by weight, the content of metal palladium is 3.0% by weight, water and impurities. The content was 1.5% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured by a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instrument Co., Ltd., model: RTS-9 dual-electric four-probe tester), and the resistivity was 1.2 kQ/sq.
  • the light transmittance at a wavelength of 550 nm is 72%, and the graphene-based conductive material has both light transmittance and conductivity, and thus can be used as a window electrode material.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the obtained graphene oxide colloid solution (containing about 600 mg of graphene oxide) was sprayed on a cleaned PET (size lO cmx lO cm) (manufactured by Germany, model: Leica EM SCD005) Spraying 0.024 ml of the obtained mixture and drying in an oven at a temperature of 80 ° C to obtain a solid substance of graphene oxide and palladium chloride on the PET sheet, and placing the solid substance in an autoclave under a hydrogen atmosphere at 0.01 MPa.
  • the reaction was carried out for 2 h under a hydrogen pressure at a temperature of 120 ° C to obtain a graphene-based conductive material having a conductive layer thickness of 1 nm.
  • the ratio of the metal atom in the conductive layer of the obtained graphene-based conductive material to the carbon atom in the graphene oxide was 0.0001, the content of the graphene was 99.999 wt%, and the content of the metal palladium was 0.001% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 50 kQ/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instrument Co., Ltd., model: RTS-9 dual-electric four-probe tester).
  • the light transmittance at a wavelength of 550 nm is 96%, and the graphene-based conductive material has both light transmittance and conductivity, and thus can be used as a window electrode material.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the dry film and the culture dish were peeled off by adding 3 wt% hydrofluoric acid, and the separately present film was taken out, and the film was again After drying at 120 ° C, the dry film was placed in an autoclave under a hydrogen atmosphere at 300 MPa hydrogen pressure and at -50 ° C for 300 hours to obtain a graphene-based conductive material having a conductive layer thickness of 1 ⁇ m. (See Figure 2). According to the calculation, the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide was 0.05, the content of graphene was 60% by weight, and the content of metal palladium was 40%.
  • the conductive layer of the graphene-based conductive material has a resistivity of 40 ⁇ /sq and can be used as a conductive material.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the solid substance was placed in an autoclave under a hydrogen atmosphere at 15 MPa hydrogen pressure, 120 ° C.
  • the reaction was carried out for 120 h (i.e., 5 days), and drying was carried out to obtain a graphene-based conductive material having a conductive layer thickness of 1 mm, which was treated with hydrofluoric acid to cause the film to fall off to obtain a freely present graphene film.
  • the ratio of the metal atom in the conductive layer of the obtained graphene-based conductive material to the carbon atom in the graphene oxide was 0.13
  • the content of graphene was 60% by weight
  • the content of metallic nickel was 40% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 0.01 Q/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instrument Co., Ltd., model: RTS-9 double-power four-probe tester).
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • a solid substance of platinum acid is placed in an autoclave under a hydrogen atmosphere at a pressure of 5 MPa hydrogen and at a temperature of 25 ° C for 12 h to obtain a graphene-based conductive material having a conductive layer thickness of 100 nm.
  • the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide is 0.002
  • the content of graphene is 98% by weight
  • the content of metal platinum is 1% by weight
  • water and impurities are examples of the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide.
  • the content of the conductive layer of the graphene-based conductive material was measured by using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 double-electric four-probe tester).
  • a four-probe resistance tester manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 double-electric four-probe tester.
  • the light transmittance at a wavelength of 550 nm is 50%. Therefore, the graphene-based conductive material has both light transmittance and conductivity and can be used as a window electrode material.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the solid substance was placed in an autoclave under a hydrogen atmosphere at 5 MPa of hydrogen.
  • the reaction was carried out for 12 h at a temperature of 25 ° C to obtain a graphene-based conductive material having a conductive layer thickness of 20 nm.
  • the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide is 0.04, the content of graphene is 64% by weight, the content of metal ruthenium is 15% by weight, water and impurities. The content was 21% by weight.
  • the probe tester measures that the conductive layer of the graphene conductive material has a resistivity of 2 kQ/sq and a light transmittance of 76% at a wavelength of 550 nm, and the graphene conductive material has both light transmittance. And conductivity, so it can be used as a window electrode material.
  • Example 8
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the solid substance was placed in an autoclave under a hydrogen atmosphere at a pressure of 5 MPa hydrogen and a temperature of 25 °C.
  • the reaction was carried out for 5 days to obtain a graphene-based conductive material having a conductive layer thickness of 16 nm.
  • the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide is 0.002
  • the content of graphene is 93.2% by weight
  • the content of metal ruthenium is 2.5% by weight
  • water and impurities The content was 4.3% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 2.5 k ⁇ /sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instrument Co., Ltd., model: RTS-9 dual-electric four-probe tester).
  • the light transmittance at a wavelength of 550 nm is 82%, and the graphene-based conductive material has both light transmittance and conductivity, and thus can be used as a window electrode material.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the reaction was carried out for 12 h at a hydrogen pressure of 5 MPa and a temperature of 25 ° C, and treated with hydrofluoric acid to obtain a graphene-based conductive material in which the thickness of the conductive layer was 2.5 ⁇ independently.
  • the ratio of the metal atom in the conductive layer of the graphene-based conductive material to the carbon atom in the graphene oxide is 0.004
  • the content of the graphene is 92.2% by weight
  • the content of the metal ruthenium is 2.7% by weight
  • water and The content of impurities was 5.1% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 80 Q/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 dual-electric four-probe tester).
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • a solid substance of graphene and ruthenium tetrachloride is placed in an autoclave under a hydrogen atmosphere at a hydrogen pressure of 5 MPa and a temperature of 25 ° C for 12 h to obtain a conductive layer having a thickness of about 2 ⁇ m.
  • Graphene based conductive material According to the calculation of the feed, the ratio of metal atoms in the conductive layer of the graphene-based conductive material to carbon atoms in graphene oxide is 0.014, the content of graphene is 87.3% by weight, the content of metal ruthenium is 9% by weight, water and impurities. The content was 3.7% by weight.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 10 Q/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 double-electric four-probe tester).
  • a four-probe resistance tester manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 double-electric four-probe tester.
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the conductivity of the conductive layer of the graphene-based conductive material was measured to be 35 Q/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instrument Co., Ltd., model: RTS-9 double-electron four-probe tester).
  • This example is intended to illustrate the preparation of the graphene-based conductive material of the present invention.
  • the conductive layer of the conductive material has a graphene content of 60%, a rhodium content of 5%, and other impurities of 35%.
  • the resistivity of the conductive layer of the graphene-based conductive material was measured to be 8 Q/sq using a four-probe resistance tester (manufactured by Guangzhou Four-Probe Instruments Co., Ltd., model: RTS-9 dual-electric four-probe tester).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Conductive Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Non-Insulated Conductors (AREA)

