JP6254431B2 - Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell - Google Patents
Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell Download PDFInfo
- Publication number
- JP6254431B2 JP6254431B2 JP2013248556A JP2013248556A JP6254431B2 JP 6254431 B2 JP6254431 B2 JP 6254431B2 JP 2013248556 A JP2013248556 A JP 2013248556A JP 2013248556 A JP2013248556 A JP 2013248556A JP 6254431 B2 JP6254431 B2 JP 6254431B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon material
- carbon
- catalyst
- boron
- alkaline fuel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims description 118
- 239000000446 fuel Substances 0.000 title claims description 56
- 229910052799 carbon Inorganic materials 0.000 title claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 184
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 77
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims description 72
- 229910052796 boron Inorganic materials 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000001721 carbon Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 239000007789 gas Substances 0.000 description 46
- 238000000034 method Methods 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 26
- 230000008569 process Effects 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 230000000694 effects Effects 0.000 description 13
- 239000010453 quartz Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo(3.3.1)nonane Chemical compound C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000010757 Reduction Activity Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polybenzoimidazole Chemical compound 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XQYHODZQMBWRQD-UHFFFAOYSA-M [Ag]Cl.[K] Chemical class [Ag]Cl.[K] XQYHODZQMBWRQD-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001088 polycarbazole Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
-
- 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
Description
本発明は、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に関し、特に、アルカリ型燃料電池用炭素触媒の活性の向上に関する。 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 activity of the carbon catalyst for an alkaline fuel cell.
従来、燃料電池の一つとして、アルカリ電解液を使用するアルカリ型燃料電池が知られており、その電極触媒としては金属触媒が使用されていた（例えば、特許文献１参照）。 Conventionally, an alkaline fuel cell using an alkaline electrolyte is known as one of the fuel cells, and a metal catalyst has been used as the electrode catalyst (see, for example, Patent Document 1).
しかしながら、従来、アルカリ型燃料電池用の炭素触媒として、十分な活性を有するものはなかった。 However, heretofore, no carbon catalyst for alkaline fuel cells has sufficient activity.
本発明は、上記課題に鑑みて為されたものであり、優れた活性を示す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を提供することをその目的の一つとする。 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. One of its purposes.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池用炭素触媒は、窒素原子及びホウ素原子を含む炭素材料を含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池用炭素触媒を提供することができる。 An alkaline fuel cell carbon catalyst according to an embodiment of the present invention for solving the above-described problems includes a carbon material containing a nitrogen atom and a boron atom. ADVANTAGE OF THE INVENTION According to this invention, the carbon catalyst for alkaline fuel cells which shows the outstanding activity can be provided.
また、前記アルカリ型燃料電池用炭素触媒において、前記炭素材料は、内部に金属を含まないこととしてもよい。また、前記炭素材料のＸ線光電子分光法により測定されるホウ素原子／炭素原子比が０．００１〜０．０５５であることとしてもよい。また、前記炭素材料のＸ線光電子分光法により測定されるホウ素原子／窒素原子比が０．１〜２．５であることとしてもよい。また、前記炭素材料のＸ線光電子分光法により測定される窒素原子／炭素原子比が０．００５〜０．０３５であることとしてもよい。また、前記炭素材料は酸素原子をさらに含むこととしてもよい。この場合、前記炭素材料のＸ線光電子分光法により測定される酸素原子／炭素原子比が０．００５〜０．１３５であることとしてもよい。 In the carbon catalyst for an alkaline fuel cell, the carbon material may not contain a metal inside. The carbon material may have a boron atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.001 to 0.055. Moreover, it is good also as a boron atom / nitrogen atom ratio measured by the X ray photoelectron spectroscopy of the said carbon material being 0.1-2.5. 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.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池用電極は、前記いずれかの炭素触媒を含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池用電極を提供することができる。 An electrode for an alkaline fuel cell according to an embodiment of the present invention for solving the above-described problems includes any one of the above carbon catalysts. ADVANTAGE OF THE INVENTION According to this invention, the electrode for alkaline fuel cells which shows the outstanding activity can be provided.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池は、前記電極を含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池を提供することができる。 An alkaline fuel cell according to an embodiment of the present invention for solving the above problems includes the electrode. According to the present invention, an alkaline fuel cell exhibiting excellent activity can be provided.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池用炭素触媒の製造方法は、炭素材料に窒素ドープ処理及びホウ素ドープ処理を施して、窒素原子及びホウ素原子を含む前記炭素材料を含むアルカリ型燃料電池用炭素触媒を得ることを含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池用炭素触媒の製造方法を提供することができる。 In order to solve the above problems, a method for producing a carbon catalyst for an alkaline fuel cell according to an embodiment of the present invention 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.
