WO2012053561A1 - Matériau d'électrode et son procédé de fabrication - Google Patents

Matériau d'électrode et son procédé de fabrication Download PDF

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WO2012053561A1
WO2012053561A1 PCT/JP2011/074069 JP2011074069W WO2012053561A1 WO 2012053561 A1 WO2012053561 A1 WO 2012053561A1 JP 2011074069 W JP2011074069 W JP 2011074069W WO 2012053561 A1 WO2012053561 A1 WO 2012053561A1
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platinum
electrode material
cnt
electrode
carbon
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PCT/JP2011/074069
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Japanese (ja)
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優 吉武
木原　直人
敦義 竹中
陽介 網野
洋一 世良
佳孝 西條
川本　昌子
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旭硝子株式会社
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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
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/925—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
    • 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 an electrode material suitable for a fuel cell, an air cell, and the like, and a manufacturing method thereof.
  • Electrode materials in which a catalyst such as platinum is supported on carbon are often used for electrodes of fuel cells and the like.
  • the electrode characteristics of the electrode material vary greatly depending on the catalyst loading method.
  • PEFC polymer electrolyte fuel cell
  • proposals such as supporting platinum fine particles in a highly dispersed manner have been made (see Patent Documents 1 and 2).
  • PEFCs for fuel cell vehicles are required to have durability against frequent start and stop.
  • High power density is also required.
  • the advantage of the platinum catalyst is that it is easy to obtain a higher output density in addition to high activity and high stability.
  • the catalyst is required to have a high loading rate.
  • carbon catalysts having a high specific surface area such as Vulcan and Ketjen Black have been used as platinum-based catalysts.
  • these high specific surface area carbon-based carriers are insufficient in durability, particularly oxidation resistance.
  • the supported platinum particles themselves are catalysts for carrier oxidation.
  • metal oxide carriers such as graphitized carbon and titania have been studied, but there is a problem that the specific surface area is small and it is difficult to increase the catalyst loading.
  • carbon nanotubes are carriers with excellent oxidation resistance and electron conductivity, but have problems such as water repellency and low specific surface area. For this reason, it has been difficult to support the catalyst using the untreated carbon nanotubes as they are. Therefore, it is often performed that carbon nanotubes are treated with a mixed acid or the like to form a functional group. However, in this case, the activity was not always sufficient. Moreover, introduction of a functional group impairs the stability of the carbon nanotube.
  • An object of the present invention is to provide an electrode material having a high catalyst loading ratio, good durability, and high activity.
  • An electrode material characterized by. (2) The electrode material according to (1) above, wherein the carbon nanotubes are heat-treated at 2000 ° C. or higher. (3) The electrode material according to (1) or (2), wherein the carbon nanotube has a diameter of 200 nm or less. (4) The electrode material according to any one of (1) to (3), wherein the carbon nanotube has an aspect ratio of 10 or more.
  • the electrode material obtained in the present invention has high activity and durability, and can be used for an electrode for a fuel cell having a high power density.
  • underpotential deposition (hereinafter also referred to as “UPD”) is a potential higher than the theoretically calculated deposition potential (noble potential) when the interaction between ions and substrate atoms is strong. ) Refers to the phenomenon of metal and hydrogen deposition.
  • CNT carbon nanotube
  • 3 to 6 are cyclic voltammograms (CV curves) showing the comparison. The potential is shown based on the Ag / AgCl electrode.
  • the broken line is the case of the gold (Au) substrate only, and the solid line is the CV curve when the carbon-based material is applied.
  • the measurement conditions for the CV curve are the same as in the examples described later.
  • the method for producing the sample electrode was in accordance with the example, and only the carbon-based material was supported on the gold substrate.
  • FIG. 3 commercially available carbon black (Ketjen Black having a specific surface area of 1200 m 2 / g) was used.
  • FIG. 4 commercially available carbon black (Vulcan XC-72 having a specific surface area of 250 m 2 / g) was used.
  • FIG. 5 cup-stacked carbon nanofibers were used.
  • the same CNT used in Example 1 of the example was used.