Description

一种石墨烯基导电材料及其制备方法
技术领域
本发明涉及一种石墨烯基导电材料的制备方法， 以及由该方法制备得 到的石墨烯基导电材料。 背景技术
石墨烯是由六方排列的 sp2碳原子组成的具有单原子厚度的二维片层， 它是石墨的组成基元。 人们发现石墨烯具有石墨所不具有的很多特性， 例 如室温量子霍尔效应、 无质量传输特性、 光学性质、 热电输运性质、 透光 性和极高的杨氏模量等。 由于石墨烯具有这些特性， 石墨烯及石墨烯基材 料在很多方面具有潜在的用途， 如显示器薄膜、 太阳能电池电极、 锂离子 电池电极、 场效应晶体管和传感器等。
一般， 通过氧化石墨烯还原的方法大批量制备石墨烯材料。 氧化石墨 烯是石墨氧化后产生的产物， 其中的元素包括碳、 氢和氧。 石墨被氧化后 不但产生缺陷， 而且其原始平面结构被破坏。 氧化石墨烯通过还原处理后， 其中氧的比例下降， 并且石墨烯片层结构得到恢复， 其导电性也得到恢复。 通过不同方法还原得到的石墨烯产物有很大差异， 这些差异主要体现在结 构和组成上。 目前还原氧化石墨烯的方法主要包括高温热处理， 肼还原， 硼氢化钠还原等方法。 一方面， 通过这些方法处理氧化石墨烯得到的石墨 烯组成和结构有很大差异。 通过热处理， 一些含氧官能团被除掉， 但是带 来比氧化过程中更大的缺陷， 一些研究报道表明热处理后其内部结构发生 重整， 形成五元环、 七元环和八元环甚至更复杂的碳结构， 与石墨烯中纯 粹的六元环在结构上有很大差异。 通过肼或硼氢化钠处理， 文献研究表明 得到的石墨烯含有氮或硼， 这些氮原子或硼原子和还原得到的石墨烯中的 碳原子形成了化学键， 因此通过这两种还原剂还原氧化石墨烯得到的石墨 烯实际上是被氮或硼化学掺杂的石墨烯， 这两种石墨烯可以称为氮掺杂石 墨烯和硼掺杂石墨烯。 另一方面， 目前采用的这些还原方法具有很多缺点， 例如高温不利于石墨烯在柔性基底材料上的沉积， 而作为还原剂的肼具有 毒性， 硼氢化钠又过于昂贵。 氢气也是一种还原剂， 可以用于还原氧化石 墨烯， 但是只用氢气还原需要很高的温度， 例如有文献报道使用 1000 °c的 氢气还原氧化石墨烯， 由于经历了热处理， 氢气的还原作用十分有限。
有文献报道了在氧化石墨烯上负载金属钯的催化剂， 但这种含有石墨 烯和金属的材料在有机反应中仅利用其中的金属钯的催化性能， 该文献并 没有提及这种材料是否具有导电性， 另外得到的石墨烯是肼还原的， 因此 其中的石墨烯是含氮的石墨烯。 还有文献报道了硼氢化钠还原氧化石墨烯 和钯的配合物得到含有石墨烯和金属钯的材料， 但是其中的石墨烯是含硼 的石墨烯。 因此， 在已有的专利和文献中还没有报道含有金属并由氢气还 原得到的固态的石墨烯基导电材料。 发明内容
为了克服现有技术中制备石墨烯材料时需要使用高温或有毒的还原剂 肼的缺点， 本发明提供一种能够在低温条件下制备且环保无污染的石墨烯 基导电材料及其制备方法。
本发明的发明人发现， 在还原氧化石墨烯的过程中， 引入金属能够催 化氧化石墨烯的还原过程， 并能够降低反应温度。 基于此发现， 本发明的 发明人提供一种可以在低温下直接制备固态石墨烯基导电材料的制备方法 及通过这种方法得到的固态石墨烯基导电材料。
本发明提供一种石墨烯基导电材料的制备方法， 该方法包括， 将氧化 石墨烯溶胶与金属盐溶液和 /或金属胶体溶液在基材层上制成固态膜， 然后 将该固态膜与基材层分离或不分离后在温度为 -50°C至 200°C、 氢气压力为 0.01-100 MPa的氢气气氛或者含氢气的还原气氛条件下放置 30秒 -10000小 时， 得到石墨烯基导电材料。
本发明还提供一种石墨烯基导电材料， 所述石墨烯基导电材料由上述 方法制备得到。
本发明的方法与现有技术相比， 具有以下有益效果：
( 1 )本发明首次通过催化氢化还原固态氧化石墨烯的方法制备石墨烯 基导电材料， 此方法利用催化剂降低了氢化还原反应的温度， 由于使用低 温的氢气还原氧化石墨烯， 氧化石墨烯的骨架结构没有被破坏， 因此其与 高温处理的氧化石墨烯具有较多缺陷不同； 并且， 没有引入杂原子， 其与 肼或硼氢化钠还原得到的石墨烯在组成上不同。 另外， 由于降低了氢化还 原反应的温度， 所以可以于室温下在一些不能忍受高温处理的高分子基底 上制备石墨烯基导电材料。
(2)在溶液中氢气还原氧化石墨烯得到的石墨烯不是固态， 且没有形 成导电材料， 采用本发明的方法， 可以克服在溶液中制备石墨烯沉淀物或 颗粒再加工为成型导电材料的繁琐之处， 操作简便， 因而可以大量制备石 墨烯基导电材料。
(3 )本发明采用催化氢化还原氧化石墨烯的方法制备石墨烯基导电材 料， 相对于使用具有毒性的肼的还原途径， 本发明提供的是完全绿色的还 原途径； 相对于昂贵的硼氢化钠和苯醌的还原途径， 本发明所使用的氢气 是廉价易得的原料。
(4)本发明所制备的石墨烯导电材料具有非常好的化学稳定性和热稳 定性， 且其可负载于柔性基底上， 因此可广泛应用于柔性器件如柔性电路、 柔性透明窗口电极以及柔性触摸屏电极等。
附图说明
图 1是根据本发明的实施例 2得到的在柔性基底 PET上的石墨烯基导 电薄膜。
图 2是根据本发明的实施例 4得到的独立存在的石墨烯导电薄膜。 图 3是根据本发明的实施例 12得到的在打印纸上的具有一定图案的石 墨烯导电薄膜。 具体实施方式
本发明提供一种石墨烯基导电材料的制备方法， 该方法包括， 将氧化 石墨烯溶胶与金属盐溶液和 /或金属胶体溶液在基材层上制成固态膜， 然后 将该固态膜与基材层分离或不分离后在温度为 -50°C至 200°C、 氢气压力为 0.01-100 MPa的氢气气氛或者含氢气的还原气氛条件下放置 30秒 -10000小 时， 得到石墨烯基导电材料。
根据本发明， 优选情况下， 所述放置的时间为 5分钟 -300小时， 更优 选为 2小时 -5天。
根据本发明， 优选情况下， 所述氢气压力为 0.2-100 MPa。
根据本发明， 特别优选情况下， 所述温度为 20-120°C， 所述氢气压力 为 l-15Mpa， 反应时间可以为 2小时 -5天。
本发明中， 当为氢气气氛时， 所述氢气压力为表压； 当为含氢气的还 原气氛例如氢气与氮气和 /或惰性气体的混合气体气氛时， 所述氢气压力为 氢分压。 由此可见， 采用本发明的制备方法， 可以在较低的温度下例如室 温下很方便地制备得到所述石墨烯基导电材料。
在本发明提供的石墨烯基导电材料的制备方法中， 通过控制氧化石墨 烯与金属盐溶液和 /或金属胶体溶液的用量， 就可以使石墨烯基导电材料中 的金属原子与石墨烯中碳原子的比例为 0.0001-0.13。 所述金属胶体溶液中 的胶体粒子直径为 0.7-lOnm, 所述氧化石墨烯溶胶的浓度为 0.5-2克 /升， 所述金属盐溶液的浓度为 1-3克 /升， 所述金属胶体的浓度为 3-7克 /升。 同 时， 通过引入少量的金属盐溶液和 /或金属胶体溶液， 即可达到催化氢化反 应的目的， 所以， 当使用贵金属或其盐作为催化剂或催化剂前体时， 可节 约贵金属的用量。 此外， 在制备过程中将金属盐作为催化剂时， 该金属盐 首先在还原反应中被还原为金属粒子， 然后该金属粒子催化氢化还原氧化 石墨烯的还原反应。
所述金属盐溶液和 /或金属胶体溶液中的金属为钯、 铂、 铑、 钌、 锇、 铱和镍中的一种或多种， 所述金属盐选自硝酸盐、 盐酸盐、 硫酸盐、 磷酸 盐、 草酸盐、 乙酸盐、 甲酸盐、 丙酸盐、 丁酸盐和戊酸盐中的一种或多种， 所述金属盐溶液中的溶剂为水、碳原子数为 1-4的低级醇、丙酮和二甲基甲 酰胺中的一种或多种， 所述氧化石墨烯溶胶的溶剂为水、 碳原子数为 1-4 的低级醇和丙酮中的一种或多种。
在本发明中， 所述将氧化石墨烯溶胶与金属盐溶液和 /或金属胶体溶液 在基材层上制成固态膜的方法包括旋涂法、 滴涂法、 喷涂法、 喷墨打印法 和加热溶液成膜法中的一种或多种。
