WO2013162097A1 - Nanomatériau carboné et son procédé de préparation - Google Patents

Nanomatériau carboné et son procédé de préparation Download PDF

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WO2013162097A1
WO2013162097A1 PCT/KR2012/003204 KR2012003204W WO2013162097A1 WO 2013162097 A1 WO2013162097 A1 WO 2013162097A1 KR 2012003204 W KR2012003204 W KR 2012003204W WO 2013162097 A1 WO2013162097 A1 WO 2013162097A1
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Prior art keywords
carbon
nitrogen
catalyst
carbon nano
gas
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PCT/KR2012/003204
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English (en)
Korean (ko)
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정두환
김상경
임성엽
백동현
이병록
김지영
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한국에너지기술연구원
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Priority to PCT/KR2012/003204 priority Critical patent/WO2013162097A1/fr
Publication of WO2013162097A1 publication Critical patent/WO2013162097A1/fr

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    • 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
    • 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
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • 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
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a carbon nanomaterial and a method for manufacturing the same, and more particularly, to a carbon nanomaterial and a method for producing the same, which are excellent in durability and capable of supporting a catalyst more efficiently.
  • the fuel cell is a power generation system that directly converts the chemical reaction energy of hydrogen and oxygen contained in a hydrocarbon-based material such as methanol, ethane, and natural gas into electrical energy.
  • Such a fuel cell is a clean energy source that can replace fossil energy, and has a merit that can produce a wide range of outputs by stacking a unit cell stack. It is attracting attention as a compact and mobile portable power source because it shows 10 times the energy density.
  • a typical example of a fuel cell is a polymer electrolyte fuel cell (PEMFC: Polymer).
  • Electrolyte Membrane Fuel Cell Electrolyte Membrane Fuel Cell
  • Direct Oxidation Fuel Cell When methanol is used as a fuel in the direct oxidation fuel cell, it is called a direct methanol fuel cell (DMFC).
  • DMFC direct methanol fuel cell
  • the present invention also aims to provide a method for producing the carbon nanomaterial.
  • a carbon nanomaterial including carbon nanofibers including nitrogen is provided.
  • the carbon nanomaterial according to the present invention has excellent durability and can support a catalyst more efficiently, and thus has excellent performance as a catalyst carrier.
  • the carbon nanomaterial of the present invention has an advantage of having excellent durability due to excellent crystallinity, carrying a catalyst more effectively, and improving dispersibility by introducing nitrogen into carbon nanofibers.
  • the carbon nanomaterial of the present invention is expected not only to be used as a support for a catalyst including an electrode catalyst of a fuel cell but also to be used for introduction and development in various fields.
  • FIG. 1 is a view schematically showing the structure of a half-unggi used in the present invention.
  • FIG. 2 is a view showing the temperature and feed gas composition profile of the reaction process performed in the embodiment of the present invention.
  • FIG. 3 is a graph showing N / C (atomic%) according to the synthesis yield and elemental analysis of the nitrogen-doped carbon nano-rubber prepared according to Examples 1 to 11.
  • FIG. 3 is a graph showing N / C (atomic%) according to the synthesis yield and elemental analysis of the nitrogen-doped carbon nano-rubber prepared according to Examples 1 to 11.
  • FIG. 4 is a cross-sectional view of nitrogen-doped carbon nanofibers prepared according to Examples 1 to 11.
  • FIG. 6 is an SEM photograph of carbon nanofibers prepared according to Examples 4 and 12.
  • FIG. 7 is a TG measurement graph of carbon nanofibers prepared according to Examples 2, 5, 7, 10, and 11.
  • FIG. 7 is a TG measurement graph of carbon nanofibers prepared according to Examples 2, 5, 7, 10, and 11.
  • FIG. 8 is a graph of measuring the specific surface area of carbon nanofibers prepared according to Examples 1-11.
  • FIG. 10 is an XPS (X-ray Photoelectron) for nitrogen of the carbon nanofibers of Example 7.
  • FIG. 10 is an XPS (X-ray Photoelectron) for nitrogen of the carbon nanofibers of Example 7.
  • FIG. 11 is a graph showing the total nitrogen content of the Hanso nanofibers prepared according to Examples 1 to 11 and the nitrogen content present on the surface of the carbon nanofibers.