  • CNT is easy to coat ionomers such as ion exchange resins when applying an electrode catalyst to a membrane electrode assembly (MEA). preferable.
  • the CNT may be a single-wall CNT or a multi-wall CNT, but is not easily oxidized as a material, and is easy to disperse and handle during electrode production (the multi-wall CNT is less likely to aggregate than the single-wall CNT. Therefore, multilayer CNT is preferable.
  • platinum is supported as highly active fine particles as compared with carbon nanohorn or the like. This is probably because platinum supported on the CNT surface composed of carbon sp 2 hybrid orbitals exhibits high activity. On the other hand, in the edge portion, sp 3 hybrid orbitals increase, and the activity of platinum existing in this portion is considered to decrease.
  • the interatomic distance of platinum as a general metal is 0.277 nm.
  • the distance between the 6-membered rings of the graphene structure composed of carbon atoms on the CNT surface is 0.246 nm. For this reason, when a strong bond is formed between platinum and CNT, platinum is subjected to compressive strain.
  • the potential at which discharge / adsorption of hydrogen ions corresponding to hydrogen ion UPD occurs is significantly higher than that on a general platinum surface. It was found that it was biased toward a nasty direction. This reason is presumed to be based on the interaction between the CNT surface and platinum atoms.
  • the CNT used in the present invention has a peak ratio (D / G) of D band and G band by Raman spectroscopy of 0.3 or less, more preferably 0.25 or less, further preferably 0.17 or less, and 10 or less is particularly preferable.
  • the peak of the D band by Raman spectroscopy is a peak near 1350 cm ⁇ 1 , which is caused by a point defect or a crystal edge defect.
  • the G band peak is a peak in the vicinity of 1580 cm ⁇ 1 and is a peak commonly observed in graphite.
  • a small value of D / G indicates that there are few defects on the surface or end of the CNT. That is, it means a long CNT with few defects and many good surfaces.
  • a small number of defects means that there are few defects that are the starting point of the oxidation reaction, which means that the durability is excellent.
  • the peak ratio between the D band and the G band by the above Raman spectroscopy is a value obtained when Raman spectroscopy is measured under the following conditions.
  • the heat treatment temperature of the CNT used in the present invention is preferably 2000 ° C. or higher. This is because the aforementioned D / G can be reduced, and the oxidation resistance is improved together with the mechanical strength. In addition, it is known that heat treatment at high temperature is also effective for removing the catalyst component used during CNT production. As this heat processing temperature, 2200 degreeC or more is more preferable, and 2400 degreeC or more is especially preferable. Although there is no upper limit on the heat treatment temperature, 3000 ° C. or less is economically preferable. (See J. Chen et al., Carbon, 45 (2007) 274.)
  • the diameter of the CNT is preferably 200 nm or less, more preferably 150 nm or less, further preferably 10 to 100 nm, and particularly preferably 10 to 60 nm. If the diameter is in the above range, it is presumed that the electrode activity increases because platinum fine particles are supported on the surface of the CNT while being dispersed as fine particles while maintaining a highly active state.
  • the diameter of the CNT is obtained from the result of image analysis of a FE-SEM (Field Emission-Scanning Electron Microscope) or TEM (Transmission Electron Microscope) photograph.
  • the aspect ratio of CNT is preferably 10 or more, and more preferably 50 or more. Although there is no particular upper limit value for the aspect ratio, it is generally 1000. If the aspect ratio is large, the D / G value tends to be small.
  • the aspect ratio of CNT can be obtained from the result of image analysis of FE-SEM or TEM photograph.
  • platinum is preferably supported directly on CNT.
  • directly supporting means that the surface of the CNT is not modified. That is, the surface of the CNT is not modified with, for example, an organic group. In particular, chemical treatment for the purpose of hydrophilization is not performed. Although the details of the mechanism of action are not necessarily clear, it is thought that the atoms present on the supported platinum surface can have a less disturbed structure by the strong bonding of platinum fine particles to the CNT surface with particularly high crystallinity. It is done. On the other hand, the distance between carbon atoms constituting the CNT surface is not the same as the distance between closest atoms (2.77 angstroms) of the platinum crystal. FIG.
