WO2015079956A1 - アルカリ型燃料電池用炭素触媒及びその製造方法、並びにアルカリ型燃料電池用電極及びアルカリ型燃料電池 - Google Patents

アルカリ型燃料電池用炭素触媒及びその製造方法、並びにアルカリ型燃料電池用電極及びアルカリ型燃料電池 Download PDF

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WO2015079956A1
WO2015079956A1 PCT/JP2014/080401 JP2014080401W WO2015079956A1 WO 2015079956 A1 WO2015079956 A1 WO 2015079956A1 JP 2014080401 W JP2014080401 W JP 2014080401W WO 2015079956 A1 WO2015079956 A1 WO 2015079956A1
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Prior art keywords
carbon material
fuel cell
carbon
alkaline fuel
boron
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English (en)
French (fr)
Japanese (ja)
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靖雄 今城
純一 尾崎
久美 成塚
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Nisshinbo Holdings Inc
Gunma University NUC
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Nisshinbo Holdings Inc
Gunma University NUC
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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
    • H01M4/9008—Organic or organo-metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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 catalyst for an alkaline fuel cell, a method for producing the same, an electrode for an alkaline fuel cell, and an alkaline fuel cell, and more particularly to an improvement in the activity of the carbon catalyst for an alkaline fuel cell.
  • an alkaline fuel cell using an alkaline electrolyte is known as one of fuel cells, and a metal catalyst has been used as the electrode catalyst (see, for example, Patent Document 1).
  • the present invention has been made in view of the above problems, and provides an alkaline fuel cell carbon catalyst that exhibits excellent activity, a method for producing the same, an alkaline fuel cell electrode, and an alkaline fuel cell.
  • an alkaline fuel cell carbon catalyst that exhibits excellent activity
  • a method for producing the same an alkaline fuel cell electrode, and an alkaline fuel cell.
  • a carbon catalyst for an alkaline fuel cell according to an embodiment of the present invention for solving the above-described problems includes a carbon material containing nitrogen atoms and boron atoms. ADVANTAGE OF THE INVENTION According to this invention, the carbon catalyst for alkaline fuel cells which shows the outstanding activity can be provided.
  • the carbon material may not contain a metal inside.
  • the boron atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of the carbon material may be 0.001 to 0.055.
  • the boron atom / nitrogen atom ratio measured by X-ray photoelectron spectroscopy of the carbon material may be 0.1 to 2.5.
  • the carbon material may have a nitrogen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.005 to 0.035.
  • the carbon material may further contain oxygen atoms. In this case, the oxygen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of the carbon material may be 0.005 to 0.135.
  • An alkaline fuel cell electrode according to an embodiment of the present invention for solving the above-described problems includes any one of the carbon catalysts described above. ADVANTAGE OF THE INVENTION According to this invention, the electrode for alkaline fuel cells which shows the outstanding activity can be provided.
  • An alkaline fuel cell according to an embodiment of the present invention for solving the above-described problems includes the electrode. According to the present invention, an alkaline fuel cell exhibiting excellent activity can be provided.
  • a method for producing a carbon catalyst for an alkaline fuel cell includes performing nitrogen doping treatment and boron doping treatment on a carbon material so that the carbon containing nitrogen atoms and boron atoms is contained. Obtaining a carbon catalyst for an alkaline fuel cell containing the material. ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the carbon catalyst for alkaline fuel cells which shows the outstanding activity can be provided.
  • the carbon material may be subjected to the nitrogen doping treatment and the boron doping treatment on the carbon material that does not contain a metal inside.
  • the carbon material may be first subjected to the nitrogen doping process, and then the boron material may be subjected to the boron doping process after the nitrogen doping process.
  • the boron doping treatment may be a treatment for heating a mixture of the carbon material and a boron atom-containing compound.
  • the boron atom-containing compound may be boric acid.
  • a carbon catalyst for an alkaline fuel cell according to an embodiment of the present invention for solving the above-described problems is manufactured by any one of the methods described above.
