WO2011136186A1 - Matériau d'électrode - Google Patents

Matériau d'électrode Download PDF

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WO2011136186A1
WO2011136186A1 PCT/JP2011/060084 JP2011060084W WO2011136186A1 WO 2011136186 A1 WO2011136186 A1 WO 2011136186A1 JP 2011060084 W JP2011060084 W JP 2011060084W WO 2011136186 A1 WO2011136186 A1 WO 2011136186A1
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platinum
electrode
electrode material
cnt
supported
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PCT/JP2011/060084
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English (en)
Japanese (ja)
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優 吉武
陽介 網野
川本　昌子
敦義 竹中
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旭硝子株式会社
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    • 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.
  • 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 have been made such that platinum fine particles are supported in a highly dispersed manner see Patent Documents 1 and 2).
  • PEFCs for fuel cell vehicles are required to have durability against frequent starting and stopping.
  • Conventional carbon-based carriers having a high specific surface area have insufficient durability, particularly oxidation resistance.
  • 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 loading rate.
  • 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.
  • a functional group is formed by treatment with a mixed acid or the like. However, in this case, the activity is not always sufficient, and the oxidation resistance is often not at the expected level.
  • 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 obtained by directly supporting platinum on carbon nanotubes (2) The electrode material according to (1), wherein carbon nanotubes are supported with platinum reduced and precipitated in a liquid phase. (3) The electrode material according to (1) or (2), wherein a peak ratio (D / G) of a D band and a G band of a carbon nanotube by Raman spectroscopy is 0.17 or less. (4) The electrode material according to any one of (1) to (3), wherein the reduction deposition in the liquid phase is performed by hydrogen reduction of a platinum salt. (5) The electrode material according to any one of (1) to (4), wherein the carbon nanotube has a diameter of 200 nm or less.
  • 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 applied as a cathode of an FED, a flat fluorescent tube, or a cold cathode tube.
  • FIG. 1 is a cyclic voltammogram (CV curve) measured using the electrode material of the present invention.
  • FIG. 2 is a CV curve measured using an electrode material in which a platinum catalyst is supported on commercially available carbon black.
  • FIG. 3 is a CV curve measured using commercially available carbon black.
  • FIG. 4 is a CV curve measured using commercially available carbon black.
  • FIG. 5 is a CV curve measured using cup-stacked carbon nanofibers.
  • FIG. 6 is a CV curve measured using multi-walled carbon nanotubes.
  • the potential is a standard hydrogen electrode reference potential.
  • CNT carbon nanotubes
  • 3 to 6 are cyclic voltammograms (CV curves) showing the comparison.
  • 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. In FIG.
  • Example 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.
  • FIG. 6 the same CNT used in Example 1 of the example was used.
  • CNTs may be single-walled CNTs or multilayered CNTs, but multilayered CNTs are preferred because they are less susceptible to oxidation and easy to handle.
  • CNTs are thought to carry platinum as highly active fine particles compared to carbon nanohorns and 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, it is considered that the sp 3 hybrid orbitals increase in the edge portion, and the activity of platinum existing in this portion decreases.
  • the CNT used in the present invention preferably has a peak ratio (D / G) of D band to G band by Raman spectroscopy of 0.17 or less, more preferably 0.10 or less.
  • 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 that there are many good surfaces with few defects and long CNTs.
  • 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 of the D band and the G band by the above Raman spectroscopy is a value when the Raman spectroscopy is measured under the following conditions.
  • 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. The upper limit of the aspect ratio is not particularly limited, but is generally 1000 or less. 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 directly supported on CNTs.
  • 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.
  • chemical treatment for the purpose of hydrophilization is not performed. This is because platinum fine particles are supported on a specific surface of CNT, or are supported on a surface on which a metal (metal other than platinum) is supported. Because.
  • platinum is preferably supported on the CNT as a catalyst as the electrode material, that is, platinum fine particles are used as the catalyst fine particles.
  • platinum fine particles are used as the catalyst fine particles.
  • 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.
  • ⁇ Reduction deposition> it is preferable to use platinum which is reduced and precipitated in the liquid phase.
  • the particles When deposited in the liquid phase, it is considered that the particles are easily supported as fine particles on the surface of the CNT.
  • the reduction is preferably performed by hydrogen reduction of a platinum salt. It is considered that hydrogen reduction is simple and hardly affected by chemically active species that hinder the expression of the activity of the platinum fine particles.