  • FIG. 12 shows N / C atomic ratios and (B) component (graphite-like structure) / (A) component (pyridine-like structure) on the surface of carbon nanofibers prepared according to Examples 1 to 11. Graph showing the ratio.
  • FIG. 13 is an X-ray diffraction (XRD) measurement graph of carbon nanofibers prepared according to Examples 1 to 11.
  • FIG. 14 is a graph showing the distance between d002 plane and Lc (002) crystal size of carbon nanofibers prepared according to Examples 1 to 11.
  • FIG. 14 is a graph showing the distance between d002 plane and Lc (002) crystal size of carbon nanofibers prepared according to Examples 1 to 11.
  • FIG. 15 is a graph showing the results of cyclic voltametry experiments measured using working electrodes using the carbon materials of Examples 4, 7 and 10, and Comparative Examples 2 to 4.
  • FIG. 16 is a graph showing the results of oxygen reduction reaction experiments using the working electrode using the carbon material of Examples 4, 7 and 10, and Comparative Examples 2 to 4.
  • FIG. 17 is a graph showing the results of cyclic voltametry experiments measured using an operating electrode using a catalyst prepared according to Examples 16 to 18 and Comparative Examples 5 to 6.
  • FIG. 18 is a graph showing the results of an oxygen reduction reaction test measured using a working electrode using a catalyst prepared according to Examples 16 to 18 and Comparative Examples 5 to 6.
  • FIG. 18 is a graph showing the results of an oxygen reduction reaction test measured using a working electrode using a catalyst prepared according to Examples 16 to 18 and Comparative Examples 5 to 6.
  • the present invention relates to carbon nanomaterials.
  • This carbon material contains nitrogen Carbon nanofibers.
  • nitrogen may be present in a doped form and distributed throughout the crystal structure of the carbon nanofiber. As such, the presence of nitrogen in the doped form can prevent the outflow of nitrogen in the blackening condition, and the nitrogen forms a structure with carbon nanofibers, thereby improving durability.
  • Nitrogen included in the carbon nanofibers may exist in various chemical states. That is, nitrogen is inserted into the carbon structure constituting the carbon nanofiber, pyridine-like
  • the component ratio (B / A) of the B component and the A component is preferably 0.3 to 2.0. , 1.0 to 2.0 is more preferred.
  • the component ratio (B / A) is included in the above range, it is effective in maintaining the structure of the carbon nanofibers while improving the activity for the oxygen reduction reaction.
  • the content of nitrogen in the carbon nanofibers may be 0.5 to 10 atomic%. When the content of nitrogen is included in the above range, it is possible to impart sufficient functionality by nitrogen doping and at the same time eliminate the structural vulnerability of the carbon nanofibers by nitrogen doping.
  • the ratio (N / C) of nitrogen to carbon is preferably 1.0 to 5.0 atomic%.
  • nitrogen is present in the above range compared to carbon, it is possible to obtain a doping effect of nitrogen in a highly crystalline structure.
  • the carbon nanofibers preferably have a herringbone structure.
  • the herringbone structure refers to a state in which the arrangement of graphenes is arranged at a constant angle in a V-shape with respect to the fiber axis in carbon having an abyssal structure having a crystalline structure. That is, the carbon nanofibers exhibit crystallinity.
  • the edges of the graphite may be exposed to the surface in abundance.
  • Such carbon nanofibers have a (002) plane peak at 20 to 30 ° when 2 ⁇ is measured by X-ray diffraction measurement using CuKa.
  • the surface between the carbon nanofibers The distance d002 is 0.340 to 0.356 mm 3 and the crystal size Lc (002) may be 1 to 7 nm.
  • the average diameter of the carbon nanofibers may be 10 to 100 nm. When the average diameter of the carbon nanofibers falls within the above range, high specific surface area as a carrier can be obtained together with structural durability.
  • the carbon nanofibers preferably have a specific surface area of 50 to 500 m 2 / g, and more preferably 70 to 490 m 2 / g.
  • the carbon nano material may be manufactured by a manufacturing method according to another embodiment of the present invention.
  • the method includes the steps of introducing nitrogen gas in a reaction vessel, in the presence of a metal catalyst supported on a carrier; Heating the temperature while supplying a mixed gas of nitrogen gas and hydrogen gas to the reaction vessel; And supplying a nitrogen containing compound to the reactor.