  • ADVANTAGE OF THE INVENTION According to this invention, the carbon catalyst for alkaline fuel cells which shows the outstanding activity can be provided.
  • An alkaline fuel cell electrode according to an embodiment of the present invention for solving the above-described problems includes a carbon catalyst produced by any one of the above methods. ADVANTAGE OF THE INVENTION According to this invention, the electrode for alkaline fuel cells which shows the outstanding activity can be provided.
  • An alkaline fuel cell according to an embodiment of the present invention for solving the above-described problems includes an electrode including a carbon catalyst manufactured by any one of the above methods. According to the present invention, an alkaline fuel cell exhibiting excellent activity can be provided.
  • an alkaline fuel cell carbon catalyst that exhibits excellent activity, a method for producing the same, an alkaline fuel cell electrode, and an alkaline fuel cell.
  • the method includes subjecting the carbon material to nitrogen doping treatment and boron doping treatment to obtain an alkaline fuel cell carbon catalyst containing the carbon material containing nitrogen atoms and boron atoms.
  • the carbon material subjected to nitrogen doping treatment and boron doping treatment is not particularly limited as long as it has a carbon structure capable of doping nitrogen atoms and boron atoms.
  • the carbon material is, for example, one or more selected from the group consisting of carbon black, carbon nanotube, carbon nanohorn, carbon nanofiber, carbon fiber, carbon fibril, activated carbon, carbon fiber, and graphite powder. Also good.
  • this method it is good also as performing a nitrogen dope process and a boron dope process to the carbon material which does not contain a metal (for example, transition metal) inside. Moreover, in this method, it is good also as performing a nitrogen dope process and a boron dope process to the carbon material which does not contain a metal (for example, transition metal) on the surface. Moreover, in this method, it is good also as performing a nitrogen dope process and a boron dope process to the carbon material which does not contain a metal (for example, transition metal) on the surface and an inside.
  • the nitrogen doping process is not particularly limited as long as it is a process of doping nitrogen atoms into the carbon structure of the carbon material.
  • the nitrogen doping treatment may be, for example, a treatment in which a carbon material is brought into contact with a nitrogen atom-containing gas under heating (for example, 400 to 1200 ° C.).
  • the nitrogen atom-containing gas is not particularly limited as long as it is a gas containing a nitrogen atom-containing compound and is a gas in which nitrogen atoms are doped into the carbon material by contacting the carbon material with heating.
  • the nitrogen atom-containing compound contained in the nitrogen atom-containing gas is a compound having a nitrogen atom in its molecule, and a compound in which the carbon material is doped with nitrogen atoms by contacting with the carbon material under heating.
  • ammonia NH 3
  • nitric oxide nitrogen dioxide
  • acetonitrile acrylonitrile
  • pyridine pyrrole
  • pyrimidine ethylamine
  • dimethylamine trimethylamine
  • piperidine piperazine
  • aniline, N, N -It may be one or more selected from the group consisting of diisopropylethylamine and tetramethylethylenediamine.
  • the content of the nitrogen atom-containing compound in the nitrogen atom-containing gas is not particularly limited as long as the nitrogen atom is doped, but the nitrogen atom-containing gas contains, for example, 5 to 100% by volume of the nitrogen atom-containing compound. It may be included. Further, the time for bringing the carbon material into contact with the nitrogen atom-containing gas is not particularly limited as long as it is in a range in which nitrogen atoms are doped, but may be, for example, 10 to 300 minutes.
  • the nitrogen doping treatment may be, for example, a nitrogen doping treatment by an ammoxidation method.
  • a carbon material is brought into contact with an ammonia-containing gas in an atmosphere containing oxygen under heating (for example, 400 to 1200 ° C.), thereby doping the carbon material with nitrogen atoms.
  • the ammonia-containing gas may be, for example, a gas containing 5 to 100% by volume of ammonia (NH 3 ).