  • a colloid protection method in which colloidal particles of a catalyst are generated and simultaneously supported has been adopted.
  • functional groups have been introduced and the surface has been hydrophilized.
  • the activity of electrode materials using CNTs with functional groups introduced was low. Its activity was equal to or about half that of the conventional carbon black.
  • by introducing a functional group it was easily oxidized at a high potential, resulting in a decrease in the oxidation resistance of CNT at a high potential, which was inappropriate.
  • platinum fine particles as a catalyst are preferably deposited on the CNT surface by reducing platinum salt in a liquid phase.
  • the use of platinum reduced and precipitated in the liquid phase in this way eliminates the need to introduce functional groups. For this reason, it becomes difficult for CNT to be oxidized at a high potential, and a desirable electrode material can be obtained.
  • a predetermined activity is expressed by supporting platinum fine particles and CNTs on a specific surface.
  • the platinum salt is preferably one containing no halogen atom.
  • the nitro salt (nitro complex) or nitroammine salt (nitroammine complex) of platinum is preferable.
  • the nitro salt include K 2 [Pt (NO 2 ) 4 ], Pt (NO 2 ) 3 (OC 2 H 5 ), and [Pt (NO 2 ) 3 (OC 2 H 5 )] H 2 .
  • Nitroammine salts include [Pt (NH 3 ) 2 (NO 2 ) 2 ], Pt (NH 3 ) 2 (NO 2 ) 3 (OC 2 H 5 ), Pt (NH 3 ) 2 (NO 2 ) 2 ( OC 2 H 5 ) (NO 3 ), Pt (NH 3 ) (NO 2 ) (OC 2 H 5 ), [Pt (NH 3 ) (NO 2 ) 2 (OC 2 H 5 )] H, Pt (NH 3 ) 2 (NO 2 ) 3 (COCH 3 ), Pt (NH 3 ) 2 (NO 2 ) (COCH 3 ), [Pt (NH 3 ) (NO 2 ) 2 (COCH 3 )] H, Pt (NH 3 ) 2 (NO 2 ) 3 (OCOCH 3 ), Pt (NH 3 ) 2 (NO 2 ) (OCOCH 3 ), [Pt (NH 3 ) (NO 2 ) 2 (OCOCH 3 )] H and the like can be exemplified.
  • the liquid phase reduction method when the liquid phase reduction method is adopted, that is, when platinum that is reduced and precipitated in the liquid phase is used, 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 removal step, causes coalescence of catalyst fine particles and causes a reduction in catalyst dispersion.
  • Examples of the hydrogen reduction method include a method of dispersing CNT in water, adding a platinum salt, and introducing hydrogen gas into water. It is known that it is difficult to stably disperse CNTs, particularly long (high aspect ratio) multilayer CNTs, in a liquid. In the present invention, a permanent distributed state is not necessarily required.
  • the concentration at which CNT is dispersed in water is preferably 100 to 900 mg / L, and more preferably 100 to 300 mg / L.
  • ultrasonic treatment for the same purpose, alcohols such as ethanol may be added.
  • alcohols short-chain alcohols are preferable, and alcohols having 1 to 10 carbon atoms are preferable.
  • monools such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-ethyl-1-hexanol, etc.
  • Polyhydric alcohols such as ethylene glycol and glycerin can be exemplified. Of these, methanol or ethanol is particularly preferred.
  • the concentration of the added alcohol is not particularly limited. For example, when ethanol is used, it is preferably 10 to 300 g / L, more preferably 20 to 200 g / L in the solution for depositing the platinum salt.
  • the platinum salt may be added as a solid or an aqueous solution to a system in which CNTs are dispersed. It is preferable to add an aqueous solution of a platinum salt to the CNT dispersion because it is easy to operate.
  • the concentration of the platinum salt is preferably 10 to 1000 mg / L in the solution for depositing the platinum salt, and more preferably 10 to 100 mg / L. It is considered that highly active platinum fine particles are precipitated by reducing a dilute solution of platinum salt.
  • the amount of hydrogen gas introduced is preferably 1 to 20 g / L ⁇ Hr.
  • the pressure at the time of introducing hydrogen gas may be a normal pressure or a pressurized pressure.
  • the inert gas argon or nitrogen gas is preferable.
  • CNT When the electrode material is extremely small, CNT is deposited on an inert substrate (eg, glassy carbon), and then an aqueous platinum salt solution is dropped, followed by exposure to an air stream containing hydrogen. Even manufacture is possible.
