WO2014021257A1 - Procédé de production de film composite comprenant des nanotubes de graphène et de carbone - Google Patents

Procédé de production de film composite comprenant des nanotubes de graphène et de carbone Download PDF

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WO2014021257A1
WO2014021257A1 PCT/JP2013/070462 JP2013070462W WO2014021257A1 WO 2014021257 A1 WO2014021257 A1 WO 2014021257A1 JP 2013070462 W JP2013070462 W JP 2013070462W WO 2014021257 A1 WO2014021257 A1 WO 2014021257A1
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composite film
producing
carbon nanotubes
graphene
nanotubes
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Japanese (ja)
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テロネス マウリシオ
トリスタン フェルディナンド
鶴岡　秀志
マグダレナ ヴェガ ディアス ソフィア
クルス シルバ ロドルフォ
遠藤　守信
モレロス アーロン
ペレア ネスター
エリアス アナ
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国立大学法人信州大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • 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
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing a composite film made of a composite carbon material in which graphene and carbon nanotubes are alternately laminated.
  • a carbon nanotube is a hollow nano-sized carbon fiber having a high aspect ratio obtained by rounding a graphene sheet into a cylindrical shape. Carbon atoms that make up the carbon skeleton of CNTs are substituted with other atoms called other-atom-doped CNTs, such as nitrogen-doped CNTs and boron-doped CNTs. Type CNT).
  • Hybrid carbon materials combining CNTs hereinafter including other-atom doped CNTs and encapsulated CNTs
  • graphene (G), graphene oxide (GO) or reduced graphene (RGO) are materials composed of a carbon skeleton and have a specific surface area. It is expected to have excellent physical properties that are not present in conventional materials, such as high mechanical stability, high mechanical stability, and high electrical and thermal conductivity. For example, application to supercapacitors, carbon electrodes, solar cell components, energy storage, sensors, etc. is expected.
  • CNT, G, GO, and RGO are all carbon crystals, and CNTs are randomly coordinated on the G, GO, and RGO surfaces. It is not impossible to mechanically or electrically align the direction of CNTs on the G, GO, and RGO planes, but it is not easy to make a laminated composite material.
  • Non-Patent Documents 1 and 2 Methods for overcoming these technical problems include filtration methods (Non-Patent Documents 1 and 2), casting of dispersion liquid (Non-Patent Documents 3), electrophoretic growth methods (Non-Patent Documents 4 and 5), layer-by-layer lamination Methods (Non-Patent Documents 6 and 7) and Langmuir-Blodgett film method (Non-Patent Document 8) have been proposed.
  • these methods are not suitable for mass production practical use because they require a lot of man-hours and take a lot of time or require operation under a microscope.
  • Patent Document 1 As a technique for simply combining CNT with G, GO, and RGO, a system in which CNT is cut when CNT is applied to an electrode and G and CNT coexist as a mixture has been proposed (Patent Document 1). ). This is to fix the cylindrical structure of CNT to the current plate (through electrode) using graphene. It cannot be said to be a laminated structure material of CNT and graphene. In addition, although it has been proposed as an electrode material to squeeze CNTs to make graphene and dope lithium (Patent Document 2), it appeals for CNT / G, CNT / GO, and CNT / RGO laminated structures. I don't mean.
  • Patent Document 3 A laminate structure in which vapor-grown carbon fibers are laminated and CNTs are arranged in gaps has been reported (Patent Document 3).
  • This structure is a composite having a structure in which a vapor-grown carbon fiber having a diameter of 100 nm or more is a basic skeleton, and the gap is filled with CNTs having a diameter of less than 100 nm. It should be noted that the description describes the rounded graphene but does not form a CNT / G stacked structure.
  • An electronic material having a structure in which graphite is deposited on the surface centering on CNT has been proposed (Patent Document 4).
  • This material should be understood that the carbon remaining in the CNT manufacturing process has a graphite structure, and is greatly different from the CNT / G laminated structure of the present invention.