  • the ammonia-containing gas may be, for example, a gas containing ammonia and oxygen (for example, a gas containing ammonia and air).
  • the nitrogen doping process may be a nitrogen doping process by a CVD (Chemical Vapor Deposition) method, for example.
  • a CVD method for example, a carbon material is brought into contact with a gas containing a nitrogen atom-containing compound such as acetonitrile under heating (for example, 400 to 1200 ° C.), thereby doping the carbon material with nitrogen atoms.
  • the gas containing a nitrogen atom-containing compound may be, for example, a gas containing the nitrogen atom-containing compound and an inert gas (for example, nitrogen (N 2 ) gas and / or helium (He) gas).
  • an inert gas for example, nitrogen (N 2 ) gas and / or helium (He) gas.
  • the nitrogen doping process may be a process of heating a mixture of a carbon material and a nitrogen atom-containing compound, for example.
  • the nitrogen atom-containing compound is not particularly limited as long as it contains a nitrogen atom in its molecule.
  • the temperature at which the mixture of the carbon material and the nitrogen atom-containing compound is heated is not particularly limited as long as the carbon material is doped with nitrogen atoms, but may be, for example, 300 to 1500 ° C.
  • the boron doping process is not particularly limited as long as it is a process of doping boron atoms into the carbon structure of the carbon material.
  • the boron doping treatment may be, for example, a treatment in which a carbon material is brought into contact with a boron atom-containing gas under heating (for example, 400 to 1200 ° C.).
  • the boron atom-containing gas is a gas containing a boron atom-containing compound, and is not particularly limited as long as it is a gas in which boron atoms are doped into the carbon material by contacting with the carbon material under heating.
  • the boron atom-containing compound contained in the boron atom-containing gas is a compound containing a boron atom in the molecule, and the boron atom is doped into the carbon material by contacting with the carbon material under heating.
  • the group consisting of boron trichloride (BCl 3 ), boron trifluoride (BF 3 ), diborane (B 2 H 6 ), and trimethylboron is good as well.
  • the gas containing a boron atom-containing compound may be, for example, a gas containing the boron atom-containing compound and an inert gas (for example, nitrogen (N 2 ) gas and / or helium (He) gas).
  • an inert gas for example, nitrogen (N 2 ) gas and / or helium (He) gas.
  • the content of the boron-containing compound in the boron atom-containing gas is not particularly limited as long as boron atoms are doped, but the boron atom-containing gas may be, for example, 0.1 to 100 volumes of the boron atom-containing compound. % May be included.
  • the boron atom-containing gas when the boron atom-containing gas contains BCl 3 , the boron atom-containing gas may contain 0.1 to 100% by volume of BCl 3 and 0.5 to 5% by volume. Is preferred.
  • the time for which the carbon material is brought into contact with the boron atom-containing gas is not particularly limited as long as it is within a range in which boron atoms are doped, but may be, for example, 5 to 300 minutes.
  • the boron doping process may be a process of heating a mixture of a carbon material and a boron atom-containing compound.
  • the boron atom-containing compound is not particularly limited as long as it contains a boron atom in its molecule.
  • boron atoms can be effectively doped into the carbon material by boron doping treatment in which a mixture of the carbon material and boric acid is heated.
  • the temperature for heating the mixture of the carbon material and the boron atom-containing compound is not particularly limited as long as the carbon material is doped with boron atoms, but may be, for example, 300 to 1500 ° C.
  • the nitrogen doping treatment and boron doping treatment described above can be performed in any combination. That is, for example, the carbon material may be first subjected to nitrogen doping treatment, and then the carbon material after the nitrogen doping treatment may be subjected to boron doping treatment.
  • a carbon material containing no nitrogen atoms and boron atoms is subjected to nitrogen doping treatment, and then the carbon material containing nitrogen atoms after the nitrogen doping treatment is subjected to boron doping treatment so that nitrogen atoms and boron atoms are obtained. It is good also as obtaining the carbon material containing.