在本发明中， 所述基材层的材质为选自玻璃片、 石英片、 硅片、 碳化 硅片、 含纤维质柔性材料、 天然柔性矿石材料和聚合物高分子薄膜中的一 种。 所述聚合物高分子薄膜为由聚苯二甲酸二乙醇酯、 聚乙烯、 聚丙烯、 聚苯乙烯或聚氯乙烯制成的透明薄膜， 所述含纤维质柔性材料为打印用纸 张， 所述天然柔性矿石材料为云母片。
在本发明提供的石墨烯基导电材料的制备方法中， 可以通过控制催化 氢化还原氧化石墨烯的还原反应所发生的条件， 例如反应时间、 固态物质 的厚度和大小等， 可以得到不同的石墨烯基导电材料。 例如， 通过控制氧 化石墨烯水溶胶与金属盐溶液和 /或金属胶体溶液的混合物的成膜厚度， 使 还原后得到的石墨烯导电材料的厚度为 1-lOOnm时， 如此得到的石墨烯基 导电材料的透光性能优异； 通过控制氧化石墨烯水溶胶与金属盐溶液和 /或 金属胶体溶液的混合物的成膜厚度， 使还原后得到的石墨烯导电材料的厚 度为 lOOnm-lmm时， 如此得到的石墨烯基导电材料的导电性优异。
所述氧化石墨烯可以采用本领域已知的各种方法来制备， 这些方法包 括 Staudenmaier、 Brodie禾口 Hummers方、法， Staudenmaier方、法米用、浓硫酸禾口 发烟硝酸混合物作为溶剂和氧化剂， 氯酸钾作为氧化剂， 以石墨为原料制 备氧化石墨， Bradie 方法采用发烟硝酸作为溶剂和氧化剂， 氯酸钾作为氧 化剂以石墨为原料制备氧化石墨， Hummers方法采用浓硫酸作为溶剂和氧 化剂， 硝酸钠和高锰酸钾作为氧化剂， 或者也可以采用以这些方法为基础 而改进的其它方法。
优选情况下， 本发明的氧化石墨烯可采用如下步骤来制备， 但不限于 以下方法得到氧化石墨烯：
( 1 )使鳞片状石墨在浓硫酸、 高锰酸钾混合氧化剂中氧化并经双氧水 处理；
(2 ) 洗涤、 过滤、 离心分离氧化后的混合物， 得到氧化石墨烯。
在本发明的一个实施方式中， 本发明的氧化石墨烯的制备方法如下： 将约 1 g的天然鳞片状石墨加入到 20-100 g的浓硫酸中， 0°C的冰浴下搅拌 过夜，然后向得到的混合物中加入 0.05-0.5 g的高锰酸钾，为防止温度升高， 搅拌 10-100 min后再加入 1-10 g的高锰酸钾并控制温度在 20°C以下； 然后 再升高温度至 20-50 V， 并保持此温度 10-100 min, 在此过程中所得混合 物变得粘稠； 然后向该混合物中加入 20-100 ml的水， 并升高温度至 90-95 V， 维持此温度 15-60 min; 之后再加入 30-60 ml的浓度为 20-50重量％的 双氧水，搅拌 10-100 min后再加入 10-100 ml的水，趁热过滤，用 20-100 ml 的浓度为 1-10重量％的盐酸洗涤， 将所得滤饼放入 400-1000 ml的水中超 声处理 0.5-2小时，将得到的分散液离心除去未被完全剥离的氧化石墨烯颗 粒（未被完全剥离的颗粒附着于离心机的内壁上）， 将离心分离后得到的分 散液离心除去少量团聚的氧化石墨烯微细颗粒， 得到胶状物， 向此胶状物 中加约 500-2000 ml的水（或乙醇和水的混合液、 甲醇和水的混合液（甲醇 或乙醇与水的体积比例范围为 0.1-10 )或二甲基甲酰胺）分散， 即得到氧化 石墨烯的胶体溶液。
本发明还提供一种石墨烯基导电材料， 所述材料由上述的方法制备得 到。
根据本发明的石墨烯基导电材料， 其中， 所述材料包括导电层， 该导 电层包含金属和石墨烯， 所述导电层的电阻率为 0.01 Q/s -50 kQ/sq, 透光 率为 0-96% , 厚度为 1 nm-1 mm。
根据本发明， 优选情况下， 所述透光率为 0-90% , 厚度为 5 nm-l mm。 根据本发明， 其中， 在所述导电层的电阻率为 100 Q/s -50 kQ/sq, 透 光率为 50-90% , 厚度为 l- 100 nm的情况下，所述导电材料可以同时具有较 好的导电性和透光性。 另外， 在所述导电层的电阻率为 Ο.ΟΙ- ΙΟΟΩ/sq, 厚度 为 100 nm- 1 mm的情况下， 该导电材料的导电性能优异， 完全可以代替金 属用作电路中的导电材料。在本发明中，单位符号 Ω/sq表示欧姆 /平方厘米， 即本发明中的电阻为方块电阻。
在本发明中， 以所述导电层的总量为基准， 所述导电层中石墨烯的含 量为 60-99.999重量％， 所述金属的含量为 0.001 -40重量％。
在本发明的导电材料中还可能含有水和杂质， 优选地， 以所述导电层 的总量为基准， 所述导电层中石墨烯的含量为 64-98重量％， 所述金属的含 量为 1-15重量％， 水和杂质的总含量为 0-35重量％。
在本发明的导电材料中， 所述金属选自钯、 铂、 铑、 钌、 锇、 铱和镍 中的一种或多种。
本发明的石墨烯基导电材料还包括基材层，所述导电层附着在所述基 材层上。 所述基材层的材质为选自玻璃片、 石英片、 硅片、 碳化硅片、 含 纤维质柔性材料、 天然柔性矿石材料和聚合物高分子薄膜中的一种。 优选 情况下， 所述聚合物高分子薄膜为由聚苯二甲酸二乙醇酯、 聚乙烯、 聚丙 烯、 聚苯乙烯或聚氯乙烯制成的透明薄膜， 所述纤维质材料为打印用纸， 所述天然柔性矿石为云母片。
以下结合实施例详细说明本发明。 实施例 1
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 将 1 g的天然鳞片状石墨加入 20g 的浓度为 95重量％的浓硫酸中， 在 0°C的冰浴下搅拌过夜， 然后向得到的 混合物中加入 0.15 g的高锰酸钾， 搅拌 30 min后再加入 3 g的高锰酸钾并 控制温度在 20°C以下； 然后再升高温度至 35 °C， 并保持此温度 30 min, 然 后向该混合物中加入 45 ml的水，升高温度至 90-95°C，维持此温度 15 min; 之后再加入 30 ml的浓度为 30重量％的双氧水，搅拌 30 min后再加入 26 ml 的水， 趁热过滤， 用 50 ml的浓度为 3重量％的盐酸洗涤 3次， 将所得滤饼 放入 400 ml的水中超声处理 1 h，将得到的分散液于 3000 r/min的条件下离 心除去未被完全剥离的氧化石墨烯颗粒 （未被完全剥离的颗粒附着于离心 机的内壁上）， 得到黑色的氧化石墨烯分散液； 将离心分离后得到的分散液 在 10000 r/min的条件下离心除去少量团聚的氧化石墨烯微细颗粒， 得到胶 状物，向此胶状物中加约 1000 ml的水分散，即得到氧化石墨烯的胶体溶液；
(2 )石墨烯导电材料的制备： 向上述 60 ml的氧化石墨烯胶体溶液（其 中约含氧化石墨烯 60 mg)中加入 3 ml的氯化钯水溶液（其浓度以钯计为 2 g/l， 北京化学试剂公司）， 在洗净的玻璃片 （2 cmx2 cm) 上滴加 2 ml所得 混合液并均匀涂布（即滴涂法）， 在烘箱中于 80 °C的温度下烘干， 得到玻璃 片上的氧化石墨烯与氯化钯的固态物质， 将此固态物质置于氢气气氛的高 压釜中在 1 MPa氢气压力、 25°C的温度下反应 12 h，得到导电层的厚度为 2 μηι的石墨烯基导电材料。 根据加料计算得到， 该石墨烯基导电材料的导电 层中金属原子与石墨烯中碳原子的比值为 0.020，石墨烯的含量为 83.1重量 %， 金属钯的含量为 15重量％， 水和杂质的含量为 1.9重量％。采用四探针 电阻测试仪（广州四探针仪器公司生产， 型号: RTS— 9双电四探针测试仪） 测得所得石墨烯基导电材料的导电层的电阻率为 ΙΟ Ω/sq, 因此可以用作电 路材料。 实施例 2
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
(1) 氧化石墨烯胶体溶液的制备： 同实施例 1的步骤 （1);