  • nitrogen gas is introduced in the reaction vessel in the presence of a metal catalyst supported on a carrier.
  • the carrier may be selected from the group consisting of MgO, MgO, Si0 2l A1 2 0 3 , zeolite, aluminosilicate carbon-based materials, and combinations thereof.
  • the carbonaceous material may be natural alum, artificial alum, carbon black, activated carbon, activated carbon fiber, carbon nanotube, carbon nanofiber, or a combination thereof.
  • the metal catalyst may be a metal selected from the group consisting of Ni, Fe, Co, and combinations thereof or alloys thereof.
  • the metal catalyst may further include a metal selected from the group consisting of Mo, Cu, Cr, Pt, Ru, Pd, or a combination thereof.
  • the reactor is heated while supplying a mixed gas of nitrogen gas and hydrogen gas.
  • Hydrogen gas prevents catalyst poisoning in the catalytic chemical vapor deposition (CCVD) process and increases the synthesis yield.
  • CCVD catalytic chemical vapor deposition
  • reaction occurs under a simple mixture of hydrogen gas and a carbonizable compound, pyrolysis occurs excessively. Side reactions may occur due to the high reaction rate, and incorporation of an inert gas such as nitrogen gas may induce an appropriate reaction rate for the growth of carbon nanofibers by catalyst reaction.
  • the mixing ratio of nitrogen gas and hydrogen gas in the mixed gas is appropriately about 160: 40 cc, but is not limited thereto.
  • the temperature raising step is a temperature of 300 to 700 ° C. at a temperature increase rate of 5 to ire / min Until it reaches. If the temperature increase rate is slower than the above range, the synthesis time increases, which leads to a decrease in productivity. Too high a temperature causes difficulty in temperature control.
  • the nitrogen-containing compound may be selected from the group consisting of acetonitrile, acrylonitrile, pi, pyridine and combinations thereof.
  • Carbon nano material according to an embodiment of the present invention can be usefully used for the cathode electrode for fuel cells.
  • the cathode electrode for a fuel cell includes the carbon nanomaterial.
  • the cathode electrode includes a cathode catalyst layer and an electrode substrate, and the carbon nanomaterial may be included in the cathode catalyst charge.
  • the carbon nanomaterial serves as a carrier of a catalyst causing a reduction reaction by reaction of oxidant, hydrogen ion and electron supplied to the cathode electrode.
  • a platinum-based catalyst generally used as a cathode electrode catalyst of a fuel cell may be used.
  • the platinum-based catalyst may be platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy or platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni). , At least one catalyst selected from the group consisting of Cu, Zn, Sn, Mo, W, Rh, and Ru).
  • platinum-based catalyst examples include Pt, Pt / Ru, Pt / W, Pt / Ni, Pt / Sn, Pt / Mo, Pt / Pd, Pt / Fe, Pt / Cr, Pt / Co, Pt / Ru / W , Pt / Ru / Mo, Pt / Ru / V, Pt / Fe / Co, Pt / Ru / Rh / Ni and Pt / Ru / Sn / W can be used.
  • the cathode catalyst layer may further include a binder resin to improve adhesion of the catalyst layer and transfer hydrogen ions.
  • a polymer resin having hydrogen ion conductivity as the binder resin, and more preferably, sulfonic acid group, carboxylic acid group, phosphoric acid group, or phosphate in the side chain.
  • Any polymer resin having a cation exchange group selected from the group consisting of a phonic acid group and derivatives thereof can be used.
  • a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a polyether ketone polymer, a polyether- It may include one or more hydrogen ion conductive polymer selected from ether-based polymer or polyphenylquinoxaline-based polymer, more preferably poly (perfluorosulfonic acid), poly (perfluorocarboxylic acid), sulfonic acid Copolymers of tetrafluoroethylene and fluorovinyl ethers containing groups, sulfonated polyetherketone aryl ketones, poly (2,2'-m-phenylene) -5,5'-bibenzimidazoles [poly (2 , 2'—in—phenylene) —5,5'-bibenzimidazole] or
  • the hydrogen ion conducting polymer may contain H, Na, K,
  • the binder resin may be used in the form of a single substance or a mixture, and may also be optionally used with a nonconductive compound for the purpose of further improving adhesion to the polymer electrolyte membrane. It is preferable to adjust the usage-amount so that it may be suitable for a purpose of use.