  • FIG. 7 shows a conceptual diagram for estimating the correlation between carbon nanotubes and platinum atoms.
  • platinum atoms form a bond on CNT as shown in FIG. 7, the distance between AB of corresponding carbon atoms (corresponding to the vertices of an equilateral triangle composed of every other vertex of the hexagon); Since it is smaller than the closest interatomic distance of the platinum single crystal for 46 angstroms, the interatomic distance of platinum is reduced. As a result, the distance between atoms changes, which is considered to express a predetermined activity by changing the electronic structure.
  • the support surface is disordered or there are bulky compounds such as polybenzimidazole or the like, such as carboxyl groups or phenolic hydroxyl groups on the surface, the supported platinum atoms and the carbon in the support CNT It is thought that the atomic bond is not sufficient or the platinum bond is disturbed. In that case, it seems that the structure pattern of the supported platinum particles is not so different from that of the unsupported platinum particles. For example, when a chemical hydrophilization treatment by a mixed acid treatment is performed, the D / G of CNT is increased, and the catalytic activity tends to be lowered.
  • polybenzimidazole or the like such as carboxyl groups or phenolic hydroxyl groups
  • PFSA perfluorosulfonic acid
  • the adsorption amount of PFSA is preferably 10 parts by mass or less with respect to 100 parts by mass of CNT.
  • Catalyst fine particles In the present invention, it is preferable to support platinum as a catalyst on the CNT as an electrode material, that is, use platinum fine particles as catalyst fine particles.
  • platinum fine particles As the catalyst, only platinum may be used, or platinum and a metal other than platinum may be used in combination. Examples of the metal other than platinum used in combination include nickel, palladium, silver, and gold.
  • ⁇ Vapor phase support> platinum is supported on CNTs in a gas phase (gas phase method). Although the details of the phenomenon are not necessarily clear, it is considered that when platinum is supported in a gas phase, it is likely to be supported as fine particles on the surface of the CNT.
  • a vacuum deposition method, a sputtering method, or an arc plasma method is preferable.
  • platinum as a target is heated, and platinum is deposited on CNTs under vacuum. Examples of the method for heating platinum include a resistance heating method, an electron beam method, a high frequency induction method, and a laser method.
  • the resistance heating vapor deposition method or the electron beam vapor deposition method is preferable because the apparatus has a relatively simple configuration.
  • the degree of vacuum is preferably about 10 ⁇ 3 to 10 ⁇ 4 Pa.
  • platinum as a target is placed in a vacuum chamber, and a rare gas element (generally using argon) ionized by applying a high voltage is collided. The platinum atoms of the target are repelled by the collision, reach the CNTs, and can carry platinum.
  • arc plasma method plasma is formed by arc discharge in vacuum, platinum (evaporation material) provided near the cathode or in the vicinity of the cathode is evaporated, and platinum is supported on the surface of the CNT.
  • platinum particles are supported on carbons by a liquid phase method (liquid phase hydrogen) in which carbons are dispersed in water, platinum salts such as chloroplatinic acid aqueous solution are added, dried and then reduced. Reduction method) is known.
  • liquid phase hydrogen liquid phase hydrogen
  • platinum salts such as chloroplatinic acid aqueous solution
  • Reduction method Reduction method
  • colloidal particles of platinum are generated using a protective agent and simultaneously supported.
  • the protective agent can be removed by treatment at a high temperature, but in the course of the high temperature treatment, the platinum fine particles aggregate and tend to grow, resulting in a decrease in activity.
  • CNT has a small specific surface area and high water repellency compared to carbon black having a high specific surface area such as Vulcan and Ketjen Black. For this reason, it has been performed that a CNT is subjected to a chemical treatment to introduce a polar functional group to make the surface hydrophilic.
  • Platinum has a very low melting point for compounds such as oxides (PtO, PtO 2 ) and chlorides (PtCl 2 , PtCl 4 ) compared to metal (Pt).