(2)石墨烯基导电材料的制备： 向 60ml的上述步骤（1)得到的氧化 石墨烯胶体溶液（其中约含氧化石墨烯 60 mg)中加入 0.5 ml的氯化钯水溶 液（其浓度以钯计为 2 g/l， 北京化学试剂公司）， 在洗净的 PET (聚苯二甲 酸乙二醇酯） 上 （2cmx2cm) 滴加 0.5 ml所得混合液， 在室温下使用旋涂 仪（中科院电子所生产， 型号: kW— 4A)在 2000r/min速度下旋涂 60秒， 得到 PET片上的氧化石墨烯与氯化钯的固态物质， 将此固态物质置于氢气 气氛的高压釜中在 5 MPa氢气压力、 25°C的温度下反应 12 h， 即得到导电 层的厚度约为 25 nm的石墨烯基导电材料（参见图 1， 该图是在一张白纸上 用黑色笔写字后， 将所得石墨烯基导电材料放置在写有字的白纸上， 可以 看到， 该石墨烯基导电材料的透光性优异）。 根据加料计算得到， 所得石墨 烯基导电材料的导电层中金属原子与氧化石墨烯中碳原子的比值为 0.002， 石墨烯的含量为 95.5重量％， 金属钯的含量为 3.0重量％， 水与杂质的含量 为 1.5重量％。 采用四探针电阻测试仪 （广州四探针仪器公司生产， 型号: RTS-9双电四探针测试仪）测得该石墨烯基导电材料的导电层的电阻率为 1.2 kQ/sq, 在波长为 550 nm处的透光率为 72%, 该石墨烯基导电材料兼具 透光性及导电性， 因此可以用作窗口电极材料。 实施例 3
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
(1) 氧化石墨烯胶体溶液的制备： 同实施例 1的步骤 （1);
(2) 石墨烯基导电材料的制备： 用微量移液枪取 0.03 ml的氯化钯水 溶液 （其浓度以钯计为 2 g/1, 北京化学试剂公司） 加入到 600 ml的上述步 骤 （1 ) 所得到的氧化石墨烯胶体溶液 （其中约含氧化石墨烯 600 mg) 中， 在洗净的 PET (尺寸 lO cmx lO cm)上使用喷涂仪（德国生产， 型号： Leica EM SCD005 ) 喷涂 0.024 ml所得混合液， 在烘箱中于 80 °C的温度下烘干， 得到 PET片上的氧化石墨烯与氯化钯的固态物质， 将此固态物质置于氢气 气氛的高压釜中在 0.01 MPa氢气压力、 120°C的温度下反应 2 h， 即得到导 电层的厚度为 l nm的石墨烯基导电材料。 根据加料计算得到， 所得石墨烯 基导电材料的导电层中金属原子与氧化石墨烯中碳原子的比值为 0.0001， 石墨烯的含量为 99.999重量％， 金属钯的含量为 0.001重量％。采用四探针 电阻测试仪（广州四探针仪器公司生产， 型号: RTS— 9双电四探针测试仪） 测得该石墨烯基导电材料的导电层的电阻率为 50 kQ/sq, 在波长为 550 nm 处的透光率为 96%, 该石墨烯基导电材料兼具透光性及导电性， 因此可以 用作窗口电极材料。
实施例 4
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1的步骤 （1 );
(2 )石墨烯基导电材料的制备： 取 60 ml的上述步骤（1 )得到的氧化 石墨烯胶体溶液 （其中约含氧化石墨烯 60 mg) 在 10000 r/min的条件下离 心后，得到沉淀物分散于 60ml丁醇中， 向得到的混合液中加入 107 ml的氯 化钯丁醇溶液 （其浓度以钯计为 2 g/l， 北京化学试剂公司）， 向培养皿 （直 径 3.5 cm) 中滴加 7 ml所得混合液， 加热到 120°C， 烘干， 得到干膜， 加 入 3重量％氢氟酸使干膜与培养皿脱落，取出该独立存在的薄膜， 并将此薄 膜再次在 120°C烘干，将此干膜置于氢气气氛的高压釜中在 100 MPa氢气压 力、 -50°C的温度下反应 300小时， 即得到导电层的厚度为 1 μηι的石墨烯 基导电材料 （参见图 2)。 根据加料计算得到， 该石墨烯基导电材料的导电 层中金属原子与氧化石墨烯中碳原子的比值为 0.05， 石墨烯的含量为 60重 量％， 金属钯的含量为 40%。 采用四探针电阻测试仪 （广州四探针仪器公 司生产， 型号： RTS— 9双电四探针测试仪）测得该石墨烯基导电材料的导 电层的电阻率为 40 Ω/sq, 可用作导电材料。 实施例 5
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1的步骤 （1 ) ;
(2 ) 石墨烯的制备： 向 600 ml的上述步骤 （1 ) 得到的氧化石墨烯胶 体溶液（其中约含氧化石墨烯 60 mg) 中加入 1070 ml的硫酸镍水溶液（其 浓度以镍计为 2 g/l，北京化学试剂公司，分析纯），在石英片上（2 cmx2 cm) 滴加 2 ml所得混合液并均匀涂布， 加热至 200°C， 烘干， 再次在该样品上 滴加 2 ml混合液并均匀涂布， 共重复此过程 500遍， 得到石英片上的氧化 石墨烯与硫酸镍的固态物质， 将此固态物质置于氢气气氛的高压釜中在 15 MPa氢气压力、 120°C的温度下反应 120 h (即 5天）， 烘干即得到导电层的 厚度为 l mm的石墨烯基导电材料， 使用氢氟酸处理， 使薄膜脱落， 得到自 由存在的石墨烯薄膜。 根据加料计算得到， 所得石墨烯基导电材料的导电 层中金属原子与氧化石墨烯中碳原子的比值为 0.13， 石墨烯的含量为 60重 量％， 金属镍的含量为 40重量％。 采用四探针电阻测试仪 （广州四探针仪 器公司生产， 型号： RTS— 9双电四探针测试仪） 测得该石墨烯基导电材料 的导电层的电阻率 0.01 Q/sq。
实施例 6
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2 )石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )所得的氧化 石墨烯胶体溶液 （其中约含氧化石墨烯 60 mg) 中加入 1 ml的氯铂酸水溶 液（其浓度以铂计为 2 g/l， 北京化学试剂公司）， 在洗净的 PET上（2 cmx2 cm) 滴加 2.5 ml所得混合液， 在室温下使用旋涂仪 （中科院电子所生产， 型号： kW— 4A) 在 2000 r/min速度下旋涂 60秒， 得到 PET片上的氧化石 墨烯与氯铂酸的固态物质，将此固态物质置于氢气气氛的高压釜中在 5 MPa 氢气压力、 25°C的温度下反应 12 h， 即得到导电层的厚度为 100 nm的石墨 烯基导电材料。 根据加料计算得到， 所得石墨烯基导电材料的导电层中金 属原子与氧化石墨烯中碳原子的比值为 0.002， 石墨烯的含量为 98重量％， 金属铂的含量为 1重量％， 水与杂质的含量为 1重量％， 采用四探针电阻测 试仪 （广州四探针仪器公司生产， 型号: RTS— 9双电四探针测试仪） 测得 该石墨烯基导电材料的导电层的电阻率为 ΙΟΟ Ω/sq, 在波长为 550 nm处的 透光率为 50%, 因此， 该石墨烯基导电材料兼具透光性及导电性， 可以用 作窗口电极材料。 实施例 7
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2)石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )得到的氧化 石墨烯胶体溶液（其中约含氧化石墨烯 60 mg) 中加入 10 ml的硝酸钌水溶 液（其浓度以钌计为 2 g/l，北京化学试剂公司），在洗净的 PVC (聚氯乙烯） 薄膜 （2 Cmx2 cm) 上滴加所得混合液 0.5 ml, 在室温下使用旋涂仪 （中科 院电子所生产， 型号： kW— 4A)在 2000 r/min速度下旋涂 60秒， 得到 PET 片上的氧化石墨烯与硝酸钌的固态物质， 将此固态物质置于氢气气氛的高 压釜中在 5 MPa氢气压力和 25°C的温度下反应 12 h， 即得到导电层的厚度 为 20 nm的石墨烯基导电材料。 根据加料计算得到， 所得石墨烯基导电材 料的导电层中金属原子与氧化石墨烯中碳原子的比值为 0.04， 石墨烯的含 量为 64重量％， 金属钌的含量为 15重量％， 水与杂质的含量为 21重量％。 采用四探针电阻测试仪 （广州四探针仪器公司生产， 型号： RTS— 9双电四 探针测试仪） 测得该石墨烯基导电材料的导电层的电阻率为 2 kQ/sq， 在波 长为 550 nm处的透光率为 76%,该石墨烯基导电材料兼具透光性及导电性， 因此可以用作窗口电极材料。 实施例 8