  • nonconductive compound examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene-nucleated fluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkylvinyl ether copolymer (PFA), and ethylene.
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-nucleated fluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoro alkylvinyl ether copolymer
  • ethylene ethylene
  • EFE ethylene / tetrafluoroethylene
  • ECTFE ethylenechlorotrifluoro-ethylene copolymer
  • PVdF-HFP polyvinylidene fluoride
  • dodecyl More preferably one or more selected from the group consisting of benzenesulfonic acid and sorbbi (Sorbitol).
  • the electrode substrate plays a role of supporting the electrode and diffuses the fuel and the oxidant into the catalyst layer so that the oxidant can easily access the catalyst layer.
  • the electrode substrate is a conductive substrate, and representative examples thereof include carbon paper, carbon cloth, carbon felt, or metal cloth (metal in fiber state).
  • the metal film is formed on the surface of the cloth formed of a porous film or polymer fibers consisting of) may be used, but is not limited thereto.
  • a water-repellent treatment with a fluorine-based resin as the electrode base material, since it is possible to prevent the reactant diffusion efficiency from being lowered by water generated when the fuel cell is driven.
  • the fluorine resin include polytetrafluoroethylene, polyvinylidene fluoride, polynuclear fluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride alkoxy vinyl ether, and fluorinated compounds. Fluorinated ethylene propylene, polychlorotrifluoroethylene or copolymers thereof can be used.
  • microporous layer for enhancing the effect of the semi-aungmul diffusion in the electrode substrate.
  • micropores are generally conductive powders of small particle size, such as carbon powder, carbon black, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotubes, carbon nanowires, carbon nano scars. -horn) or it may include a carbon nano ring (carbon nano ring).
  • the microporous layer is prepared by coating a composition comprising a conductive powder, a binder resin, and a solvent on the electrode substrate.
  • the binder resin include polytetrafluoroethylene, polyvinylidene fluoride, polynuclear fluoropropylene, polyperfluoroalkyl vinyl ether, polyperfluorosulfonyl fluoride, alkoxy vinyl ether, polyvinyl alcohol, and cells. Loose acetate or copolymers thereof and the like can be preferably used.
  • alcohols such as ethane-isopropyl alcohol, n-propyl alcohol, butyl alcohol, etc., water, dimethylacetamide, dimethyl sulfoxide, N-methylpyridone, tetrahydrofuran, etc. may be preferably used.
  • the coating process may be used, such as screen printing, spray coating or coating using a doctor blade, but is not limited thereto.
  • the carbon nanomaterial of the present invention is used as a catalyst carrier of a cathode electrode of a fuel cell.
  • the carbon nanomaterial of the present invention can be used as a carrier of various other catalysts, and furthermore, to develop materials in various fields. It can be widely used.
  • the aqueous solutions and citric acid were added to a 100 ml beaker. At this time, the amount of citric acid was used to be 0.625 times the total moles of metal contained in the aqueous solution.
  • the phase was 150 over 1 hour at (25 ° C).
  • the semi-unggi shown in FIG. 1 was prepared.
  • a moisture trap was installed at the nitrogen gas outlet to remove moisture in the quartz tube and nitrogen gas.
  • nitrogen gas was supplied at 200 cc / min for 15 minutes.
  • Nitrogen gas and hydrogen gas were supplied into the quartz tube at a supply amount of 160 cc / min and 40 cc / min, respectively.
  • the collected nitrogen-doped carbon nanotubes were mixed with 120 g of HCl and 300 g of distilled water, and the mixture was sealed and stirred for 24 hours.
  • HC1 and distilled water were removed from the stirred product, 10% by weight of HC1 was added again, followed by further stirring for 24 hours. Subsequently, the stirred product was sufficiently washed with distilled water and filtered to obtain a carbon nano-leube doped with nitrogen.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1 above, except that the reaction temperature of the step of raising the temperature of the quartz rib was performed to 340 ° C.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1, except that the reaction temperature of the quartz tube was raised to 380 ° C.