また、前記製造方法において、前記炭素材料は、内部に金属を含まない前記炭素材料に前記窒素ドープ処理及び前記ホウ素ドープ処理を施すこととしてもよい。また、前記製造方法において、まず前記炭素材料に前記窒素ドープ処理を施し、次いで、前記窒素ドープ処理後の前記炭素材料に前記ホウ素ドープ処理を施すこととしてもよい。また、前記製造方法において、前記ホウ素ドープ処理は、前記炭素材料とホウ素原子含有化合物との混合物を加熱する処理であることとしてもよい。この場合、前記ホウ素原子含有化合物は、ホウ酸であることとしてもよい。 Moreover, in the said manufacturing method, the said carbon material is good also as performing the said nitrogen dope process and the said boron dope process to the said carbon material which does not contain a metal inside. In the manufacturing method, 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. In the manufacturing method, the boron doping treatment may be a treatment for heating a mixture of the carbon material and a boron atom-containing compound. In this case, the boron atom-containing compound may be boric acid.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池用炭素触媒は、前記いずれかの方法により製造されたことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池用炭素触媒を提供することができる。 A carbon catalyst for an alkaline fuel cell according to an embodiment of the present invention for solving the above-mentioned 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.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池用電極は、前記いずれかの方法により製造された炭素触媒を含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池用電極を提供することができる。 An electrode for an alkaline fuel cell 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.
上記課題を解決するための本発明の一実施形態に係るアルカリ型燃料電池は、前記いずれかの方法により製造された炭素触媒を含む電極を含むことを特徴とする。本発明によれば、優れた活性を示すアルカリ型燃料電池を提供することができる。 An alkaline fuel cell according to an embodiment of the present invention for solving the above problems includes an electrode including a carbon catalyst produced by any one of the above methods. According to the present invention, an alkaline fuel cell exhibiting excellent activity can be provided.
本発明によれば、優れた活性を示す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を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the carbon catalyst for alkaline fuel cells which shows the outstanding activity, its manufacturing method, the electrode for alkaline fuel cells, and an alkaline fuel cell can be provided.
以下に、本発明の一実施形態について説明する。なお、本発明は本実施形態で示す例に限られない。 Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the example shown in the present embodiment.
まず、本実施形態に係るアルカリ型燃料電池用炭素触媒の製造方法（本方法）について説明する。本方法は、炭素材料に窒素ドープ処理及びホウ素ドープ処理を施して、窒素原子及びホウ素原子を含む当該炭素材料を含むアルカリ型燃料電池用炭素触媒を得ることを含む。 First, the manufacturing method (this method) of the carbon catalyst for alkaline fuel cells which concerns on this embodiment is demonstrated. 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.
本方法において、窒素ドープ処理及びホウ素ドープ処理を施す炭素材料は、窒素原子及びホウ素原子をドープできる炭素構造を有する材料であれば特に限られない。具体的に、炭素材料は、例えば、カーボンブラック、カーボンナノチューブ、カーボンナノホーン、カーボンナノファイバー、カーボンファイバー、カーボンフィブリル、活性炭、炭素繊維及び黒鉛粉末からなる群より選択される１種以上であることとしてもよい。 In this method, the carbon material subjected to nitrogen doping treatment and boron doping treatment is not particularly limited as long as it is a material having a carbon structure capable of doping nitrogen atoms and boron atoms. Specifically, 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.
また、本方法においては、内部に金属（例えば、遷移金属）を含まない炭素材料に窒素ドープ処理及びホウ素ドープ処理を施すこととしてもよい。また、本方法においては、表面に金属（例えば、遷移金属）を含まない炭素材料に窒素ドープ処理及びホウ素ドープ処理を施すこととしてもよい。また、本方法においては、表面及び内部に金属（例えば、遷移金属）を含まない炭素材料に窒素ドープ処理及びホウ素ドープ処理を施すこととしてもよい。 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) 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.
窒素ドープ処理は、炭素材料の炭素構造に窒素原子をドープする処理であれば、特に限られない。窒素ドープ処理は、例えば、炭素材料を加熱下（例えば、４００〜１２００℃）で窒素原子含有ガスと接触させる処理であることとしてもよい。 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.).
窒素原子含有ガスは、窒素原子含有化合物を含むガスであって、炭素材料と加熱下で接触することにより、当該炭素材料に窒素原子がドープされるようなガスであれば特に限られない。 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.
窒素原子含有ガスに含まれる窒素原子含有化合物は、その分子内に窒素原子を有する化合物であって、炭素材料と加熱下で接触することにより、当該炭素材料に窒素原子がドープされるような化合物であれば特に限られないが、例えば、アンモニア（ＮＨ３）、一酸化窒素、二酸化窒素、アセトニトリル、アクリロニトリル、ピリジン、ピロール、ピリミジン、エチルアミン、ジメチルアミン、トリメチルアミン、ピペリジン、ピペラジン、アニリン、Ｎ，Ｎ−ジイソプロピルエチルアミン及びテトラメチルエチレンジアミンからなる群より選択される１種以上であることとしてもよい。 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. For example, 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.
窒素原子含有ガスにおける窒素原子含有化合物の含有量は、窒素原子がドープされる範囲であれば特に限られないが、当該窒素原子含有ガスは、例えば、当該窒素原子含有化合物を５〜１００体積％含むこととしてもよい。また、炭素材料を窒素原子含有ガスと接触させる時間は、窒素原子がドープされる範囲であれば特に限られないが、例えば、１０〜３００分であることとしてもよい。 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 is, for example, 5 to 100% by volume of the nitrogen atom-containing compound. It may be included. Moreover, the time for which the carbon material is brought into contact with the nitrogen atom-containing gas is not particularly limited as long as it is a range in which nitrogen atoms are doped, but may be, for example, 10 to 300 minutes.