  • a nitrogen doping treatment is performed in which a carbon material is brought into contact with a nitrogen atom-containing gas under heating, and then a boron doping treatment in which the mixture of the carbon material and the boron atom-containing compound after the nitrogen doping treatment is heated. It may be done.
  • the carbon material after nitrogen doping treatment, boric acid, boron trifluoride (BF 3 ) methanol complex, 9-BBN (9-borabicyclo [3.3.1] nonane), boron carbide (B 4 C) and the boron doped may be performed by heating a mixture of at least one member selected from the group consisting of boron oxide (B 2 O 3).
  • boron atoms can be effectively doped into the carbon material by performing a boron doping treatment in which a mixture of the carbon material and the boric acid after the nitrogen doping treatment is heated.
  • a nitrogen doping treatment is performed in which a carbon material is brought into contact with a nitrogen atom-containing gas under heating, and then a boron doping treatment in which the carbon material after the nitrogen doping treatment is brought into contact with a boron atom-containing gas under heating. It may be done.
  • the above nitrogen doping treatment and boron doping treatment are performed to obtain a carbon material doped with nitrogen atoms and boron atoms.
  • the carbon material containing nitrogen atoms and boron atoms thus obtained itself exhibits catalytic activity as a carbon catalyst for alkaline fuel cells. Therefore, in this method, a carbon material containing nitrogen atoms and boron atoms after the above nitrogen doping treatment and boron doping treatment may be obtained as a carbon catalyst for an alkaline fuel cell.
  • This catalyst is a carbon catalyst for alkaline fuel cells containing a carbon material containing nitrogen atoms and boron atoms. That is, the carbon material of the present catalyst has a carbon structure containing nitrogen atoms and boron atoms. This carbon material itself exhibits catalytic activity in an alkaline fuel cell.
  • the catalyst is a carbon catalyst used for an alkaline fuel cell (more specifically, a carbon catalyst used for an electrode of an alkaline fuel cell).
  • the present catalyst is preferably produced by the above-described method. That is, this catalyst is good also as a carbon material containing a nitrogen atom and a boron atom obtained by performing a nitrogen dope process and a boron dope process to a carbon material as mentioned above.
  • the carbon material of the catalyst may not contain a metal (for example, a transition metal) inside. That is, in this case, the catalyst contains a carbon material containing nitrogen atoms and boron atoms, and containing no metal inside. Further, the present catalyst includes a carbon material containing nitrogen atoms and boron atoms obtained by subjecting a carbon material containing no metal to nitrogen inside and boron doping, and containing no carbon inside. Also good.
  • a metal for example, a transition metal
  • the carbon material of the present catalyst may not include a metal (for example, a transition metal) on the surface.
  • the carbon material of this catalyst is good also as a surface containing no noble metal.
  • the carbon material of this catalyst is good also as not including a metal (for example, transition metal) in the surface and an inside.
  • the boron atom / carbon atom ratio (B / C ratio) measured by X-ray photoelectron spectroscopy of the carbon material of the present catalyst may be 0.001 to 0.055. It is preferable that the B / C ratio of the carbon material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the B / C ratio of the carbon material of the present catalyst may be, for example, 0.003 to 0.055. It is more preferable that the B / C ratio of the carbon material of the present catalyst is within this range in view of excellent catalytic activity of the present catalyst.
  • the B / C ratio of the carbon material of the present catalyst may be, for example, 0.006 to 0.055, 0.010 to 0.055, or 0.020 to 0.00. It may be 055, 0.030 to 0.055, or 0.040 to 0.055. It is particularly preferable that the B / C ratio of the carbon material of the present catalyst is within these ranges in view of the excellent catalytic activity of the present catalyst. Moreover, there exists a tendency for the catalyst activity of this catalyst to improve as the B / C ratio of the carbon material of this catalyst increases.