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2 )石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )得到的氧化 石墨烯胶体溶液 （其中约含氧化石墨烯 60 mg) 中加入 1 ml的硝酸铱水溶 液（其浓度以铱计为 2 g/l，北京化学试剂公司），在洗净的 PET薄膜（2 cmx2 cm) 上滴加 0.4 ml所得混合液， 室温下使用旋涂仪 （中科院电子所生产， 型号： kW— 4A) 在 2000 r/min速度下旋涂 60秒， 得到 PET片上的氧化石 墨烯与硝酸铱的固态物质，将此固态物质置于氢气气氛的高压釜中在 5 MPa 氢气压力和 25°C的温度下反应 5天， 即得到导电层的厚度为 16 nm的石墨 烯基导电材料。 根据加料计算得到， 所得石墨烯基导电材料的导电层中金 属原子与氧化石墨烯中碳原子的比值为 0.002，石墨烯的含量为 93.2重量％， 金属铱的含量为 2.5重量％， 水与杂质的含量为 4.3重量％。 采用四探针电 阻测试仪 （广州四探针仪器公司生产， 型号： RTS— 9双电四探针测试仪） 测得该石墨烯基导电材料的导电层的电阻率为 2.5 kQ/sq， 在波长为 550 nm 处的透光率为 82%, 该石墨烯基导电材料兼具透光性及导电性， 因此可以 用作窗口电极材料。 实施例 9
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2 )石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )得到的 石墨烯胶体溶液（其中约含氧化石墨烯 60 mg)中加入 0.3 ml的三氯化铑水 溶液 （其浓度以铑计为 2 g/l， 北京化学试剂公司）， 在洗净的 PET薄膜 （2 cmx2 cm) 上滴加 2.5 ml所得混合液， 在 80°C的温度下烘干， 得到 PET片 上的氧化石墨烯与三氯化铑的固态物质， 将此固态物质置于氢气气氛的高 压釜中在 5 MPa氢气压力和 25°C的温度下反应 12 h， 通过氢氟酸处理， 即 得到导电层的厚度为 2.5 μηι独立存在的石墨烯基导电材料。 根据加料计算 得到， 所得该石墨烯基导电材料的导电层中金属原子与氧化石墨烯中碳原 子的比值为 0.004， 石墨烯的含量为 92.2重量％， 金属铑的含量为 2.7重量 %， 水与杂质的含量为 5.1重量％。 采用四探针电阻测试仪 （广州四探针仪 器公司生产， 型号： RTS— 9双电四探针测试仪） 测得该石墨烯基导电材料 的导电层的电阻率为 80 Q/sq。
实施例 10
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2)石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )得到的氧化 石墨烯胶体溶液（其中约含氧化石墨烯 60 mg)中加入 3.5 ml的四氯化锇水 溶液 （其浓度以锇计为 2 g/l， 北京化学试剂公司）， 在洗净的 PET薄膜 （2 cmx2 cm)上滴加 2 ml所得混合液， 在 80°C的温度下烘干， 得到 PET片上 的氧化石墨烯与四氯化锇的固态物质， 将此固态物质置于氢气气氛的高压 釜中在 5 MPa氢气压力和 25 °C的温度下反应 12 h， 即得到导电层的厚度约 为 2 μηι的石墨烯基导电材料。 根据加料计算得到， 所得石墨烯基导电材料 的导电层中金属原子与氧化石墨烯中碳原子的比值为 0.014， 石墨烯的含量 为 87.3重量％， 金属锇的含量为 9重量％， 水与杂质的含量为 3.7重量％。 采用四探针电阻测试仪 （广州四探针仪器公司生产， 型号: RTS— 9双电四 探针测试仪） 测得该石墨烯基导电材料的导电层的电阻率为 10 Q/sq。 实施例 11
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2 ) 铂胶体纳米粒子溶液的制备： 向 50 ml的含 1.04 g的氢氧化钠的 乙二醇溶液中加入 50 ml 的浓度为 7.4 g/1的氯铂酸的乙二醇溶液， 搅拌 30 min后， 在氮气保护的条件下于 180°C的温度下反应 3 h， 冷却后即得到铂 胶体纳米粒子溶液 （浓度 3.7 g/l， 以铂计， 北京化学试剂公司）， 其中铂胶 体的尺寸范围为 0.7-3.5 nm;
(3 )石墨烯基导电材料的制备： 向 60 ml的上述步骤（1 )得到的氧化 石墨烯胶体溶液（其中约含氧化石墨烯 60 mg)中加入 1 ml的上述步骤（2 ) 得到的铂胶体纳米粒子溶液 （其浓度以铂计为 3.7 g/1为， 北京化学试剂公 司）， 在洗净的云母片上 （2 cmx2 cm) 滴加 2 ml所得混合液， 在 80°C的温 度下烘干， 得到 PET片上的氧化石墨烯与铂胶体纳米粒子的固态物质， 将 此固态物质置于氢气气氛的高压釜中在 5 MPa氢气压力和 25 °C的温度下反 应 12 h， 即得到导电层的厚度为 2 μηι的石墨烯基导电材料。 根据加料计算 得到， 所得石墨烯基导电材料的导电层中金属原子与氧化石墨烯中碳原子 的比值为 0.007， 石墨烯的含量为 91重量％， 金属铂的含量为 5.6重量％， 水与杂质的含量为 3.4重量％。 采用四探针电阻测试仪（广州四探针仪器公 司生产， 型号： RTS— 9双电四探针测试仪）测得该石墨烯基导电材料的导 电层的电阻率为 35 Q/sq。
实施例 12
该实施例用于说明本发明的石墨烯基导电材料的制备方法。
( 1 ) 氧化石墨烯胶体溶液的制备： 同实施例 1步骤 （1 );
(2 ) 钌胶体的制备： 将 1 g六水合三氯化钌 （北京化学试剂公司） 溶 于 50 ml水中， 加入聚乙烯基吡咯垸酮 （平均分子量， 40000， 北京化工厂 生产） 3 g， 加热回流该溶液， 6 h后得到钌的胶体溶液， 该溶液浓度为 6.4 g/l(以钌计：)， 钌胶体粒子的尺寸范围为 2.5-10 nm。
(3 ) 向 60 ml的上述步骤（1 )得到的氧化石墨烯胶体溶液（其中约含 氧化石墨烯 60 mg)中加入步骤（2 )得到的钌胶体（其浓度以钌计为 6.4g/l， 北京化学试剂公司） 0.54 ml, 再向所得混合液中加入 0.5 ml的异丙醇， 将 所得混合液混合均匀后， 充入喷墨打印机墨盒中 （HP816) , 用惠普打印机 (HP2468)在纸上打印 20遍， 得到预计的图案， 将在打印纸上得到的物质 置于氢气气氛的高压釜中在 5 MPa氢气压力和 25°C的温度下反应 12 h， 即 得到具有图案的石墨烯基导电材料， 该导电层的厚度为 20 μηι (参见图 3 )。 该导电材料的导电层中石墨烯的含量为 60%, 钌的含量为 5%， 其它杂质的 含量为 35%。 采用四探针电阻测试仪 （广州四探针仪器公司生产， 型号： RTS-9双电四探针测试仪）测得该石墨烯基导电材料的导电层的电阻率为 8 Q/sq。