窒素ドープ処理は、例えば、アンモオキシデーション法による窒素ドープ処理であることとしてもよい。アンモオキシデーション法においては、例えば、炭素材料を加熱下（例えば、４００〜１２００℃）で、酸素を含む雰囲気中、アンモニア含有ガスと接触させることにより、当該炭素材料に窒素原子をドープする。 The nitrogen doping process may be, for example, a nitrogen doping process by an ammoxidation method. In the ammoxidation method, for example, 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.
アンモニア含有ガスは、例えば、アンモニア（ＮＨ３）を５〜１００体積％含むガスであることとしてもよい。なお、アンモニア含有ガスは、例えば、アンモニアと酸素とを含むガス（例えば、アンモニアと空気とを含むガス）であることとしてもよい。 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).
また、窒素ドープ処理は、例えば、ＣＶＤ（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）法による窒素ドープ処理であることとしてもよい。ＣＶＤ法においては、例えば、炭素材料を加熱下（例えば、４００〜１２００℃）、アセトニトリル等の窒素原子含有化合物を含むガスと接触させることにより、当該炭素材料に窒素原子をドープする。 Further, the nitrogen doping treatment may be, for example, a nitrogen doping treatment by a CVD (Chemical Vapor Deposition) method. In the CVD method, for example, the 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.
窒素原子含有化合物を含むガスは、例えば、当該窒素原子含有化合物と不活性ガス（例えば、窒素（Ｎ２）ガス及び／又はヘリウム（Ｈｅ）ガス）とを含むガスであることとしてもよい。 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).
また、窒素ドープ処理は、例えば、炭素材料と窒素原子含有化合物との混合物を加熱する処理であることとしてもよい。窒素原子含有化合物は、その分子内に窒素原子を含む化合物であれば特に限られず、例えば、アクリロニトリル、ポリアクリロニトリル、メラミン、メラミン樹脂、ピロール、ポリピロール、３−メチルポリピロール、ポリビニルピロール、チアゾール、ピラゾール、ビニルピリジン、ポリビニルピリジン、ピリダジン、ピリミジン、ピペラジン、イミダゾール、１−メチルイミダゾール、２−メチルイミダゾ−ル、キノキサリン、アニリン、ポリアニリン、ベンゾイミダゾ−ル、ポリベンゾイミダゾ−ル、ヒドラジン、ポリカルバゾール、トリアジン、ポリカルボジイミド、キレート樹脂、ポリアミドイミド樹脂、ポリアクリロニトリル−ポリメタクリル酸共重合体、オキサゾール、モルホリン、コハク酸ジヒドラジド、アジピン酸ジヒドラジド、ポリビスマレイミド、ポリアミノビスマレイミド、ポリイミド、ポリアクリルアミド、ポリアミド、キチン、キトサン、タンパク質、ペプチド、アミノ酸、ポリアミノ酸、核酸、ヒドラジド、尿素、サレン、ポリウレタン及びポリアミドアミンからなる群より選択される１種以上であることとしてもよい。 Further, the nitrogen doping treatment may be, for example, a treatment for heating a mixture of a carbon material and a nitrogen atom-containing compound. The nitrogen atom-containing compound is not particularly limited as long as the compound contains a nitrogen atom in the molecule, for example, acrylonitrile, polyacrylonitrile, melamine, melamine resin, pyrrole, polypyrrole, 3-methylpolypyrrole, polyvinylpyrrole, thiazole, pyrazole, Vinylpyridine, polyvinylpyridine, pyridazine, pyrimidine, piperazine, imidazole, 1-methylimidazole, 2-methylimidazole, quinoxaline, aniline, polyaniline, benzimidazole, polybenzoimidazole, hydrazine, polycarbazole, triazine, Polycarbodiimide, chelate resin, polyamideimide resin, polyacrylonitrile-polymethacrylic acid copolymer, oxazole, morpholine, succinic dihydrazide, adipic acid dihydride 1 selected from the group consisting of zido, polybismaleimide, polyaminobismaleimide, polyimide, polyacrylamide, polyamide, chitin, chitosan, protein, peptide, amino acid, polyamino acid, nucleic acid, hydrazide, urea, salen, polyurethane and polyamidoamine It may be more than seeds.
炭素材料と窒素原子含有化合物との混合物を加熱する温度は、当該炭素材料に窒素原子がドープされる温度であれば特に限られないが、例えば、３００〜１５００℃であることとしてもよい。 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.
ホウ素ドープ処理は、炭素材料の炭素構造にホウ素原子をドープする処理であれば、特に限られない。ホウ素ドープ処理は、例えば、炭素材料を加熱下（例えば、４００〜１２００℃）でホウ素原子含有ガスと接触させる処理であることとしてもよい。 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.).
ホウ素原子含有ガスは、ホウ素原子含有化合物を含むガスであって、炭素材料と加熱下で接触することにより、当該炭素材料にホウ素原子がドープされるようなガスであれば特に限られない。 The boron atom-containing gas is not particularly limited as long as it is a gas containing a boron atom-containing compound and is a gas in which boron atoms are doped into the carbon material by contacting the carbon material with heating.