  • the boron atom / nitrogen atom ratio (B / N ratio) measured by X-ray photoelectron spectroscopy of the carbon material of the present catalyst may be 0.1 to 2.5. It is preferable that the B / N ratio of the carbon material of the present catalyst is within this range in view of the excellent catalytic activity of the present catalyst.
  • the B / N ratio of the carbon material of the present catalyst may be, for example, 0.3 to 2.5, 0.5 to 2.5, 1.0 to 2. 5 or 1.5 to 2.5. It is particularly preferable that the B / N ratio of the carbon material of the present catalyst is within these ranges in view of the excellent catalytic activity of the present catalyst. Moreover, there exists a tendency for the catalyst activity of this catalyst to improve as the B / N ratio of the carbon material of this catalyst increases.
  • the nitrogen atom / carbon atom ratio (N / C ratio) measured by X-ray photoelectron spectroscopy of the carbon material of the present catalyst may be 0.005 to 0.035. It is preferable that the N / C ratio of the carbon material of the present catalyst is within this range in order that the present catalyst exhibits excellent catalytic activity.
  • the N / C ratio of the carbon material of the present catalyst may be, for example, 0.015 to 0.035, or 0.02 to 0.035. It is more preferable that the N / C ratio of the carbon material of the present catalyst is within these ranges in view of the excellent catalytic activity of the present catalyst.
  • the carbon material of the present catalyst may further contain oxygen atoms.
  • the oxygen atom / carbon atom ratio (O / C ratio) measured by X-ray photoelectron spectroscopy of the carbon material of the present catalyst may be 0.005 to 0.135. It is preferable that the O / C ratio of the carbon material of the present catalyst is within this range in view of the excellent catalytic activity of the present catalyst.
  • the O / C ratio of the carbon material of the present catalyst may be, for example, 0.050 to 0.135. It is more preferable that the O / C ratio of the carbon material of the present catalyst is within this range in view of the excellent catalytic activity of the present catalyst.
  • the O / C ratio of the carbon material of the present catalyst may be, for example, 0.100 to 0.135. It is particularly preferable that the O / C ratio of the carbon material of the present catalyst is within this range in view of the excellent catalytic activity of the present catalyst.
  • the B / C ratio, N / C ratio, B / N ratio, and O / C ratio described above are arbitrarily combined. That is, for example, the B / C ratio of the carbon material of the present catalyst may be 0.001 to 0.055, and the B / N ratio of the carbon material may be 0.1 to 2.5. In this case, the N / C ratio of the carbon material of the present catalyst may be 0.005 to 0.035. Further, the O / C ratio of the carbon material of the present catalyst may be 0.005 to 0.135. It is preferable that the surface element ratio of the carbon material of the present catalyst is a combination of these ranges in order that the present catalyst exhibits excellent catalytic activity.
  • the B / C ratio of the carbon material of the present catalyst may be 0.003 to 0.055, and the B / N ratio of the carbon material may be 0.1 to 2.5.
  • the N / C ratio of the carbon material of the present catalyst may be 0.015 to 0.035.
  • the O / C ratio of the carbon material of the present catalyst may be 0.050 to 0.135. It is more preferable that the surface element ratio of the carbon material of the present catalyst is a combination of these ranges in order that the present catalyst exhibits excellent catalytic activity.
  • the B / C ratio of the carbon material of the present catalyst may be 0.006 to 0.055, and the B / N ratio of the carbon material may be 0.3 to 2.5.
  • the B / C ratio of the carbon material of the present catalyst may be 0.010 to 0.055, 0.020 to 0.055, or 0.030 to 0.055. It may be, or may be 0.040 to 0.055.
  • the B / N ratio of the carbon material may be 0.5 to 2.5, or may be 1.0 to 2.5.
  • the N / C ratio of the carbon material of the present catalyst may be 0.015 to 0.035, or may be 0.02 to 0.035.
  • the O / C ratio of the carbon material of the present catalyst may be 0.100 to 0.135. It is particularly preferable that the surface element ratio of the carbon material of the present catalyst is a combination of these ranges in view of the superior catalytic activity of the present catalyst.