  • the temperature during the reduction is not particularly limited, but is preferably 5 to 95 ° C, more preferably 20 to 60 ° C. After the reduction is completed, CNTs are collected by filtration and dried to form an electrode material.
  • the drying temperature is preferably 20 to 150 ° C, more preferably 50 to 80 ° C.
  • the electrode material of the present invention uses the above electrode material. Specifically, for example, an electrode material can be kneaded with a binder and formed into a required shape to obtain an electrode.
  • the binder include a fluorinated resin having a sulfonic acid.
  • the fluorine-containing resin having a sulfonic acid 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 to cathodes of FED (Field Emission Display), flat fluorescent tubes, and cold cathode tubes.
  • FED Field Emission Display
  • Examples 1 to 3 and 8 are examples, and examples 4 to 7 and 9 are comparative examples.
  • Example 1 As the CNT, MWNT-7 manufactured by Hodogaya Chemical Co., Ltd. was used. 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. 3 mg of the CNT was put into 30 mL (liter) of the mixed solvent A and dispersed by irradiation with 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). From this solution 1A, 70 ⁇ L was taken with a pipette, dropped onto the disk electrode of the rotating electrode, and dried to deposit CNTs.
  • the disk electrode is an electrode made of glassy carbon having a diameter of 5 mm.
  • a platinum salt solution manufactured by Ishifuku Metal Industry Co., Ltd., dinitrodiammine platinum nitric acid solution, platinum concentration 100.93 g / L) ([Pt ( 200 ⁇ L of NH 3 ) 2 (NO 2 ) 2 ] / HNO 3 solution) was added and stirred well to obtain Solution 1B. 15 ⁇ L of this solution 1B was collected using a micropipette and dropped onto the CNT deposited on the disk electrode.
  • the disk electrode was set in a reaction tube (made of quartz, cylinder having an inner diameter of 17 mm and a length of 19 cm), and hydrogen gas was introduced at 0.1 g / Hr at normal pressure. The temperature was 25 ° C. The introduction of hydrogen gas was stopped after 1 hour, and the electrode was taken out after replacing with helium gas. The reason for substituting with helium gas is to remove hydrogen on the catalyst surface and prevent overheating and deterioration of the catalyst surface due to oxidation in the air. An ionomer dispersion solution (manufactured by DuPont, Nafion solution) was dropped and dried to obtain a sample electrode 1. This sample electrode 1 was subjected to electrode characteristic evaluation.
  • FIG. 1 is a CV curve in the case of using the sample electrode 1 measured according to the conditions described later.
  • an adsorption / desorption peak of hydrogen was observed at a considerably lower potential than that of a general catalyst, that is, a portion close to the equilibrium potential of hydrogen.
  • 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. From the equilibrium potential of hydrogen that occurs as UPD (underpotential deposition) of hydrogen, an adsorption phenomenon of hydrogen atoms at a noble potential was observed.
  • Example 2 A solution 2A was prepared by dispersing 14 mg of the same CNT as in Example 1 in 100 g of the mixed solvent B. The same dinitrodiammine platinum nitric acid solution as in Example 1 was diluted with ultrapure water to obtain a solution 2B containing 0.2 g / L of platinum. 30 mL of Solution 2B was added to Solution 2A. Hydrogen gas was introduced into this mixed solution by bubbling at normal pressure at 0.1 g / Hr. The temperature was 25 ° C. One hour later, the introduction of hydrogen gas was stopped, and the resulting liquid was collected by suction filtration (filter paper: No. 2, manufactured by Advantech, diameter: 110 mm). This was dried in air at 80 ° C.
  • Example 2 An electrode material of 30 mass% Pt / CNT (calculated value). 3 mg of this material was dispersed in 30 mL of mixed solvent A. 70 ⁇ L was collected with a micropipette, dropped onto the same disk electrode as in Example 1, treated with an ionomer dispersion solution as in Example 1, and dried to obtain a sample electrode 2. This sample electrode 2 was subjected to electrode characteristic evaluation. The CV curve was the same as in Example 1.
  • Example 3 As the CNT, Thin-MWCNT manufactured by Microphase was used. It is a multi-walled CNT having a D / G of 0.08, a diameter of 25 nm, and an aspect ratio of about 30 or more.