  • a method for producing a CNT / G, CNT / GO, and CNT / RGO laminated composite carbon material in which CNT and graphene are laminated has not been established so far, and has not yet reached a practical stage.
  • a composite film having a structure in which carbon nanotubes (CNT) are sandwiched between layers made of graphene, and layers made of graphene and layers made of carbon nanotubes are alternately stacked is applied to a long-time reaction treatment with a large number of steps. It is an object of the present invention to provide a method that enables easy production without performing work under a microscope.
  • the method for producing a composite film according to the present invention is a method for producing a composite film having a structure in which nanosheet structures and nanocarbon structures are alternately laminated, a.
  • d. It is effective to include a step of reducing the composite film.
  • the reduction treatment method thermal or chemical reduction treatment can be used.
  • thermal reduction treatment a treatment of heating to a high temperature sufficient to reduce the nanosheet structure such as graphene oxide in the atmosphere can be used.
  • chemical reduction treatment treatment using hydrazine monohydrate, hydroquinone, gaseous hydrogen, alkaline solution (NaOH, KOH, etc.), vitamin C, sodium borohydride can be used.
  • the composite film means a film made of a composite carbon material in which nanosheet structures and nanocarbon structures are alternately laminated.
  • the composite film is subjected to the reduction treatment in step d and the reduction treatment in step d. Includes both not.
  • a composite film subjected to a reduction treatment is used in order to obtain the conductivity or toughness of the film, but a composite film that has not been subjected to the reduction treatment can be used depending on the application.
  • any one of graphene, graphene oxide, reduced graphene, graphite oxide, or reduced graphite can be used.
  • Graphene oxide (GO) has a structure in which part of carbon in graphene is substituted with oxygen or a structure in which oxygen is bonded to carbon, and can be synthesized by oxidizing graphite.
  • Reduced graphene (RGO) is obtained by reducing graphene oxide. In the reduced graphene obtained by reducing graphene oxide, a portion where graphene is oxidized remains slightly, and in this sense, it is not completely the same as graphene.
  • Graphite oxide is obtained by oxidizing graphite, and reduced graphite is obtained by reducing graphite oxide.
  • Graphite oxide can be obtained by a method of chemically oxidizing graphite. Note that graphite is formed by stacking a plurality of graphenes.
  • graphene used as a nanosheet structure does not have a structure in which carbon and oxygen are combined, its action is different from graphene oxide or the like. However, it can be dispersed in a solvent by a method such as using a surfactant, and a composite film can be formed using the same steps as other nanosheet structures.
  • a composite film is manufactured using graphene, the structure is similar to that of graphene oxide in which carbon is replaced with oxygen or bonded to oxygen by passing the treatment process. Therefore, the reduction treatment step d has an effective effect of improving the electrical conductivity of the composite film even when graphene is used as the nanosheet structure.
  • a peelable layered material made of a divalent or trivalent chalcogenide of a transition metal can be used instead of graphene, graphene oxide, reduced graphene, or the like.
  • transition metal chalcogenides include MoS 2 , WS 2 , NbS 3 , and MnPS 3 .
  • a layered material such as boron nitride can also be used.
  • carbon nanotubes As the nanocarbon structure, carbon nanotubes, other atom-doped carbon nanotubes, encapsulated carbon nanotubes, fullerenes, and graphene nanoribbons can be used.
  • carbon nanotubes single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), triple-walled carbon nanotubes (TWCNT), and multi-walled carbon nanotubes (MWCNT) can be used.
  • SWCNT single-walled carbon nanotubes
  • DWCNT double-walled carbon nanotubes
  • TWCNT triple-walled carbon nanotubes
  • MWCNT multi-walled carbon nanotubes
  • the atoms to be doped as other atom-doped carbon nanotubes are not particularly limited, but single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), triple-walled carbon nanotubes (TWCNT), multi-walled carbon nanotubes (MWCNT) ), Carbon nanotubes doped with nitrogen or boron can be suitably used. Carbon nanotubes can be synthesized using, for example, a CVD method (Non-patent Documents 17 and 18).