  • This catalyst exhibits, for example, oxygen reduction activity as one of its catalytic activities.
  • the oxygen reduction activity of the present catalyst is evaluated by, for example, the current density when the present catalyst is used as an electrode catalyst in an alkaline electrolyte.
  • this current density is, for example, data indicating the relationship between voltage and current density obtained when a potential is swept and applied using a rotating ring disk electrode device having a working electrode coated with this catalyst (oxygen reduction voltammogram).
  • the current density at a voltage of 0 (zero) V is obtained.
  • the catalysts include, for example, is good, it may show 0.30 mA / cm 2 or more of the current density as to exhibit a 0.20mA / cm 2 or more of the current density, 0.40mA / cm more preferably to exhibit 2 or more of the current density, more preferably to exhibit 0.50 mA / cm 2 or more of the above current density, it is particularly preferable to indicate the 0.60mA / cm 2 or more of the current density.
  • the upper limit value of the current density is not particularly limited, but the current density may be, for example, 4.0 mA / cm 2 or less.
  • oxygen reduction activity of the present catalyst is evaluated by, for example, the oxygen reduction starting potential when the present catalyst is used as an electrode catalyst in an alkaline electrolyte.
  • Oxygen reduction starting potential is, for example, data indicating the relationship between voltage and current density obtained by sweeping the potential using a rotating ring disk electrode device having a working electrode coated with this catalyst (oxygen reduction voltammogram). Is obtained as a voltage (E O2 ) when a reduction current of ⁇ 10 ⁇ A / cm 2 flows.
  • the present catalyst is, for example, oxygen of 0.07 V (vs. NHE) or more (more specifically, for example, 0.07 V (vs. NHE) or more and 1.2 V (vs. NHE) or less).
  • a reduction start potential may be indicated, and an oxygen reduction start potential of 0.08 V (vs. NHE) or more is preferable.
  • the electrode for an alkaline fuel cell (main electrode) is an electrode for an alkaline fuel cell including the above-described catalyst. That is, this electrode is, for example, an electrode on which the present catalyst is supported. Specifically, the present electrode is an electrode including, for example, an electrode base material and the present catalyst supported on the electrode base material. This electrode is used, for example, as a cathode (oxygen electrode) for an alkaline fuel cell.
  • the alkaline fuel cell (main battery) according to the present embodiment includes the above-described main electrode. That is, this battery is, for example, an alkaline fuel cell that includes the above-described electrode as a cathode (oxygen electrode).
  • the carbon material was doped with nitrogen atoms. That is, 300 mg of carbon black (Vulcan: XC-72) as a carbon material was fixed in a quartz tube, and the quartz tube was placed in an electric furnace. In the electric furnace, the carbon material in the quartz tube was heated in a nitrogen atmosphere to increase the temperature from room temperature to 600 ° C.
  • carbon black Vulcan: XC-72
  • the carbon material was held at 600 ° C. for 2 hours while flowing a mixed gas of ammonia (NH 3 ) and air (NH 3 concentration: 70 vol%) at a flow rate of 200 mL / min in the electric furnace. Then, the electric furnace was opened and air-cooled, and the carbon material was taken out. Thus, a carbon material containing a nitrogen atom was obtained by the ammoxidation method.
  • NH 3 ammonia
  • air NH 3 concentration: 70 vol%
  • boron atoms were doped into the carbon material. That is, by immersing 1000 mg of the carbon material containing nitrogen atoms obtained as described above in 200 mL of an aqueous solution containing boric acid at a concentration of 1250 mg / L at 80 ° C. for 1 hour, 100 parts by weight of the carbon material 20 parts by weight of boric acid was mixed, and the carbon material was impregnated with boric acid.
  • the carbon material was held at 1000 ° C. for 1 hour in an electric furnace. Then, the electric furnace was opened and air-cooled, and the carbon material was taken out. Thus, a carbon material containing nitrogen atoms and boron atoms was obtained as a carbon catalyst for an alkaline fuel cell.