ホウ素原子含有ガスに含まれるホウ素原子含有化合物は、その分子内にホウ素原子を含む化合物であって、炭素材料と加熱下で接触することにより、当該炭素材料にホウ素原子がドープされるような化合物であれば特に限られないが、例えば、三塩化ホウ素（ＢＣｌ３）、三フッ化ホウ素（ＢＦ３）、ジボラン（Ｂ２Ｈ６）及びトリメチルボロンからなる群より選択される１種以上であることとしてもよい。 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. Although not particularly limited, for example, one or more selected from the group consisting of boron trichloride (BCl 3 ), boron trifluoride (BF 3 ), diborane (B 2 H 6 ), and trimethylboron. It is good as well.
また、ホウ素原子含有化合物を含むガスは、例えば、当該ホウ素原子含有化合物と不活性ガス（例えば、窒素（Ｎ２）ガス及び／又はヘリウム（Ｈｅ）ガス）とを含むガスであることとしてもよい。 Moreover, 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). .
ホウ素原子含有ガスにおけるホウ素含有化合物の含有量は、ホウ素原子がドープされる範囲であれば特に限られないが、当該ホウ素原子含有ガスは、例えば、当該ホウ素原子含有化合物を０．１〜１００体積％含むこととしてもよい。 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.
より具体的に、例えば、ホウ素原子含有ガスがＢＣｌ３を含む場合、当該ホウ素原子含有ガスは、ＢＣｌ３を０．１〜１００体積％含むこととしてもよく、０．５〜５体積％含むことが好ましい。炭素材料をホウ素原子含有ガスと接触させる時間は、ホウ素原子がドープされる範囲であれば特に限られないが、例えば、５〜３００分であることとしてもよい。 More specifically, for example, 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.
また、ホウ素ドープ処理は、炭素材料とホウ素原子含有化合物との混合物を加熱する処理であることとしてもよい。ホウ素原子含有化合物は、その分子内にホウ素原子を含む化合物であれば特に限られず、例えば、ホウ酸、三フッ化ホウ素（ＢＦ３）メタノール錯体、９−ＢＢＮ（９−ボラビシクロ［３．３．１］ノナン）、炭化ホウ素（Ｂ４Ｃ）及び酸化ホウ素（Ｂ２Ｏ３）からなる群より選択される１種以上であることとしてもよい。特に、炭素材料とホウ酸との混合物を加熱するホウ素ドープ処理により、当該炭素材料に、ホウ素原子を効果的にドープすることができる。 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. For example, boric acid, boron trifluoride (BF 3 ) methanol complex, 9-BBN (9-borabicyclo [3.3. 1] One or more selected from the group consisting of nonane), boron carbide (B 4 C), and boron oxide (B 2 O 3 ). In particular, 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.
炭素材料とホウ素原子含有化合物との混合物を加熱する温度は、当該炭素材料にホウ素原子がドープされる温度であれば特に限られないが、例えば、３００〜１５００℃であることとしてもよい。 The temperature at which the mixture of the carbon material and the boron atom-containing compound is heated is not particularly limited as long as the carbon material is doped with boron atoms, but may be, for example, 300 to 1500 ° C.
本方法において、上述した窒素ドープ処理とホウ素ドープ処理とは、任意に組み合わせて行うことができる。すなわち、例えば、まず炭素材料に窒素ドープ処理を施し、次いで、当該窒素ドープ処理後の当該炭素材料にホウ素ドープ処理を施すこととしてもよい。 In this method, the nitrogen doping process and the boron doping process 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.
この場合、例えば、まず窒素原子及びホウ素原子を含まない炭素材料に窒素ドープ処理を施し、次いで、当該窒素ドープ処理後の窒素原子を含む炭素材料にホウ素ドープ処理を施して、窒素原子及びホウ素原子を含む炭素材料を得ることとしてもよい。 In this case, for example, first, 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.
また、例えば、まず炭素材料を加熱下で窒素原子含有ガスと接触させる窒素ドープ処理を行い、次いで、当該窒素ドープ処理後の当該炭素材料とホウ素原子含有化合物との混合物を加熱するホウ素ドープ処理を行うこととしてもよい。 Further, for example, first, 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.
この場合、例えば、窒素ドープ処理後の炭素材料と、ホウ酸、三フッ化ホウ素（ＢＦ３）メタノール錯体、９−ＢＢＮ（９−ボラビシクロ［３．３．１］ノナン）、炭化ホウ素（Ｂ４Ｃ）及び酸化ホウ素（Ｂ２Ｏ３）からなる群より選択される１種以上との混合物を加熱するホウ素ドープ処理を行うこととしてもよい。特に、窒素ドープ処理後の炭素材料とホウ酸との混合物を加熱するホウ素ドープ処理を行うことにより、当該炭素材料にホウ素原子を効果的にドープすることができる。 In this case, for example, 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). In particular, 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.
また、例えば、まず炭素材料を加熱下で窒素原子含有ガスと接触させる窒素ドープ処理を行い、次いで、当該窒素ドープ処理後の当該炭素材料を加熱下でホウ素原子含有ガスと接触させるホウ素ドープ処理を行うこととしてもよい。 In addition, for example, first, 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.