  • inorganic nanotubes such as boron nitride nanotubes, tungsten disulfide nanotubes, molybdenum disulfide nanotubes, titanium oxide nanotubes, chalcogenide nanotubes, and boron-carbon-nitrogen (BCN) nanotubes can be used.
  • BCN boron-carbon-nitrogen
  • step a As a method for functionalizing the nanocarbon structure cationically (step a), the methods already disclosed (Non-Patent Documents 12, 13, 14, and 15) can be used.
  • a method for functionalizing the nanocarbon structure cationically there is a method using a surfactant, a polymer, or a polyelectrolyte.
  • a nanocarbon structure such as a carbon nanotube
  • the nanocarbon structure can be suitably dispersed in a polar solvent such as water, alcohol, acetone, or aldehydes.
  • step b of the method of the present invention the dispersion liquid of the functionalized nanocarbon structure and the dispersion liquid of the nanosheet structure are mixed to obtain a mixed suspension containing the nanocarbon structure and the nanosheet structure.
  • the mixed suspension is meant to include both nanocarbon structures and nanosheet structures.
  • a polar solvent as the dispersion, the functionalized nanocarbon structure becomes cationic and is suitably dispersed in the polar solvent, and the nanosheet structure is anionic and suitably dispersed in the polar solvent.
  • the polar solvent a solvent can be appropriately used, and it is of course possible to use water. When water is used, the treatment operation can be easily performed, which is preferable.
  • nanocarbon structure dispersion little by little into the nanosheet structure dispersion. What is necessary is just to mix a nanocarbon structure.
  • a method of dropping the nanosheet structure dispersion into the nanocarbon structure dispersion may be used.
  • the nanocarbon structure and the nanosheet structure can be effectively dispersed and mixed by mixing the dispersion while applying ultrasonic vibration. Ultrasonic vibration, a stirrer, and a vortex generator can be used in combination.
  • the dispersion of nanocarbon structure and nanosheet structure is mixed, the structure in which the nanocarbon structure and nanosheet structure are alternately stacked gradually by the cation-anion action of the nanocarbon structure and nanosheet structure. Will be built.
  • Step c is a step of removing the dispersion medium from the mixed suspension to form a film.
  • a method for forming a film using the mixed suspension a method of casting the mixed suspension on the surface of the substrate and allowing it to stand to remove a dispersion medium such as moisture from the mixed suspension can be used.
  • the mixed suspension is cast on the surface of the base material, it is made of a composite carbon material in which nanocarbon structures and nanosheet structures are alternately stacked on the surface of the base material by heating gently to remove the dispersion medium. A film is produced.
  • a composite film is a composite carbon material in which nanocarbon structures and nanosheet structures are alternately laminated in a plurality of layers in a sheet shape, and the composite carbon materials are accumulated in various directions in the film. However, in the vicinity of the surface of the composite film, the composite carbon materials are arranged so that the plane of the nanosheet structure is parallel to the surface of the composite film.
  • the composite film formed on the substrate surface is used after being detached (peeled) from the substrate surface. Therefore, the substrate on which the mixed suspension is cast is preferably a water-repellent substrate.
  • the method of forming a film using the mixed suspension is not limited to the casting method, and a method used in the paper manufacturing process can be used.
  • the method of casting the mixed suspension on the surface of the substrate to form a composite film can arbitrarily set the width, length, thickness, etc. of the composite film.
  • FIG. 1 shows a process of forming a composite carbon material of carbon nanotubes and graphene when carbon nanotubes are used as nanocarbon structures and graphene oxide is used as nanosheet structures.
  • Steps A and B are processes in which the graphene oxide 10 and the carbon nanotubes 12 are each stably dispersed in the dispersion.