  • the carbon material was doped with nitrogen atoms. That is, 200 mg of carbon black (Vulcan: XC-72) as a carbon material was fixed in a quartz tube, and the quartz tube was placed in an electric furnace. In the electric furnace, the carbon material in the quartz tube was heated in a nitrogen atmosphere to increase the temperature from room temperature to 600 ° C.
  • carbon black Vulcan: XC-72
  • the carbon material was held at 600 ° C. for 2 hours while flowing a mixed gas of ammonia (NH 3 ) and air (NH 3 concentration: 70 vol%) at a flow rate of 200 mL / min in the electric furnace.
  • a mixed gas of ammonia (NH 3 ) and air NH 3 concentration: 70 vol%) at a flow rate of 200 mL / min in the electric furnace.
  • the carbon material was doped with boron atoms. That is, after doping the carbon material with nitrogen atoms as described above, the mixed gas of ammonia (NH 3 ) and air is first replaced with nitrogen (N 2 ) gas without lowering the temperature in the electric furnace. Then, the nitrogen (N 2 ) gas was replaced with a BCl 3 / N 2 mixed gas (BCl 3 concentration was 1% by volume).
  • Example 3 First, in the same manner as in Example 1, the carbon material (carbon black (Vulcan: XC-72)) was doped with nitrogen atoms by an ammoxidation method.
  • the carbon material was doped with boron atoms. That is, 100 mg of the carbon material containing nitrogen atoms obtained as described above was mixed with 12 mL of boron trifluoride (BF 3 ) methanol complex (BF 3 : 15%).
  • this mixture was heated in an electric furnace and held at 1000 ° C. for 1 hour. Then, the electric furnace was opened and air-cooled, and the carbon material was taken out. Thus, a carbon material containing nitrogen atoms and boron atoms was obtained.
  • Example 2 A carbon material doped with nitrogen atoms and not doped with boron atoms was prepared. That is, in the same manner as in Example 1 described above, carbon atoms doped with nitrogen atoms were obtained by doping carbon black (Vulcan: XC-72) with nitrogen atoms.
  • Example 3 A carbon material in which nitrogen atoms are doped and boron atoms are not doped was prepared.
  • the carbon material was subjected to heat treatment after doping with nitrogen atoms. That is, first, in the same manner as in Example 1, the carbon material (carbon black (Vulcan: XC-72)) was doped with nitrogen atoms. Thereafter, the mixed gas of ammonia (NH 3 ) and air in the electric furnace was replaced with nitrogen (N 2 ) gas.
  • a carbon material doped with boron atoms and not doped with nitrogen atoms was prepared. That is, by immersing 1000 mg of carbon black (Vulcan: XC-72) in 200 mL of an aqueous solution containing boric acid at a concentration of 1250 mg / L for 1 hour at room temperature, 20 parts by weight of boric acid was added to 100 parts by weight of the carbon material. Was impregnated.
  • carbon black Vulcan: XC-72
  • the carbon material was held at 1000 ° C. for 1 hour in an electric furnace. Then, the electric furnace was opened and air-cooled, and the carbon material was taken out. Thus, a carbon material doped with boron atoms was obtained.
  • X-ray photoelectron spectroscopy The carbon material obtained as described above was analyzed by X-ray photoelectron spectroscopy (XPS). That is, the surface element of the carbon material was analyzed by an X-ray photoelectron spectrometer (Kratos AXIS NOVA, manufactured by Shimadzu Corporation) (X-ray: AlK ⁇ ray, output: 10 mA ⁇ 15 kV). Specifically, the surface element concentrations (%) of carbon atoms, boron atoms, nitrogen atoms and oxygen atoms are determined from the area of each peak of the spectrum obtained by XPS measurement and the detection sensitivity coefficient, and the concentration of each element is calculated.