Claims

权利要求
1、 一种石墨烯基导电材料的制备方法， 其特征在于， 该方法包括， 将 氧化石墨烯溶胶与金属盐溶液和 /或金属胶体溶液在基材层上制成固态膜， 然后将该固态膜与基材层分离或不分离后在温度为 -50°C至 200 °C、 氢气压 力为 0.01-100 MPa 的氢气气氛或者含氢气的还原气氛条件下放置 30 秒 -10000小时， 得到石墨烯基导电材料。
2、 根据权利要求 1所述的制备方法， 其中， 所述放置的时间为 5分钟 -300小时。
3、 根据权利要求 2所述的制备方法， 其中， 所述放置的时间为 2小时 -5天。
4、 根据权利要求 1 所述的制备方法， 其中， 所述氢气压力为 0.2-100 MPa。
5、 根据权利要求 1所述的制备方法， 其中， 所述石墨烯基导电材料中 的金属原子与石墨烯中碳原子的比例为 0.0001-0.13， 所述金属胶体溶液中 的胶体粒子直径为 0.7-lOnm, 所述氧化石墨烯溶胶的浓度为 0.5-2克 /升， 所述金属盐溶液的浓度为 1-3克 /升， 所述金属胶体的浓度为 3-7克 /升。
6、 根据权利要求 1 或 5所述的制备方法， 其中， 所述金属盐溶液和 / 或金属胶体溶液中的金属为钯、 铂、 铑、 钌、 锇、 铱和镍中的一种或多种， 所述金属盐选自硝酸盐、 盐酸盐、 硫酸盐、 磷酸盐、 草酸盐、 乙酸盐、 甲 酸盐、 丙酸盐、 丁酸盐和戊酸盐中的一种或多种， 所述金属盐溶液中的溶 剂为水、 碳原子数为 1-4的低级醇、 丙酮和二甲基甲酰胺中的一种或多种， 所述氧化石墨烯溶胶的溶剂为水、碳原子数为 1-4的低级醇和丙酮中的一种 或多种。
7、 根据权利要求 1所述的制备方法， 其中， 所述将氧化石墨烯溶胶与 金属盐溶液和 /或金属胶体溶液在基材层上制成固态膜的方法包括旋涂法、 滴涂法、 喷涂法、 喷墨打印法和加热溶液成膜法中的一种或多种。
8、 根据权利要求 1或 7所述的制备方法， 其中， 所述基材层的材质为 选自玻璃片、 石英片、 硅片、 碳化硅片、 含纤维质柔性材料、 天然柔性矿 石材料和聚合物高分子薄膜中的一种。
9、 根据权利要求 8所述的制备方法， 其中， 所述聚合物高分子薄膜为 由聚苯二甲酸二乙醇酯、 聚乙烯、 聚丙烯、 聚苯乙烯或聚氯乙烯制成的透 明薄膜， 所述含纤维质柔性材料为打印用纸张， 所述天然柔性矿石材料为 云母片。
10、 一种石墨烯基导电材料， 其特征在于， 所述石墨烯基导电材料由 权利要求 1-9中的任意一项所述的方法制备得到。
11、 根据权利要求 10所述的石墨烯基导电材料， 其中， 所述石墨烯基 导电材料包括导电层， 该导电层包含金属和石墨烯， 所述导电层的电阻率 为 0.01 Q/sq-50 kQ/sq, 透光率为 0-96%, 厚度为 1 nm-1 mm。
12、 根据权利要求 11所述的石墨烯基导电材料， 其中， 所述透光率为 0-90%, 厚度为 5 nm-1 mm。
13、 根据权利要求 11所述的石墨烯基导电材料， 其中， 所述导电层的 电阻率为 100 Q/sq-50 kQ/sq， 透光率为 50-90%, 厚度为 1-100 nm; 或者， 所述导电层的电阻率为 0.01-100 Ω/sq, 厚度为 lOO nm-1 mm。
14、 根据权利要求 11或 13所述的石墨烯基导电材料， 其中， 以所述 导电层的总量为基准， 所述导电层中的石墨烯含量为 60-99.999重量％， 金 属含量为 0.001-40重量％。
15、 根据权利要求 11所述的石墨烯基导电材料， 其中， 所述导电层中 还含有水和杂质， 以所述导电层的总量为基准， 所述导电层中的石墨烯含 量为 64-98重量％， 金属含量为 1-15重量％， 水和杂质的总含量为 0-35重 量0 /0。
16、 根据权利要求 11所述的石墨烯基导电材料， 其中， 所述石墨烯基 导电材料还包括基材层， 所述导电层附着在所述基材层上。
17、 根据权利要求 16所述的石墨烯基导电材料， 其中， 所述基材层的 材质为选自玻璃片、 石英片、 硅片、 碳化硅片、 含纤维质柔性材料、 天然 柔性矿石材料和聚合物高分子薄膜中的一种。
18、 根据权利要求 17所述的石墨烯基导电材料， 其中， 所述聚合物高 分子薄膜为由聚苯二甲酸二乙醇酯、 聚乙烯、 聚丙烯、 聚苯乙烯或聚氯乙 烯制成的透明薄膜， 所述含纤维质柔性材料为打印用纸张， 所述天然柔性 矿石材料为云母片。
PCT/CN2011/074117 2010-05-18 2011-05-16 一种石墨烯基导电材料及其制备方法 WO2011144010A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2013510491A JP5540151B2 (ja) 2010-05-18 2011-05-16 グラフェン系導電材料およびその調製方法
US13/698,517 US20130059143A1 (en) 2010-05-18 2011-05-16 Graphene based conductive material and preparation method thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010179290.2 2010-05-18
CN2010101792902A CN102254582B (zh) 2010-05-18 2010-05-18 一种石墨烯基导电材料及其制备方法