  • Graphene oxide can be dispersed in a dispersion as an anionic polyelectrolyte by addition of carboxylic acid or itself, and carbon nanotubes can be dispersed in a dispersion as a cationic polyelectrolyte by the functionalization treatment described above. .
  • the graphene oxide dispersion and the carbon nanotube dispersion are mixed to prepare a suspension (mixed suspension) in which the graphene oxide 10 and the carbon nanotubes 12 are mixed with each other (step C). ).
  • the mixed suspension the graphene oxide and the carbon nanotubes interact with each other by a cation-anion action, and the graphene oxide and the carbon nanotubes are gradually arranged alternately.
  • the mixed suspension of graphene oxide and carbon nanotubes is cast into a mold (substrate surface), heated gently to remove the dispersion medium (dispersion), and the graphene oxide and carbon nanotubes are re-coordinated.
  • Step D shows one composite carbon material in which graphene oxide 10 and carbon nanotubes 12 have a laminated structure.
  • Step E is a state in which the film is subjected to a reduction treatment to finally obtain a composite film (hybrid film).
  • the composite film of graphene oxide and carbon nanotube is a film having a structure in which graphene oxide (GO) is reduced to reduced graphene (RGO) by reduction treatment, and reduced graphene and carbon nanotubes are alternately laminated.
  • a composite film of graphene (G) and carbon nanotubes is obtained.
  • a hybrid film (composite carbon material) composed of graphene and carbon nanotubes can have a laminated structure that is a combination of CNT / GO, CNT / RGO, and CNT / G.
  • carbon nanotubes and graphene oxide are stacked by the action of Self-Assemble by utilizing the cation-anion reaction between carbon nanotubes (CNT) and graphene oxide (GO).
  • CNT carbon nanotubes
  • GO graphene oxide
  • a hybrid laminated structure can be configured easily.
  • This method can be applied not only to carbon nanotubes, but also to other atom-doped carbon nanotubes, encapsulated carbon nanotubes, fullerenes, graphene nanoribbons, etc. that can be modified (functionalized) using a polyelectrolyte. it can.
  • CNT / GO hybrid film produced using graphene oxide can adjust its physical properties by adjusting the degree of reduction of GO. Since the hybrid film is basically a carbon composite, it has high heat stability. A fully reduced CNT / G hybrid film is chemically stable. Further, since the composite carbon material is formed by the self-stacking reaction, it is not necessary to form a support structure between the graphene layers, and the number of steps can be significantly reduced as a method of manufacturing the composite carbon material (hybrid film).
  • the composite film obtained by the method of the present invention is composed of a regular composite, and the fibrous CNT (nanocarbon structure) and the planar G, GO, RGO (nanosheet structure) are in contact at multiple points. Therefore, it exhibits a low electric resistance of 10 ⁇ 3 ⁇ ⁇ cm or less.
  • the band gap can be controlled, so that it can be applied as a carbon semiconductor.
  • it since it is made of carbon, it has high heat resistance, chemical resistance, and rust resistance.
  • the range of applications includes supercapacitors, fuel cells and other electrochemical fields, metal-free catalyst fields, scaffolding materials and other tissue engineering fields, metal replacement materials such as electric wires, wire harnesses, mobile vehicle bodies, and aircraft.
  • fibers, heat-resistant fabrics and the like are fibers, heat-resistant fabrics and the like.
  • a composite film having a structure in which nanocarbon structures and nanosheet structures are alternately laminated can be easily and efficiently produced.
  • the composite film which can be utilized for various uses from a physical characteristic can be provided.
  • MWNT multi-walled carbon nanotube
  • GO graphene oxide
  • Multi-walled CNTs use a mixture of 6 wt% ferrocene and 94 wt% toluene, and CVD (chemical) with argon flow (2.5 L / min), 825 ° C, normal pressure This was obtained by performing annealing and purification after synthesis by vapor deposition).