  • oxides PtO, PtO 2
  • chlorides PtCl 2 , PtCl 4
  • Pt metal
  • the temperature of the process of carrying these on a carrier such as carbon and carrying out the drying treatment or reduction is usually 150 to several hundred degrees C., and the aggregation of fine particles tends to occur.
  • CNT having a small specific surface area
  • special measures are required.
  • the Huettig temperature is about 300 ° C. or higher, and it can be said that the aggregation of fine particles is less likely to occur compared to oxides and chlorides.
  • platinum is supported by a vapor phase method.
  • platinum fine particles as a catalyst are supported on the CNT surface.
  • the gas phase method of the present invention no aggregation inhibitor is used.
  • Anti-agglomeration agents are generally used in colloid protection methods. Since no anti-aggregation agent is used, the removal step is also unnecessary. Heating, which is a general anti-aggregating agent removal step, causes aggregation of platinum fine particles and causes a decrease in the degree of dispersion. Further, the gas phase method has an advantage that no waste liquid or the like is generated.
  • the electrode material of the present invention uses the above electrode material. Specifically, for example, an electrode material is kneaded with a binder and formed into a necessary shape to obtain an electrode.
  • the binder include a fluorinated resin having a sulfonic acid group.
  • the fluorine-containing resin having a sulfonic acid group include a resin (trade name: Flemion) manufactured by Asahi Glass Co., Ltd. and a resin (trade name: Nafion) manufactured by DuPont.
  • the electrode of the present invention is suitable for a fuel cell electrode (hydrogen electrode or air electrode). It can also be applied to the air electrode of an air battery. Furthermore, it is expected to be applied as a cathode for FED (Field Emission Display), flat fluorescent tubes, and cold cathode tubes.
  • FED Field Emission Display
  • Examples 1 to 6 and 10 are examples, and examples 7 to 9 and 11 are comparative examples.
  • Example 1 EB deposition / CNT
  • MWNT-7 manufactured by Hodogaya Chemical Co., Ltd.
  • It is manufactured through a heat treatment at about 2200 ° C.
  • It is a multi-walled CNT having a D / G of 0.08, a diameter of 60 nm, and an aspect ratio of about 120.
  • 10 mg of the CNT was put into 50 mL of the mixed solvent A and dispersed by irradiating ultrasonic waves for 15 minutes to obtain a solution 1A.
  • the mixed solvent A is a solvent obtained by mixing tetrahydrofuran and HFE-347pc-f (CF 3 CH 2 OCF 2 CF 2 H, manufactured by Asahi Glass Co., Ltd.) at 1: 1 (mass ratio). 5 mL of this solution 1A was pipetted and dropped onto an ethylene-tetrafluoroethylene copolymer resin film (hereinafter also referred to as ETFE film) and dried to deposit CNTs.
  • the ETFE film on which the CNTs were deposited was placed in an electron beam (EB) vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.) and maintained at a vacuum degree of about 8 ⁇ 10 ⁇ 4 Pa.
  • EB electron beam
  • the acceleration voltage was 10 kV, the current value was 260 mA, and an electron beam was applied to the platinum crucible.
  • platinum particles were deposited 1 nm on the ETFE film carrying CNTs. From the ETFE film, CNT supporting platinum was scraped off.
  • the loading ratio of platinum was measured by the following method. Aqua regia was added to the weighed catalyst (CNT supporting platinum) to dissolve platinum. Platinum was quantified by ICP emission spectroscopy, and the loading rate was calculated therefrom. 5 mg of this CNT carrying platinum was put into 50 mL of the mixed solvent A and dispersed by irradiating with ultrasonic waves for 15 minutes to obtain a solution AC-1.
  • FIG. 1 is a CV curve in the case of using the sample electrode 1 measured according to the conditions described later. As shown in FIG. 1, from the CV curve, the hydrogen adsorption / desorption peak was observed at a considerably lower potential than that of a general catalyst, that is, a portion close to the equilibrium potential of hydrogen. Furthermore, the characteristic characteristic of the electrode material of the present invention that the oxidation-reduction potential of platinum was higher than that of a general catalyst was confirmed.