そして、本方法においては、上述のような窒素ドープ処理及びホウ素ドープ処理を行って、窒素原子及びホウ素原子がドープされた炭素材料を得る。こうして得られた窒素原子及びホウ素原子を含む炭素材料は、それ自身が、アルカリ型燃料電池用炭素触媒としての触媒活性を示す。したがって、本方法においては、上述の窒素ドープ処理及びホウ素ドープ処理後の窒素原子及びホウ素原子を含む炭素材料を、アルカリ型燃料電池用炭素触媒として得ることとしてもよい。 And in this method, the above nitrogen dope process and boron dope process are performed, and the carbon material by which the nitrogen atom and the boron atom were doped is obtained. 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.
次に、本実施形態に係るアルカリ型燃料電池用炭素触媒（本触媒）について説明する。本触媒は、窒素原子及びホウ素原子を含む炭素材料を含むアルカリ型燃料電池用炭素触媒である。すなわち、本触媒の炭素材料は、窒素原子及びホウ素原子を含む炭素構造を有する。この炭素材料は、それ自身がアルカリ型燃料電池における触媒活性を示す。そして、本触媒は、アルカリ型燃料電池に使用される炭素触媒（より具体的には、アルカリ型燃料電池の電極に使用される炭素触媒）である。 Next, the alkaline fuel cell carbon catalyst (the present catalyst) according to the present embodiment will be described. 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).
本触媒は、上述した本方法により好ましく製造される。すなわち、本触媒は、上述のとおり、炭素材料に窒素ドープ処理及びホウ素ドープ処理を施して得られた、窒素原子及びホウ素原子を含む炭素材料を含むこととしてもよい。 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.
本触媒の炭素材料は、内部に金属（例えば、遷移金属）を含まないこととしてもよい。すなわち、この場合、本触媒は、窒素原子及びホウ素原子を含み、且つ内部に金属を含まない炭素材料を含む。また、本触媒は、内部に金属を含まない炭素材料に窒素ドープ処理及びホウ素ドープ処理を施して得られた、窒素原子及びホウ素原子を含み、且つ内部に金属を含まない炭素材料を含むこととしてもよい。 The carbon material of this catalyst is good also as not containing a metal (for example, 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.
また、本触媒の炭素材料は、表面に金属（例えば、遷移金属）を含まないこととしてもよい。また、本触媒の炭素材料は、表面に貴金属を含まないこととしてもよい。また、本触媒の炭素材料は、表面及び内部に金属（例えば、遷移金属）を含まないこととしてもよい。 Moreover, the carbon material of this catalyst is good also as not including a metal (for example, transition metal) on the surface. Moreover, the carbon material of this catalyst is good also as a surface containing no noble metal. Moreover, the carbon material of this catalyst is good also as not including a metal (for example, transition metal) in the surface and an inside.
本触媒の炭素材料のＸ線光電子分光法により測定されるホウ素原子／炭素原子比（Ｂ／Ｃ比）は、０．００１〜０．０５５であることとしてもよい。本触媒の炭素材料のＢ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上で好ましい。 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.
また、本触媒の炭素材料のＢ／Ｃ比は、例えば、０．００３〜０．０５５であることとしてもよい。本触媒の炭素材料のＢ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上でより好ましい。 Moreover, the B / C ratio of the carbon material of this catalyst is good also as being 0.003-0.055, for example. 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.
さらに、本触媒の炭素材料のＢ／Ｃ比は、例えば、０．００６〜０．０５５であることとしてもよく、０．０１０〜０．０５５であることとしてもよく、０．０２０〜０．０５５であることとしてもよく、０．０３０〜０．０５５であることとしてもよく、０．０４０〜０．０５５であることとしてもよい。本触媒の炭素材料のＢ／Ｃ比がこれらの範囲内であることは、本触媒が優れた触媒活性を示す上で特に好ましい。また、本触媒の炭素材料のＢ／Ｃ比が増加するにつれて、本触媒の触媒活性が向上する傾向がある。 Furthermore, 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, may be 0.030 to 0.055, and may be 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.
本触媒の炭素材料のＸ線光電子分光法により測定されるホウ素原子／窒素原子比（Ｂ／Ｎ比）は、０．１〜２．５であることとしてもよい。本触媒の炭素材料のＢ／Ｎ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上で好ましい。 The boron atom / nitrogen atom ratio (B / N ratio) measured by X-ray photoelectron spectroscopy of the carbon material of the 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.
また、本触媒の炭素材料のＢ／Ｎ比は、例えば、０．３〜２．５であることとしてもよく、０．５〜２．５であることとしてもよく、１．０〜２．５であることとしてもよく、１．５〜２．５であることとしてもよい。本触媒の炭素材料のＢ／Ｎ比がこれらの範囲内であることは、本触媒が優れた触媒活性を示す上で特に好ましい。また、本触媒の炭素材料のＢ／Ｎ比が増加するにつれて、本触媒の触媒活性が向上する傾向がある。 In addition, 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, or 1.0 to 2. It may be 5 or may be 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.