  • Nitrogen-doped carbon nanotubes were prepared in the same manner as in Example 1 except that the reaction temperature of the quartz tube sublimation process was performed up to 42 CTC.
  • Nitrogen-doped carbon nanotubes were prepared in the same manner as in Example 1, except that reaction temperature of the quartz tube was raised to 460 ° C.
  • Nitrogen-doped carbon nano-Lube was prepared in the same manner as in Example 1 except that the reaction temperature of the process of subliming the quartz tube was 5 (xrc). It was.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1, except that reaction temperature of the process of subliming the quartz tube was performed up to 52 CTC.
  • Nitrogen-doped carbon nanotubes were prepared in the same manner as in Example 1 except that the reaction temperature of the process of raising the temperature of the quartz rib was performed up to 540 ° C.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1 except that the reaction temperature of the process of heating the quartz tube was performed up to 600 ° C.
  • Nitrogen-doped carbon nano-Lube was prepared in the same manner as in Example 1, except that the reaction temperature of the process of raising the quartz tube was performed up to 640 ° C.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1 except that the reaction temperature of the step of raising the temperature of the quartz tube was performed up to 680 ° C.
  • Nitrogen-doped carbon nanotubes were prepared in the same manner as in Example 4 except that the reaction was maintained at a reaction temperature (42C C) for 3 hours (reaction time).
  • Nitrogen-doped carbon nanotubes were prepared in the same manner as in Example 7, except that the reaction was maintained at a reaction temperature (52 CTC) for 3 hours (reaction time).
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 10 except that the reaction was maintained at a reaction temperature (640 ° C.) for 3 hours (reaction time).
  • the semi-unggi shown in FIG. 1 was prepared.
  • the alumina plate prepared by spreading the catalyst evenly was placed in the center of the semi-ungung quartz tube shown in FIG. 1 and then sealed using Teflon tape.
  • a moisture tram was installed at the outlet of the helium gas to remove moisture in the quartz tube and helium gas.
  • helium gas was supplied at 200 cc / min for 15 minutes.
  • the quartz tube was then heated to the reaction temperature (30 (rC) for 1 hour while helium gas and hydrogen gas were supplied in a 4: 1 volume ratio into the quartz stream.
  • reaction temperature When the reaction temperature was reached, 0.035 ml / min of acetonitrile was supplied through the micropump and maintained at the reaction temperature for 1 hour (reaction time). At this time, carbon nanotubes doped with nitrogen were formed.
  • the collected nitrogen-doped carbon nanotubes were mixed with 120 g of HC1 and 300 g of distilled water, and the mixture was sealed and stirred for 24 hours.
  • HC1 and distilled water were removed from the stirred product, and HC1 at a concentration of 10% by weight was added again, followed by further stirring for 24 hours. Subsequently, the stirred product was sufficiently washed with distilled water and filtered to obtain a carbon nanotube doped with nitrogen.
  • Carbon nanotubes doped with nitrogen were prepared in the same manner as in Example 1 except that the reaction temperature of the step of raising the temperature of the quartz tube was performed up to 420 ° C.
  • the yield is extremely low at the reaction temperature of 300 ° C. (Example 1), whereas the production yield is rapidly increased at 340 ° C. (Example 2), and the reaction temperature is 420 °. Slightly increased to C.
  • the synthesis yield showed a marked decrease trend up to the reaction temperature of 520 ° C, showed almost the same yield in the range of 520 ° C to 650 ° C, and then rapidly decreased at 680 ° C.
  • the N / C (atomic%) is continuously increased from 300 ° C (Example 1) to 520 ° C (Example 7), and slowly decreases to 650 ° C, 680 At ° C, it showed a tendency to decrease rapidly.
  • reaction temperature is not yet equipped with the shape of the fiber at 340 ° C or less.
  • the carbon nanofibers prepared according to Example 3 having a reaction temperature of 380 ° C. are 30 to
  • TG was measured using a TG analyzer (device: STA 409 PC, NETZSCH) under an air atmosphere.
  • the temperature was measured at a temperature of 5 K / min from 100 ° C to 900 ° C.
  • Nitrogen isotherm adsorption and desorption experiments were performed on the carbon nanofibers prepared according to Examples 1 to 11 to measure specific surface areas. Nitrogen isothermal adsorption and desorption experiment
  • the sample was prepared by treating the prepared carbon nanofibers in a 10 wt% HC1 solution for 48 hours, washing with distilled water and drying for 3 hours in a drying oven at 80 ° C.