  • Example 2 Sputtering / CNT
  • the ETFE film on which CNTs obtained in the same manner as in Example 1 were deposited was placed in a sputtering apparatus (manufactured by Tokki Co., Ltd.) and kept at a vacuum of about 6.7 ⁇ 10 ⁇ 4 Pa.
  • Argon (Ar) gas was introduced into the chamber at a rate of 50 sccm to 0.3 Pa.
  • 1 sccm means a flow rate of 1 cm 3 per second in terms of the standard state.
  • a plasma was generated by applying a DC voltage with a power of 50 W.
  • Platinum was deposited to 1 nm on CNT by using platinum as a target, opening and closing the shutter, and controlling the film formation time.
  • Example 2 From the ETFE film, CNT supporting platinum was scraped, and 3 mg of this material was put into 30 mL of the mixed solvent A and dispersed by irradiating with ultrasonic waves for 15 minutes to obtain a solution AC-2.
  • This solution AC-2 was dropped onto the rotating electrode with a pipette to deposit CNTs. Further, the same ionomer dispersion solution as in Example 1 was dropped and dried to obtain a sample electrode 2.
  • the CV curve was almost the same as in Example 1.
  • Example 3 Arc plasma / CNT
  • the ETFE film on which CNTs having different diameters obtained using the same preparation conditions as in Example 1 were deposited was placed in an arc plasma apparatus (manufactured by ULVAC-RIKO), and the degree of vacuum was about 1 ⁇ 10 ⁇ 3 Pa. Retained. Platinum was deposited on the CNTs with a repetitive pulse having a pulse width of 200 ⁇ s. Thereafter, a sample electrode 3 was obtained in the same manner as in Example 1, and the electrode characteristics were evaluated. As in the case of Example 1, the CV curve was such that the hydrogen UPD was biased toward a base potential.
  • Example 4 EB deposition / hydrophilized CNT
  • BET surface area becomes (25 m 2 / g in untreated) 37m 2 / g
  • D / G was about 3-fold compared to that of untreated becomes 0.23.
  • an electrode material of 30% by mass Pt / CNT (calculated value) was prepared in the same manner as in Example 1, sample electrode 4 was obtained, and electrode characteristics were evaluated.
  • the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 5 Sputtering / hydrophilic CNT
  • Example 1 The same CNT as in Example 1 was hydrophilized in the same manner as in Example 4, and platinum was supported under the same conditions as in Example 2.
  • the obtained sample electrode 5 was evaluated for electrode characteristics in the same manner as in Example 1.
  • the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 6 Arc plasma / hydrophilic CNT
  • Example 4 Arc plasma / hydrophilic CNT
  • Example 4 The same CNT as in Example 1 was hydrophilized in the same manner as in Example 4, and platinum was supported under the same conditions as in Example 3.
  • the obtained sample electrode 6 was evaluated for electrode characteristics in the same manner as in Example 1.
  • the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 7 Sputtering / Vulcan
  • Carbon black (Vulcan) was used as a carrier, and platinum was supported in the same manner as in Example 1.
  • the obtained sample electrode 7 was evaluated for electrode characteristics in the same manner as in Example 1.
  • the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 8 Arc plasma / Ketjen Black
  • Carbon black (Ketjen Black) was used as a carrier, and platinum was supported in the same manner as in Example 3.
  • the obtained sample electrode 8 was similarly evaluated for characteristics.
  • the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 9 Commercial Catalyst / Catalyst Society Fuel Cell Related Catalysts Research Committee Reference Catalyst / Evaluation Method Study Group Common Catalyst FC-I1
  • FC-I1 manufactured by Ishifuku Metal Industry Co., Ltd.
  • This catalyst is prepared by supporting a platinum salt on a Vulcan carrier, drying it, and then reducing it.
  • the CV curve (FIG. 2) showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Electrode characteristic evaluation> The electrode characteristics were determined by the following electrochemical measurement.
  • a cell manufactured by Hokuto Denko Co., Ltd. was used as the cell.
  • As the working electrode each sample electrode prepared in each of the above examples was used. Glassy carbon was used for the counter electrode.
  • As the reference electrode a double junction type silver / silver chloride electrode was used.