本触媒の前記炭素材料のＸ線光電子分光法により測定される窒素原子／炭素原子比（Ｎ／Ｃ比）は、０．００５〜０．０３５であることとしてもよい。本触媒の炭素材料のＮ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上で好ましい。 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.
また、本触媒の炭素材料のＮ／Ｃ比は、例えば、０．０１５〜０．０３５であることとしてもよく、０．０２〜０．０３５であることとしてもよい。本触媒の炭素材料のＮ／Ｃ比がこれらの範囲内であることは、本触媒が優れた触媒活性を示す上でより好ましい。 Moreover, N / C ratio of the carbon material of this catalyst is good also as being 0.015-0.035, for example, and good also as being 0.02-0.035. 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.
また、本触媒の炭素材料は酸素原子をさらに含むこととしてもよい。この場合、本触媒の炭素材料のＸ線光電子分光法により測定される酸素原子／炭素原子比（Ｏ／Ｃ比）は、０．００５〜０．１３５であることとしてもよい。本触媒の炭素材料のＯ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上で好ましい。 Moreover, the carbon material of this catalyst is good also as an oxygen atom further being included. In this case, 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.
また、本触媒の炭素材料のＯ／Ｃ比は、例えば、０．０５０〜０．１３５であることとしてもよい。本触媒の炭素材料のＯ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上でより好ましい。 Further, 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.
また、本触媒の炭素材料のＯ／Ｃ比は、例えば、０．１００〜０．１３５であることとしてもよい。本触媒の炭素材料のＯ／Ｃ比がこの範囲内であることは、本触媒が優れた触媒活性を示す上で特に好ましい。 Moreover, 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.
上述したＢ／Ｃ比、Ｎ／Ｃ比、Ｂ／Ｎ比及びＯ／Ｃ比は、任意に組み合わされる。すなわち、例えば、本触媒の炭素材料のＢ／Ｃ比は０．００１〜０．０５５であり、当該炭素材料のＢ／Ｎ比は０．１〜２．５であることとしてもよい。この場合、本触媒の炭素材料のＮ／Ｃ比は０．００５〜０．０３５であることとしてもよい。また、本触媒の炭素材料のＯ／Ｃ比は０．００５〜０．１３５であることとしてもよい。本触媒の炭素材料の表面元素比がこれらの範囲の組み合わせであることは、本触媒が優れた触媒活性を示す上で好ましい。 The aforementioned B / C ratio, N / C ratio, B / N ratio, and O / C ratio 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.
また、例えば、本触媒の炭素材料のＢ／Ｃ比は０．００３〜０．０５５であり、当該炭素材料のＢ／Ｎ比は０．１〜２．５であることとしてもよい。この場合、本触媒の炭素材料のＮ／Ｃ比は０．０１５〜０．０３５であることとしてもよい。また、本触媒の炭素材料のＯ／Ｃ比は０．０５０〜０．１３５であることとしてもよい。本触媒の炭素材料の表面元素比がこれらの範囲の組み合わせであることは、本触媒が優れた触媒活性を示す上でより好ましい。 Further, for example, 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. In this case, the N / C ratio of the carbon material of the present catalyst may be 0.015 to 0.035. Further, 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.
また、例えば、本触媒の炭素材料のＢ／Ｃ比は０．００６〜０．０５５であり、当該炭素材料のＢ／Ｎ比は０．３〜２．５であることとしてもよい。この場合、本触媒の炭素材料のＢ／Ｃ比は０．０１０〜０．０５５であることとしてもよく、０．０２０〜０．０５５であることとしてもよく、０．０３０〜０．０５５であることとしてもよく、０．０４０〜０．０５５であることとしてもよい。また、これらの場合、炭素材料のＢ／Ｎ比は０．５〜２．５であることとしてもよく、１．０〜２．５であることとしてもよい。さらに、これらの場合、本触媒の炭素材料のＮ／Ｃ比は０．０１５〜０．０３５であることとしてもよく、０．０２〜０．０３５であることとしてもよい。また、本触媒の炭素材料のＯ／Ｃ比は０．１００〜０．１３５であることとしてもよい。本触媒の炭素材料の表面元素比がこれらの範囲の組み合わせであることは、本触媒が優れた触媒活性を示す上で特に好ましい。 Further, for example, 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. In this case, the B / C ratio of the carbon material of the catalyst may be 0.010 to 0.055, may be 0.020 to 0.055, and is 0.030 to 0.055. It may be present, or may be 0.040 to 0.055. In these cases, the B / N ratio of the carbon material may be 0.5 to 2.5, or may be 1.0 to 2.5. Furthermore, in these cases, 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. Moreover, 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.
本触媒は、その触媒活性の一つとして、例えば、酸素還元活性を示す。本触媒の酸素還元活性は、例えば、当該本触媒をアルカリ電解液中で電極触媒として使用した場合における電流密度により評価される。 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.
すなわち、この電流密度は、例えば、本触媒を塗布した作用電極を有する回転リングディスク電極装置を用いて電位を掃引印加した場合に得られる電圧と電流密度との関係を示すデータ（酸素還元ボルタモグラム）における、電圧０（ゼロ）Ｖでの電流密度として求められる。 That is, 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.