Publications (1)

Publication Number Publication Date
WO2011144010A1 true WO2011144010A1 (zh) 2011-11-24

Family

ID=44981785

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/074117 WO2011144010A1 (zh) 2010-05-18 2011-05-16 一种石墨烯基导电材料及其制备方法

Country Status (4)

Country Link
US (1) US20130059143A1 (zh)
JP (1) JP5540151B2 (zh)
CN (1) CN102254582B (zh)
WO (1) WO2011144010A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543269A (zh) * 2012-01-20 2012-07-04 中国科学院上海硅酸盐研究所 高质量石墨烯透明导电膜及其制备方法
CN103680765A (zh) * 2013-12-24 2014-03-26 苏州纳微生物科技有限公司 一种环保型的导电复合微球制备方法
JP2014136657A (ja) * 2013-01-15 2014-07-28 Tokyo Electron Ltd グラフェンのパターニング方法、及びパターンニング用部材
CN104201350A (zh) * 2014-08-22 2014-12-10 南京中储新能源有限公司 基于石墨烯气凝胶/硫复合材料的二次电池
CN109233142A (zh) * 2018-07-27 2019-01-18 旌德县源远新材料有限公司 一种导电玻璃纤维布及其加工方法
JP2020140970A (ja) * 2012-02-17 2020-09-03 株式会社半導体エネルギー研究所 リチウム二次電池