  • the electrode material of 30 mass% Pt / CNT (calculated value) was obtained in the same manner as in Example 2 except that CNT was changed. This material was treated in the same manner as in Example 2 and 3 mg was dispersed in 30 mL of mixed solvent A. 70 ⁇ L was collected with a micropipette, dropped onto the same disk electrode as in Example 1, treated with an ionomer dispersion solution in the same manner as in Example 1, and dried to obtain a sample electrode 3. This sample electrode 3 was subjected to electrode characteristic evaluation. The CV curve was the same as in Example 1.
  • Example 5 instead of CNTs, cup-stacked carbon nanofibers (CNF) were used. D / G is 0.18. The diameter was 50 nm. An electrode material of 30% by mass Pt / CNF (calculated value) was prepared in the same manner as in Example 1 to obtain a sample electrode 5, and the characteristics were evaluated in the same manner. Similar to FIG. 2 of Example 7, the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • CNF cup-stacked carbon nanofibers
  • Example 6 70 mg of CNT (same as Example 3) hydrophilized in the same manner as in Example 4 was dispersed in ethanol, and an ultrasonic wave was irradiated for 30 minutes to prepare a CNT dispersion solution.
  • a dinitrodiammine platinum nitrate solution (same as Example 1) manufactured by Ishifuku Metal Industry Co., Ltd. was evaporated to dryness at 80 ° C. using a rotary evaporator to obtain a tan powder. While maintaining the temperature at 50 ° C. or lower, ethanol was gradually added to the tan powder to prepare a platinum ammine ethoxide complex solution having a platinum concentration of 50 g / L.
  • This ethanol solution containing 30 mg in terms of platinum amount was added to the CNT dispersion solution and irradiated with ultrasonic waves for 30 minutes. It heated to 60 degreeC using the hot stirrer, and dried slowly. Thereafter, reduction was performed in an argon stream containing 10% hydrogen (volume ratio) to obtain an electrode material of 30% by mass Pt / CNT (calculated value). The temperature during the reduction was slowly raised from room temperature to 60 ° C., then raised to 120 ° C. at a rate of 5 ° C. per minute, and held for 1 hour. Thereafter, the temperature was raised to 200 ° C. at a rate of 5 ° C. per minute, held for 2 hours, and then slowly cooled to room temperature. A sample electrode 6 was obtained using this material, and the characteristics were evaluated in the same manner. Similar to FIG. 2 of Example 7, the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential.
  • Example 7 A sample electrode 7 was obtained using a commercially available catalyst (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., TEC10E50E), and the characteristics were similarly evaluated. As shown in FIG. 2, the CV curve showed a general shape in which hydrogen adsorption / desorption occurs at a relatively high potential. In particular, the oxidation / reduction current peak of hydrogen became broad, and the activity of the catalyst also decreased.
  • the peak potential of the reduction current of platinum oxide recognized around 0.6 V (Ag / AgCl electrode reference) has a difference of 70 mV. This is presumably because platinum is hardly oxidized in the electrode material of the present invention.
  • the mass activity at 0.85 V when the electrode material shown here was swept cathodic at a rate of 1.2 V to 5 mV / sec was 0.041 A / mg Pt for the electrode material of the present invention, and 0. 0051 A / mg Pt. It can be seen that the electrode material of the present invention provides high oxygen reduction activity.
  • the activity was determined by the following electrochemical measurement.
  • a cell manufactured by Hokuto Denko Co., Ltd. was used.
  • 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 measurement was performed while rotating the sample electrode at 1000 rpm. In this state, cyclic voltammetry (CV) measurement was performed.
  • Table 1 Samples 1 to 7 correspond to Examples 1 to 7 above.
  • the mass activity ratio was determined as follows.
  • the electrode material of the present invention showed an activity exceeding 2.8 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.
  • Examples 4 and 6 use CNTs subjected to hydrophilic treatment. For this reason, it is thought that platinum does not express high activity. As shown in Example 5, the activity was low even in CNF having a high D / G.
  • Example 8 In the same manner as in Example 1, 30% by mass of platinum was supported on CNTs. 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] Repeated 300 times The mass activity before and after this potential step cycle test was compared, and the reduction rate of activity was calculated.
  • Example 9 An electrode was prepared and a potential step cycle test was conducted in the same manner as in Example 8 except that ketjen black having a large specific surface area was used instead of CNT as the support.