具体的に、本触媒は、例えば、０．２０ｍＡ／ｃｍ２以上の上記電流密度を示すこととしてもよく、０．３０ｍＡ／ｃｍ２以上の上記電流密度を示すことが好ましく、０．４０ｍＡ／ｃｍ２以上の上記電流密度を示すことがより好ましく、０．５０ｍＡ／ｃｍ２以上の上記電流密度を示すことがさらに好ましく、０．６０ｍＡ／ｃｍ２以上の上記電流密度を示すことが特に好ましい。この電流密度の上限値は、特に限られないが、当該電流密度は、例えば、４．０ｍＡ／ｃｍ２以下であることとしてもよい。 More specifically, the present catalyst, 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.
また、本触媒の酸素還元活性は、例えば、当該本触媒をアルカリ電解液中で電極触媒として使用した場合における酸素還元開始電位により評価される。酸素還元開始電位は、例えば、本触媒を塗布した作用電極を有する回転リングディスク電極装置を用いて電位を掃引印加し、このとき得られる電圧と電流密度との関係を示すデータ（酸素還元ボルタモグラム）に基づき、−１０μＡ/ｃｍ２の還元電流が流れたときの電圧（ＥＯ２）として求められる。 In addition, the 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 μA / cm 2 flows.
具体的に、本触媒は、例えば、０．０７Ｖ（ｖｓ．ＮＨＥ）以上（より具体的には、例えば、０．０７Ｖ（ｖｓ.ＮＨＥ）以上、１．２Ｖ（ｖｓ.ＮＨＥ）以下）の酸素還元開始電位を示すこととしてもよく、０．０８Ｖ（ｖｓ．ＮＨＥ）以上の酸素還元開始電位を示すことが好ましい。 Specifically, 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.
本実施形態に係るアルカリ型燃料電池用電極（本電極）は、上述した本触媒を含む、アルカリ型燃料電池の電極である。すなわち、本電極は、例えば、本触媒が担持された電極である。具体的に、本電極は、例えば、電極基材と、当該電極基材に担持された本触媒と、を含む電極である。本電極は、例えば、アルカリ型燃料電池用カソード（酸素極）として使用される。 The alkaline fuel cell electrode (main electrode) according to the present embodiment is an electrode of 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.
本実施形態に係るアルカリ型燃料電池（本電池）は、上述した本電極を含む。すなわち、本電池は、例えば、上述した本電極をカソード（酸素極）として含むアルカリ型燃料電池である。 The alkaline fuel cell (main battery) according to the present embodiment includes the main electrode described above. That is, this battery is, for example, an alkaline fuel cell that includes the above-described electrode as a cathode (oxygen electrode).
次に、本実施形態に係る具体的な実施例について説明する。 Next, specific examples according to the present embodiment will be described.
［実施例１］
まず、炭素材料に窒素原子をドープした。すなわち、炭素材料であるカーボンブラック（バルカン：ＸＣ−７２）３００ｍｇを石英管中に固定し、当該石英管を電気炉中に置いた。電気炉内において、窒素雰囲気下で石英管内の炭素材料を加熱して、その温度を室温から６００℃まで上昇させた。
[Example 1]
First, 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.
次いで、電気炉内において、アンモニア（ＮＨ３）と空気との混合ガス（ＮＨ３濃度：７０体積％）を流量２００ｍＬ／分で流通させながら、炭素材料を６００℃で２時間保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうしてアンモオキシデーション法により、窒素原子を含む炭素材料を得た。 Next, 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.
さらに、炭素材料にホウ素原子をドープした。すなわち、上述のようにして得られた窒素原子を含む炭素材料１０００ｍｇを、ホウ酸を１２５０ｍｇ／Ｌの濃度で含む水溶液２００ｍＬ中に８０℃で１時間浸漬することにより、当該炭素材料１００重量部とホウ酸２０重量部とを混合し、当該炭素材料にホウ酸を含浸させた。 Further, the carbon material was doped with boron atoms. 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.
次いで、ホウ酸を担持した炭素材料１００ｍｇを石英管中に固定し、当該石英管を電気炉中に置いた。電気炉内において、窒素雰囲気下で石英管内の炭素材料を加熱して、その温度を室温から１０００℃まで上昇させた。 Next, 100 mg of a carbon material carrying boric acid 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 1000 ° C.
さらに、電気炉内において、炭素材料を１０００℃で１時間保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうして、窒素原子及びホウ素原子を含む炭素材料を、アルカリ型燃料電池用炭素触媒として得た。 Further, 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.
［実施例２］
まず、炭素材料に窒素原子をドープした。すなわち、炭素材料であるカーボンブラック（バルカン：ＸＣ−７２）２００ｍｇを石英管中に固定し、当該石英管を電気炉中に置いた。電気炉内において、窒素雰囲気下で石英管内の炭素材料を加熱して、その温度を室温から６００℃まで上昇させた。
[Example 2]
First, 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.
次いで、電気炉内において、アンモニア（ＮＨ３）と空気との混合ガス（ＮＨ３濃度：７０体積％）を流量２００ｍＬ／分で流通させながら、炭素材料を６００℃で２時間保持した。 Next, 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.