  • the measured specific surface area results are shown in FIG. 8.
  • the carbon nanofibers prepared according to Examples 1 to 11 obtained specific surface areas in the range of about 70 to 480 m 7 g.
  • the specific surface area tends to decrease slightly as the reaction temperature increases.
  • XPS X—ray Photoelectron Spectroscopy
  • the carbon, nitrogen, and oxygen components of each sample were analyzed at binding energy (C: 280 to 295 eV, N: 393 sowl 410 eV, 0: 520 to 540 eV).
  • FIGS. 9 and 10 XPS spectrum results for nitrogen of the carbon nanofibers of Examples 3 and 7 are shown in FIGS. 9 and 10.
  • (A), (B) and (C) shown in FIGS. 9 and 10 are pyridine-like structures or pyridine-like structures nitrogen components (A) and graphite-like, respectively.
  • the total nitrogen content measured from the measured XPS results and the nitrogen content present on the carbon nanofiber surface are shown in FIG. 11. .
  • the nitrogen content (about 1 to 9 atom 3 ⁇ 4) present on the surface is higher than the total nitrogen content (about 1 to 5 atom%), and the N / C atomic ratio at the surface is the total N / C source. It can be seen that about two times higher than mercy. Since the actual catalyst reaction is made on the surface of the catalyst and the carrier, the composition of the surface is important, and if there is more nitrogen on the surface of the total nitrogen content, the effect of nitrogen on the reaction can be seen more.
  • the ratio of N / C atomic ratio and the component (B) (graphite-like structure) / (A) component (pyridine-like structure) at the measured surface is shown in FIG. 12. As shown in FIG. 12, it can be seen that as the reaction temperature increases, the relative -nitrogen nitrogen component increases relatively.
  • X-ray scarcity (XRD) analysis was performed. XRD analysis was performed using RINT2000 (Rigaku) and scanning speed of 0.02 per minute from 10 degrees ( ° ) to 80 degrees ( ° ) in 2 ⁇ / ⁇ scanning mode. Among the measurement results, 2 ⁇ shows a peak corresponding to the (002) lattice plane near 26 degrees ⁇ ) in FIG. 13. As shown in FIG. 13, Examples 1 to 2. FIG. Carbon nanofibers prepared according to 11 can be seen that the peak of the (002) plane appears. In addition, it can be seen that as the reaction temperature increases, the peak central axis moves to a high angle, and the peak width narrows, thereby increasing the crystallinity. In addition, as the reaction temperature increases, the 10-band becomes apparent.
  • a catalyst slurry was prepared by mixing 20nig of carbon nanofibers prepared in Examples 4, 7 and 10, 10 wt% 3 ⁇ 4 concentration Napi silver solution (water solvent, Dupont) 40 ⁇ , distilled water 40kPa and ethanol lg. It was. The catalyst slurry was coated with 10, glass carbon having an IcHf area, and dried to prepare a working electrode.
  • a working electrode was prepared in the same manner as described above using Vulcan XC72R).
  • a working electrode was prepared in the same manner as described above using CNFCSsuntel RP-610: CNF1).
  • a working electrode was prepared in the same manner as described above using carbon nanofibers (CNF 2) synthesized at 52 CTC using ethylene as a carbon source instead of the carbon nanotubes prepared in Example 4 as a comparative example.
  • CNF 2 carbon nanofibers
  • ⁇ i6i> Working electrode manufactured, platinum mesh with counter electrode, Ag / AgCKALS as reference electrode. Electrochemical experiments were carried out with a three-electrode system using RE-IB, standard hydrogen electrode (denoted NHE).
  • HC10 4 in aqueous solution was conducted in the 0.0 to 1.2V with NHE reference electrode, an oxygen reduction reaction (Oxygen Reduction React ion: 0RR) experiment in 0.1M HC10 purged sufficiently with oxygen layer 4 aqueous solution as reference electrode NHE 1.2 to It was carried out at 0.2V. Also, the potential sweep rate was fixed at 2 () mV / sec.
  • Examples 4, 7 and 10, and Comparative Examples 2 to 4 all carbon materials exhibit a rectangular pattern by typical electric double layer formation.