  • Platinum has a small distance between particles on a carrier having a small specific surface area and is likely to deteriorate. Therefore, the potential fluctuation resistance of the electrode material in which platinum was supported on carbon black (KB) having a very large specific surface area by the liquid phase hydrogen reduction method and the electrode material of the present invention were compared by a potential step cycle test. As a result, as shown in Table 2, it was confirmed that the rate of decrease in activity was small even though the specific surface area of CNT was extremely small. In other words, it was shown that the activity as an electrode material hardly decreases and the durability is excellent.
  • 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. Further, it can be applied as a cathode of FED, flat fluorescent tube, and cold cathode tube. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2010-101279 filed on April 26, 2010 are cited herein as disclosure of the specification of the present invention. Incorporated.

Abstract

L'invention concerne un matériau d'électrode montrant un taux élevé de maintien, une bonne durabilité et une activité élevée, qui est formé en supportant directement du platine sur des nanotubes de carbone. En particulier, le platine supporté sur des nanotubes de carbone a été précipité de manière optimale par réduction en phase liquide. De plus, le taux crête (D / G) de la bande D et de la bande G, déterminé par spectroscopie Raman des nanotubes de carbone, est de 0,17 ou moins de façon optimale. En outre, lorsque le platine précipité par réduction en phase liquide est supporté sur des nanotubes de carbone, une extraction par réduction en phase liquide est effectuée de manière optimale par réduction hydrogénée de sel de platine.
PCT/JP2011/060084 2010-04-26 2011-04-25 Matériau d'électrode WO2011136186A1 (fr)

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JP2014504428A (ja) * 2010-12-01 2014-02-20 ハイドロ−ケベック リチウム空気バッテリ
JP2014504201A (ja) * 2010-11-26 2014-02-20 バイオニア コーポレーション 有害物質除去装置
WO2016009935A1 (fr) * 2014-07-15 2016-01-21 東レ株式会社 Matière d'électrode pour batterie métal-air
JP2019512441A (ja) * 2016-02-12 2019-05-16 フラウンホーファ−ゲゼルシャフト ツァー フォルデルング デア アンゲバンデン フォルシュンク エー． ファオ．Ｆｒａｕｎｈｏｆｅｒ−Ｇｅｓｅｌｌｓｃｈａｆｔ Ｚｕｒ Ｆｏｒｄｅｒｕｎｇ Ｄｅｒ Ａｎｇｅｗａｎｄｔｅｎ Ｆｏｒｓｃｈｕｎｇ Ｅ． Ｖ． グラフェン及びグラフェンの生産
WO2023139862A1 (fr) * 2022-01-18 2023-07-27 恒林日本株式会社 Catalyseur à nanotubes de carbone à parois multiples pour cathode de pile à combustible, et procédé de préparation dudit catalyseur

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JP2014504428A (ja) * 2010-12-01 2014-02-20 ハイドロ−ケベック リチウム空気バッテリ
US11398656B2 (en) 2010-12-01 2022-07-26 Hydro-Quebec Lithium-air battery
WO2016009935A1 (fr) * 2014-07-15 2016-01-21 東レ株式会社 Matière d'électrode pour batterie métal-air
CN106471656A (zh) * 2014-07-15 2017-03-01 东丽株式会社 金属空气电池用电极材料
JPWO2016009935A1 (ja) * 2014-07-15 2017-04-27 東レ株式会社 金属空気電池用電極材料
US10249881B2 (en) 2014-07-15 2019-04-02 Toray Industries, Inc. Electrode material for metal-air battery
JP2019512441A (ja) * 2016-02-12 2019-05-16 フラウンホーファ−ゲゼルシャフト ツァー フォルデルング デア アンゲバンデン フォルシュンク エー． ファオ．Ｆｒａｕｎｈｏｆｅｒ−Ｇｅｓｅｌｌｓｃｈａｆｔ Ｚｕｒ Ｆｏｒｄｅｒｕｎｇ Ｄｅｒ Ａｎｇｅｗａｎｄｔｅｎ Ｆｏｒｓｃｈｕｎｇ Ｅ． Ｖ． グラフェン及びグラフェンの生産
JP6993343B2 (ja) 2016-02-12 2022-01-13 アヴァダイン、 エルエルシー グラフェン及びグラフェンの生産
JP2022008546A (ja) * 2016-02-12 2022-01-13 アヴァダイン、 エルエルシー グラフェン及びグラフェンの生産
WO2023139862A1 (fr) * 2022-01-18 2023-07-27 恒林日本株式会社 Catalyseur à nanotubes de carbone à parois multiples pour cathode de pile à combustible, et procédé de préparation dudit catalyseur

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