  • the cell temperature was 60 ° C., 0.5 M sulfuric acid aqueous solution was used, and nitrogen gas was bubbled for measurement.
  • the redox activity was measured while rotating the sample electrode at 1000 rpm.
  • the sweep speed is 50 mV / s, and the sweep range is 0.05 V to 1.2 V (standard hydrogen electrode standard) (The description of FIGS.
  • the mass activity ratio was determined as follows. When the commercially available catalyst (Example 9) was 1, the ratio of the current value per the same platinum amount at 0.85 V was determined as the activity ratio. As shown in Examples 1 to 3, the electrode material of the present invention using CNTs that had not been subjected to a hydrophilization treatment exhibited a mass activity that was more than four times that of a commercially available catalyst. This is probably because the D / G was as small as 0.1 or less, and the platinum fine particles were directly supported on the CNT without performing the hydrophilic treatment. Further, as shown in Examples 4 to 6, even when the hydrophilization treatment is performed, if D / G is 0.3 or less, the mass activity is about 6 to 10 times that of a commercially available catalyst. was gotten.
  • Example 10 In the same manner as in Example 3, 15% by mass of platinum was supported on the CNT obtained in the same manner as in Example 1. Using this electrode, a potential step cycle test was conducted in a 0.5 M sulfuric acid aqueous solution at 60 ° C. under the following conditions. [1.3 V, hold for 30 seconds: 0.9 V, hold for 30 seconds] was repeated 300 times. The mass activity (A / mgPt) before and after this potential step cycle test was compared, and the reduction rate of mass activity at 0.8 V and 0.9 V was calculated.
  • Example 11 An electrode was prepared and a potential step cycle test was conducted in the same manner as in Example 10 except that ketjen black having a large specific surface area was used instead of CNT as the support.
  • the electrode material of the present invention is suitable for an electrode (hydrogen electrode or air electrode) of a fuel cell and an air electrode of an air cell, and can also be used as a cathode of an FED, a flat fluorescent tube and a cold cathode tube.

Abstract

Cette invention concerne un matériau d'électrode, à taux élevé de maintien, à durabilité satisfaisante et à activité élevée. Le matériau d'électrode est formé par dépôt de platine sur des nanotubes de carbone en phase gazeuse. Le taux de crête (D/G) de la bande D et de la bande G déterminé par spectroscopie Raman ne dépasse pas 0,3. Les nanotubes de carbone sont de préférence soumis à un traitement thermique d'au moins 2000°C. De plus, le diamètre des nanotubes de carbone n'est de préférence pas supérieur à 200 nm et leur rapport de forme n'est de préférence pas inférieur à 10.
PCT/JP2011/074069 2010-10-19 2011-10-19 Matériau d'électrode et son procédé de fabrication WO2012053561A1 (fr)

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WO2014132957A1 (fr) * 2013-02-28 2014-09-04 東レ株式会社 Agrégat à nanotubes de carbone et procédé de fabrication associé
JP2015017029A (ja) * 2013-06-11 2015-01-29 東レ株式会社 カーボンナノチューブ集合体およびその製造方法
JP2018028122A (ja) * 2016-08-16 2018-02-22 古河電気工業株式会社 カソード電極
JP2018142519A (ja) * 2017-02-28 2018-09-13 学校法人東京理科大学 白金ナノ粒子と炭素系担体との複合体及びその製造方法

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CN105008276A (zh) * 2013-02-28 2015-10-28 东丽株式会社 碳纳米管聚集体及其制造方法
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JPWO2014132957A1 (ja) * 2013-02-28 2017-02-02 東レ株式会社 カーボンナノチューブ集合体およびその製造方法
US9922745B2 (en) 2013-02-28 2018-03-20 Toray Industries, Inc. Aggregate of carbon nanotubes, and production method therefor
JP2015017029A (ja) * 2013-06-11 2015-01-29 東レ株式会社 カーボンナノチューブ集合体およびその製造方法
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JP2018142519A (ja) * 2017-02-28 2018-09-13 学校法人東京理科大学 白金ナノ粒子と炭素系担体との複合体及びその製造方法

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