  • Nitrogen-doped CNTs were synthesized by a CVD (chemical vapor deposition) method using a mixture of ferrocene 6wt% and benzylamine 94wt%, argon flow (2.5L / min), 850 °C, normal pressure, and annealed in the same way Obtained by processing.
  • CVD chemical vapor deposition
  • Boron-doped CNTs were first synthesized using a continuous reaction vessel using a continuous reaction system using a cylindrical reaction vessel, using ferrocene as a catalyst precursor, toluene as a carbon supply source, and hydrogen as a carrier gas.
  • a toluene solution containing 2-3 wt% of the ferrocene compound was fed into the reaction vessel with a supply pump (25 g / min) and reacted at about 1200 ° C.
  • the obtained carbon nanotubes were mixed with boric acid (5 wt%), and the mixture was heat-treated at 2400 ° C. in an argon atmosphere to obtain boron-doped CNTs.
  • the carbon nanotube can be functionalized as a cationic polyelectrolyte by a method already disclosed (Non-Patent Documents 12, 13, 14, and 15).
  • a polar solvent such as water, alcohol, acetone, and aldehydes, and are uniformly dispersed in the solvent.
  • the carbon nanotubes were functionalized as follows. First, 10 mg of carbon nanotubes were heat-treated at 800 ° C. in the presence of oxygen (air flow rate: 0.5 L / min) to remove amorphous carbon on the surface of carbon nanotubes and impurities (solvent, hydrocarbon, etc.) remaining on the surface. By this heat treatment, it becomes possible to slightly oxidize the surface of the carbon nanotube and form an anchor site functionalized by the polyelectrolyte.
  • oxygen air flow rate: 0.5 L / min
  • the carbon nanotubes subjected to the heat treatment were uniformly dispersed in water by applying ultrasonic waves to form a suspension, and this suspension was applied to the 2 mg / L cationic polyelectrolyte solution while applying ultrasonic waves. It was dripped.
  • Carbon nanotubes (MWCNT), nitrogen-doped carbon nanotubes, and boron-doped carbon nanotubes can be functionalized cationically with amines or amines, imines or imines, and this operation enables functionalized carbon nanotubes. Is uniformly dispersed in the electrolyte solution.
  • a functionalized carbon nanotube was obtained by removing excess polyelectrolyte using a washing method using a centrifugal separation method.
  • this suspension (mixed suspension) containing graphene oxide and carbon nanotubes is cast on the surface of a PTFE (polytetrafluoroethylene) substrate and heated at 60 ° C. to dissipate moisture.
  • a film was formed on the material surface.
  • the obtained film is a composite film made of a composite carbon material in which graphene oxide, multilayer CNT, nitrogen-doped multilayer CNT, and boron-doped multilayer CNT are alternately laminated.
  • the reduction treatment of the composite film was performed by heating the film detached from the substrate surface to 800 ° C. under Ar flow.
  • a suspension containing only graphene oxide is stirred for 30 minutes using an ultrasonic stirrer, cast on the substrate surface, a film is formed by the same method as described above, and comparative measurement is performed. went.
  • Table 1 shows carbon, oxygen, and nitrogen before and after reduction treatment by heating at 800 ° C. for 10 minutes in air for a composite film made of multi-walled carbon nanotubes, nitrogen-doped carbon nanotubes, boron-doped carbon nanotubes and graphene oxide.
  • the result of having measured the content of is shown.
  • the content of carbon, oxygen and the like can be measured by obtaining a core level spectrum of each element using XPS.
  • the measurement results show that oxygen is greatly reduced by reduction treatment for any composite film. However, oxygen is not completely lost by the reduction treatment.
  • the amount of nitrogen in the sample using nitrogen-doped carbon nanotubes does not change much before and after the reduction treatment.
  • FIG. 2 shows a composite film produced by the above-described method using multi-walled carbon nanotubes and graphene oxide.
  • the composite film shown here is the one before the reduction treatment.