  • Examples 4, 7 and 10 In the case of using carbon nanofibers, it can be seen that the inner area is large. As such, the large internal area indicates a large amount of ion adsorption, which means that the ion adsorption capacity is excellent, and as a result, it can be predicted that the catalyst supporting characteristics and the interaction between the catalyst and the carrier will be excellent when used as a catalyst carrier for fuel cells. have.
  • the carbon nanofibers of Examples 4, 7 and 10 has an oxygen reduction activity
  • the carbon material of Comparative Examples 2 to 4 does not have an oxygen reduction activity. From this result, the carbon nanofibers of Examples 4, 7 and 10 can It can be seen that it can also be used as a catalyst for the sword electrode.
  • a catalyst precursor solution was prepared by stirring a platinum precursor (Chloroplatinic acid hydride 99.9%, Aldrich), a carbon nanofiber carrier prepared according to Example 11, and 400 ml of distilled water for 48 hours.
  • NaBH 4 was prepared by dissolving it in 400 ml of distilled water in an amount of 15 times the molar ratio of the amount of metal to be supported. The mixture was stirred well for 30 minutes and then stirred for 48 hours to prepare a NaBH 4 solution. The catalyst precursor solution was added to NaBH 4 solution, and stirred for 1 hour to reduce the solution. The reduced product was washed with 1 L of distilled water and filtered, and dried for 2 hours in an oven at 80 ° C to prepare a Pt / carbon nanofiber catalyst (Pt / N640).
  • the platinum precursor (Chloroplatinic acid hydride 99.9%, Aldrich), except that the carbon nanofiber carrier prepared according to Example 13 and 400 ml of distilled water were stirred for 48 hours to prepare a catalyst precursor solution.
  • a Pt / carbon nanofiber catalyst (Pt / N523) was prepared.
  • Pt precursor Chloroplatinic acid hydride 99.9%, Aldrich
  • carbon black carrier 400 ml
  • the catalyst precursor solution was prepared in the same manner as in Example 16, Pt Carbon nanofiber catalysts (Pt / CB) were prepared.

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Abstract

La présente invention concerne un nanomatériau carboné, et son procédé de préparation. Le nanomatériau carboné selon la présente invention comprend une nanofibre de carbone contenant de l'azote. Le procédé de préparation du nanomatériau carboné selon la présente invention comprend les étapes consistant à : introduire de l'azote gazeux dans un réacteur en présence d'un catalyseur métallique supporté sur un support ; augmenter la température tout en fournissant un mélange gazeux d'azote gazeux et d'hydrogène gazeux dans le réacteur ; et fournir un composé contenant de l'azote dans le réacteur. Selon la présente invention, le nanomatériau carboné présente une durabilité remarquable et peut supporter plus efficacement un catalyseur et ainsi avoir un comportement excellent comme support de catalyseur. Le nanomatériau carboné selon la présente invention présente une durabilité remarquable du fait de son excellente cristallinité obtenue par l'introduction d'azote dans une nanofibre de carbone, supporte plus efficacement un catalyseur et peut améliorer la dispersabilité. Le nanomatériau carboné selon la présente invention pourra être utilisé comme support d'un catalyseur, y compris d'un catalyseur d'électrode d'une pile à combustible et pourra être appliqué au développement d'un matériau dans différents domaines.
PCT/KR2012/003204 2012-04-26 2012-04-26 Nanomatériau carboné et son procédé de préparation WO2013162097A1 (fr)

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Citations (1)

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Publication number Priority date Publication date Assignee Title
KR20100100890A (ko) * 2007-12-20 2010-09-15 바이엘 테크놀로지 서비시즈 게엠베하 질소 도핑된 탄소 나노튜브의 제조 방법

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20100100890A (ko) * 2007-12-20 2010-09-15 바이엘 테크놀로지 서비시즈 게엠베하 질소 도핑된 탄소 나노튜브의 제조 방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ISMAGILOV, ZINFER R. ET AL., CARBON, vol. 47, 24 March 2009 (2009-03-24), pages 1922 - 1929 *
KIM, CHAN ET AL., ADV. FUNCT. MATER., vol. 16, 27 October 2006 (2006-10-27), pages 2393 - 2397 *

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