  • XPS X-ray photoelectron spectroscopy
  • the ratio of boron atom to carbon atom (B / C ratio), ratio of nitrogen atom to carbon atom (N / C ratio), and ratio of oxygen atom to carbon atom (O / C ratio) on the surface Calculated.
  • the background for quantitative calculation was determined by the Shirley method.
  • a catalyst slurry was prepared. Specifically, 5 mg of the carbon material obtained as described above, 25 ⁇ L of binder solution (Nafion (registered trademark), DuPont), 200 ⁇ L of ultrapure water, 175 ⁇ L of ethanol, and 2 cups of spatula (About 15 particles) glass beads (diameter 1 mm) were mixed and subjected to ultrasonic treatment for 20 minutes to obtain a catalyst slurry.
  • binder solution Nafion (registered trademark), DuPont
  • 200 ⁇ L of ultrapure water 175 ⁇ L of ethanol
  • 2 cups of spatula (About 15 particles) glass beads were mixed and subjected to ultrasonic treatment for 20 minutes to obtain a catalyst slurry.
  • 1.8 ⁇ L of the catalyst slurry described above was sucked up with a pipette and applied to the disk electrode (0.1256 cm 2 ) of the rotating ring disk electrode device (RRDE-3A Ver. 1.2S, manufactured by BAS Inc.).
  • the working electrode was prepared by drying.
  • a platinum electrode was used as the ring electrode.
  • a saturated potassium chloride / silver chloride (Ag / AgCl) electrode was used as a reference electrode.
  • As the alkaline electrolyte a 0.1 M aqueous potassium hydroxide solution in which oxygen was dissolved at room temperature was used.
  • linear sweep voltammetry was performed using an electrochemical analyzer (CHI700B, manufactured by ALS Co., Ltd.).
  • CHI700B manufactured by ALS Co., Ltd.
  • NHE standard hydrogen electrode
  • the measurement was started.
  • the electrode was rotated at a rotational speed of 1500 rpm, and at 25 ° C., the sweep speed was 1 mV / second and the voltage was 0.1 V (vs. Ag / AgCl) to ⁇ 0.6 V (vs. Ag). / AgCl), the potential was swept, and the value of the current flowing through the working electrode was measured. That is, in terms of the standard hydrogen electrode (NHE) reference value, the potential was swept from 0.3 V (vs. NHE) to -0.4 V (vs. NHE).
  • NHE standard hydrogen electrode
  • the current flowing at this time was recorded as a function of potential. From the obtained polarization curve, the voltage when a reduction current of ⁇ 10 ⁇ A / cm 2 flows was recorded as “oxygen reduction starting potential (EO 2 )” (V vs. NHE). The current density (mA / cm 2 ) when a potential of 0 V (vs. NHE) was applied was also recorded as “I 0 V ”.
  • FIG. 1 shows the surface element ratio and the catalytic activity evaluated for each carbon material. That is, FIG. 1 shows the B / C ratio, N / C ratio, B / N ratio, and O / C ratio on the surface of each carbon material, and the current density at a voltage of 0 V (I 0v (mA / cm 2 )). And the oxygen reduction starting potential (E Albany 2 (V vs. NHE)).
  • Example 1 in which boron doping treatment for heating a mixture of a carbon material and boric acid after nitrogen doping treatment was performed, boron atoms could be effectively doped into the carbon material.
  • the B / N ratio of the carbon material obtained in Example 1 was significantly larger than that in Examples 2 and 3. Further, as shown in “O / C ratio” of FIG. 1, in Examples 1 to 3 and Comparative Examples 2 to 4, it was confirmed that oxygen atoms were introduced into the carbon material.
  • the carbon materials of Examples 1 to 3 showed significantly superior catalytic activity as compared with the carbon materials of Comparative Examples 1 to 4. Further, the carbon materials of Examples 1 and 2 showed a larger current density than the carbon material of Example 3, and the carbon material of Example 1 showed a particularly large current density.

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