  • 2 (a)) shows a state where the composite film is bent
  • FIGS. 2 (b) and 2 (c) show a state where the composite film is twisted
  • FIG. 2 (d) shows a state where the composite film is twisted and further bent.
  • the composite film is a highly flexible film.
  • FIG. 3 (a) shows the state before and after the reduction treatment of the MWCNT / GO
  • FIG. 3 (b) shows the N-MWCNT / GO
  • FIG. 3 (c) shows the B-MWCNT / GO composite film.
  • the composite film before the reduction treatment has a darker color than the composite film after the reduction treatment. This is mainly due to the carbon nanotubes present between the graphene oxide sheets.
  • the composite film exhibits a silver metallic color as shown in FIG.
  • FIGSEM observation) 4, 5, and 6 show SEM images of a hybrid film (composite carbon material) of multilayer CNT, nitrogen-doped multilayer CNT, boron-doped multilayer CNT, and graphene oxide.
  • (a), (b), and (c) are before the reduction treatment and have different magnifications
  • (d) is the one subjected to the reduction treatment at 800 ° C. in an argon atmosphere.
  • the carbon nanotubes are randomly and uniformly distributed in the film plane and are sandwiched between the graphene oxide layers.
  • FIG. 7 shows the results of Raman spectroscopic analysis before and after the reduction treatment of the composite film of MWCNT / GO, N-MWCNT / GO, and B-MWCNT / GO and the GO film.
  • 7A and 7B show the measurement results before the reduction treatment
  • FIGS. 7C and 7D show the measurement results after the reduction treatment.
  • Table 2 shows the peak value of the Raman band.
  • FIG. 8 shows the thermogravimetric analysis results.
  • the first change around 200 ° C indicates an exothermic reaction when GO is reduced.
  • the change around 500 °C indicates the oxidation of carbon with graphite structure.
  • the difference in the oxidation reaction temperature of each sample is due to the influence of other atom doping on CNT. That is, other atoms dope a defect in the carbon crystal lattice and shift the oxidation start temperature to the low temperature side. From these results, it can be seen that the graphene-CNT hybrid film (laminated composite carbon material) produced by the method of the present invention has different physical properties from graphene or graphene oxide.
  • Table 3 shows the resistance values of CNT / GO and GO. Although the resistance of single-walled CNT has been reported to be 10 ⁇ 4 ⁇ cm, the effective value is 10 0 ⁇ cm. The resistance value of graphene oxide was 4.26 ⁇ 10 ⁇ 3 ⁇ cm. As shown in Table 3, the resistance value of the composite film of carbon nanotubes (MWCNT) and graphene oxide (after reduction treatment) according to the present invention is much smaller than the resistance value of graphene oxide. This means that the electrical conductivity has been improved by the addition of carbon nanotubes.

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Abstract

Le problème décrit par la présente invention est de pourvoir à un procédé de production d'un film composite permettant de produire aisément et de manière efficace un film composite ayant une structure obtenue par stratification alternée de nanotubes de graphène et de carbone. La solution selon l'invention porte sur un procédé de production d'un film composite pourvu d'une structure obtenue par stratification alternée d'une structure de nanofeuille (10) et d'une nanostructure de carbone (12), lequel procédé est caractérisé en ce qu'il comprend les étapes suivantes : a. une étape dans laquelle la nanostructure de carbone (12) est fonctionnalisée par un cation; b. une étape dans laquelle un liquide de dispersion de la nanostructure de carbone (12) fonctionnalisée et un liquide de dispersion de la structure de nanofeuille (10) sont mélangés de sorte à produire une suspension contenant la nanostructure de carbone et la structure de nanofeuille; et c. une étape dans laquelle le milieu de dispersion est retiré de la suspension de sorte à produire un film.
PCT/JP2013/070462 2012-07-30 2013-07-29 Procédé de production de film composite comprenant des nanotubes de graphène et de carbone WO2014021257A1 (fr)

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