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6016597B2 (ja) * 2011-12-16 2016-10-26 株式会社半導体エネルギー研究所 リチウムイオン二次電池用正極の製造方法
CN112661139A (zh) * 2011-12-21 2021-04-16 加州大学评议会 互连波纹状碳基网络
US9360905B2 (en) * 2012-04-09 2016-06-07 Nanotek Instruments, Inc. Thermal management system containing an integrated graphene film for electronic devices
JP6077347B2 (ja) * 2012-04-10 2017-02-08 株式会社半導体エネルギー研究所 非水系二次電池用正極の製造方法
US9899120B2 (en) 2012-11-02 2018-02-20 Nanotek Instruments, Inc. Graphene oxide-coated graphitic foil and processes for producing same
US10566482B2 (en) 2013-01-31 2020-02-18 Global Graphene Group, Inc. Inorganic coating-protected unitary graphene material for concentrated photovoltaic applications
US10087073B2 (en) 2013-02-14 2018-10-02 Nanotek Instruments, Inc. Nano graphene platelet-reinforced composite heat sinks and process for producing same
CN103390507B (zh) * 2013-07-04 2016-04-13 宁国市龙晟柔性储能材料科技有限公司 一种石墨烯/铂纳米粒子复合纤维电极材料及其制备方法
CN103386483B (zh) * 2013-07-05 2016-03-30 谭彬 一种纳米石墨烯复合材料及其制备方法
WO2015040630A1 (en) * 2013-09-17 2015-03-26 Tata Steel Limited A process for synthesizng reduced graphene oxide on a substrate from seedlac
CN103545053B (zh) * 2013-10-25 2016-03-09 深圳市华星光电技术有限公司 透明导电薄膜的制备方法及具有该导电薄膜的cf基板的制备方法
WO2015089130A1 (en) * 2013-12-10 2015-06-18 University Of South Carolina Ultrathin, graphene-based membranes for water treatment and methods of their formation and use
CN104538453B (zh) 2014-12-29 2018-10-19 京东方科技集团股份有限公司 薄膜晶体管、阵列基板及其制造方法和显示器件
CN105217606A (zh) * 2015-08-19 2016-01-06 厦门大学 一种低温还原氧化石墨烯的方法
JP2018538231A (ja) * 2015-09-29 2018-12-27 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 多層構造を作製する方法
US20180273388A1 (en) * 2015-09-29 2018-09-27 Rohm And Haas Electronic Materials Llc A method of making a graphitic carbon sheet
CN105513676B (zh) * 2015-12-24 2016-12-21 佛山市智巢电子科技有限公司 一种喷墨打印制备石墨烯导电薄膜的方法
IL260398B (en) 2016-01-22 2022-08-01 Univ California high voltage devices
CN109074966A (zh) 2016-03-23 2018-12-21 加利福尼亚大学董事会 用于高电压和太阳能应用的装置和方法
CN106095182A (zh) * 2016-06-14 2016-11-09 天津宝兴威科技有限公司 用石墨烯金属复合材料制作触摸屏的方法
CN106698402A (zh) * 2017-01-05 2017-05-24 东南大学 金属纳米粒子掺杂的柔性自支撑石墨烯薄膜的制备方法
CN106835082A (zh) * 2017-01-11 2017-06-13 东南大学 金属纳米粒子掺杂的柔性自支撑石墨烯薄膜的制备方法
US9793214B1 (en) 2017-02-21 2017-10-17 Texas Instruments Incorporated Heterostructure interconnects for high frequency applications
US10181521B2 (en) 2017-02-21 2019-01-15 Texas Instruments Incorporated Graphene heterolayers for electronic applications
GB201707428D0 (en) * 2017-05-09 2017-06-21 Applied Graphene Mat Plc ] Composite moulding materials
CN109295694B (zh) * 2018-09-29 2022-02-11 上海工程技术大学 一种提升棉纤维导电性能的方法
CN115571873A (zh) * 2019-05-30 2023-01-06 常州第六元素材料科技股份有限公司 卤化氢还原氧化石墨烯膜的除杂方法
CN111410872B (zh) * 2020-04-15 2022-05-31 广东康烯科技有限公司 一种铂量子点掺杂石墨烯基导电油墨的制备方法及导电油墨和应用
CN111447698B (zh) * 2020-04-15 2022-03-29 广东康烯科技有限公司 一种柔性石墨烯发热膜及其制备方法
CN111447694B (zh) * 2020-04-15 2022-03-29 广东康烯科技有限公司 一种钯量子点掺杂石墨烯基电加热板及电加热装置
CN111423769B (zh) * 2020-04-15 2022-05-31 广东康烯科技有限公司 一种钯量子点掺杂石墨烯基导电油墨的制备方法及导电油墨和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492835A (zh) * 2008-01-24 2009-07-29 中国科学院半导体研究所 由绝缘衬底上超薄六方相碳化硅膜外延石墨烯的方法
US20090235721A1 (en) * 2008-03-20 2009-09-24 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Reduced graphene oxide film
CN101976608A (zh) * 2010-09-27 2011-02-16 彩虹集团公司 染料敏化太阳能电池对电极的制备方法
CN102040217A (zh) * 2009-10-26 2011-05-04 国家纳米科学中心 一种石墨烯的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003176117A (ja) * 2001-12-07 2003-06-24 Mitsubishi Gas Chem Co Inc 炭素からなる骨格を持つ薄膜状粒子の積層集合体
JP2003231097A (ja) * 2002-02-08 2003-08-19 Mitsubishi Gas Chem Co Inc 炭素からなる骨格を持つ薄膜状粒子を基板に載せた構造物およびその作製方法
JP4591666B2 (ja) * 2003-07-23 2010-12-01 三菱瓦斯化学株式会社 炭素からなる骨格を持つ薄膜状粒子を含む分散液、導電性塗膜および導電性複合材料ならびにこれらの製造方法
US8696938B2 (en) * 2008-08-25 2014-04-15 Nanotek Instruments, Inc. Supercritical fluid process for producing nano graphene platelets
US20100092809A1 (en) * 2008-10-10 2010-04-15 Board Of Trustees Of Michigan State University Electrically conductive, optically transparent films of exfoliated graphite nanoparticles and methods of making the same
CN101474898A (zh) * 2009-01-16 2009-07-08 南开大学 基于石墨烯的导电碳膜及制备方法和应用
US9117568B2 (en) * 2009-04-03 2015-08-25 Vorbeck Materials Corp. Polymer compositions containing carbonaceous fillers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101492835A (zh) * 2008-01-24 2009-07-29 中国科学院半导体研究所 由绝缘衬底上超薄六方相碳化硅膜外延石墨烯的方法
US20090235721A1 (en) * 2008-03-20 2009-09-24 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Reduced graphene oxide film
CN102040217A (zh) * 2009-10-26 2011-05-04 国家纳米科学中心 一种石墨烯的制备方法
CN101976608A (zh) * 2010-09-27 2011-02-16 彩虹集团公司 染料敏化太阳能电池对电极的制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543269A (zh) * 2012-01-20 2012-07-04 中国科学院上海硅酸盐研究所 高质量石墨烯透明导电膜及其制备方法
JP2020140970A (ja) * 2012-02-17 2020-09-03 株式会社半導体エネルギー研究所 リチウム二次電池
JP2014136657A (ja) * 2013-01-15 2014-07-28 Tokyo Electron Ltd グラフェンのパターニング方法、及びパターンニング用部材
CN103680765A (zh) * 2013-12-24 2014-03-26 苏州纳微生物科技有限公司 一种环保型的导电复合微球制备方法
CN103680765B (zh) * 2013-12-24 2016-08-17 苏州纳微科技有限公司 一种环保型的导电复合微球制备方法
CN104201350A (zh) * 2014-08-22 2014-12-10 南京中储新能源有限公司 基于石墨烯气凝胶/硫复合材料的二次电池
CN109233142A (zh) * 2018-07-27 2019-01-18 旌德县源远新材料有限公司 一种导电玻璃纤维布及其加工方法

Also Published As

Publication number Publication date
CN102254582A (zh) 2011-11-23
CN102254582B (zh) 2013-05-15
JP2013533189A (ja) 2013-08-22
JP5540151B2 (ja) 2014-07-02
US20130059143A1 (en) 2013-03-07

Similar Documents

Publication Publication Date Title
WO2011144010A1 (zh) 一种石墨烯基导电材料及其制备方法
Liu et al. Fabrication of platinum-decorated single-walled carbon nanotube based hydrogen sensors by aerosol jet printing
Mou et al. Facile preparation of stable reactive silver ink for highly conductive and flexible electrodes
Xu et al. Graphene as transparent electrodes: fabrication and new emerging applications
CN103043654B (zh) 一种含有石墨烯和/或氧化石墨烯的薄膜及其制备方法
US8623938B2 (en) Inkjet ink and method for making the same
Ma et al. Preparation and characterization of monodispersed PS/Ag composite microspheres through modified electroless plating
Deetuam et al. Synthesis of well dispersed graphene in conjugated poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate via click chemistry
JP2007517760A (ja) カーボンナノチューブペーストおよび使用方法
CN104292984A (zh) 石墨烯油墨及石墨烯线路的制作方法
CN102017012A (zh) 用于透明导电用途的碳纳米管-透明导电无机纳米颗粒混杂薄膜
KR20080112799A (ko) 금속 나노입자를 포함하는 탄소 나노튜브(ｃｎｔ) 박막 및그 제조방법
MX2012010130A (es) Metodo para hacer un articulo revestido, recubrimiento que incluye una paelicula delgada de nanotubos de carbono aleada.
TW200818562A (en) Method for manufacturing a parts of electric circuit
US20200284749A1 (en) Technologies Using Pseudo-Graphite Composites
CN107221387A (zh) 基于短暂性构架的高电导率石墨烯薄膜的制备方法
WO2020239143A1 (zh) 一种石墨烯导电油墨及其制备方法
CN107163686B (zh) 一种石墨烯复合导电油墨的制备方法及其应用
JP2014529353A (ja) 金属ナノワイヤを官能基化する方法及び電極を作製する方法
CN107761081A (zh) 一种高致密度的石墨烯/银复合材料及其制备方法
KR101371289B1 (ko) 탄소 나노박막의 제조방법
JP2013152928A (ja) 透明導電膜
Anusak et al. Enhanced Joule heating performance of flexible transparent conductive double-walled carbon nanotube films on sparked Ag nanoparticles
KR101319559B1 (ko) 그라핀을 함유하는 코팅막의 제조방법
TWI578335B (zh) 高分散、黏度可控的碳奈米管透明電極墨水

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11782927

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13698517

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2013510491

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11782927

Country of ref document: EP

Kind code of ref document: A1