続いて、炭素材料にホウ素原子をドープした。すなわち、上述のようにして炭素材料に窒素原子をドープした後、電気炉内の温度を低下させることなく、まずアンモニア（ＮＨ３）と空気との混合ガスを窒素（Ｎ２）ガスに置換し、次いで、当該窒素（Ｎ２）ガスをＢＣｌ３／Ｎ２混合ガス（ＢＣｌ３濃度は１体積％）に置換した。 Subsequently, 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).
そして、このＢＣｌ３／Ｎ２混合ガスの流通下、窒素原子がドープされた炭素材料を６００℃で４５分保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうして、窒素原子及びホウ素原子を含む炭素材料を得た。 Then, under the flow of this BCl 3 / N 2 mixed gas, the carbon material doped with nitrogen atoms was held at 600 ° C. for 45 minutes. 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.
［実施例３］
まず、上述の実施例１と同様にして、アンモオキシデーション法により炭素材料（カーボンブラック（バルカン：ＸＣ−７２））に窒素原子をドープした。
[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.
さらに、炭素材料にホウ素原子をドープした。すなわち、上述のようにして得られた窒素原子を含む炭素材料１００ｍｇを、三フッ化ホウ素（ＢＦ３）メタノール錯体（ＢＦ３：１５％）１２ｍＬと混合した。 Further, 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%).
次いで、この混合物を電気炉内で加熱して、１０００℃で１時間保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうして、窒素原子及びホウ素原子を含む炭素材料を得た。 The mixture was then 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.
［比較例１］
窒素原子及びホウ素原子がドープされていない炭素材料として、上述の実施例１〜３で使用された、未処理のカーボンブラック（バルカン：ＸＣ−７２）を用意した。
[Comparative Example 1]
An untreated carbon black (Vulcan: XC-72) used in Examples 1 to 3 described above was prepared as a carbon material not doped with nitrogen and boron atoms.
［比較例２］
窒素原子がドープされ、ホウ素原子はドープされていない炭素材料を用意した。すなわち、上述の実施例１と同様にして、カーボンブラック（バルカン：ＸＣ−７２）に窒素原子をドープすることにより、窒素原子がドープされた炭素材料を得た。
[Comparative 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.
［比較例３］
窒素原子がドープされ、ホウ素原子はドープされていない炭素材料であって、窒素原子のドープ後に熱処理が施された炭素材料を用意した。すなわち、まず、上述の実施例１と同様にして、炭素材料（カーボンブラック（バルカン：ＸＣ−７２））に窒素原子をドープした。その後、電気炉内のアンモニア（ＮＨ３）と空気との混合ガスを窒素（Ｎ２）ガスに置換した。
[Comparative 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.
そして、このＮ２ガスの流通下、窒素原子がドープされた炭素材料を加熱して、１０００℃で１時間保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうして、窒素原子がドープされ、熱処理が施された炭素材料を得た。 Then, under the flow of this N 2 gas, the carbon material doped with nitrogen atoms was heated 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 doped with nitrogen atoms and subjected to heat treatment was obtained.
［比較例４］
ホウ素原子がドープされ、窒素原子はドープされていない炭素材料を用意した。すなわち、カーボンブラック（バルカン：ＸＣ−７２）１０００ｍｇを、ホウ酸を１２５０ｍｇ／Ｌの濃度で含む水溶液２００ｍＬ中に室温で１時間浸漬することにより、当該炭素材料１００重量部に２０重量部のホウ酸を含浸させた。
[Comparative Example 4]
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 at room temperature for 1 hour, 20 parts by weight of boric acid is added to 100 parts by weight of the carbon material. Was impregnated.
次いで、ホウ酸を担持した炭素材料１００ｍｇを石英管中に固定し、当該石英管を電気炉中に置いた。電気炉内において、窒素雰囲気下で石英管内の炭素材料を加熱して、その温度を室温から１０００℃まで上昇させた。 Next, 100 mg of a carbon material carrying boric acid 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 1000 ° C.
さらに、電気炉内において、炭素材料を１０００℃で１時間保持した。その後、電気炉を開けて空冷し、炭素材料を取り出した。こうして、ホウ素原子がドープされた炭素材料を得た。 Further, 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線光電子分光法］
上述のようにして得られた炭素材料をＸ線光電子分光法（ＸＰＳ）により分析した。すなわち、Ｘ線光電子分光装置（Ｋｒａｔｏｓ ＡＸＩＳ ＮＯＶＡ、株式会社島津製作所製）（Ｘ線：ＡｌＫα線、出力：１０ｍＡ×１５ｋＶ）により、炭素材料の表面元素を分析した。具体的に、ＸＰＳ測定により得られたスペクトルの各ピークの面積と検出感度係数とから、炭素原子、ホウ素原子、窒素原子及び酸素原子の表面元素濃度（％）を求め、当該各元素の濃度の比として、表面におけるホウ素原子の炭素原子に対する比（Ｂ／Ｃ比）、窒素原子の炭素原子に対する比（Ｎ／Ｃ比）、及び酸素原子の炭素原子に対する比（Ｏ／Ｃ比）の値を算出した。また、定量計算の際のバックグラウンドはＳｈｉｒｌｅｙ法により決定した。
[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: AlKα 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. As the ratio, 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.
［触媒活性］
また、上述のようにして得られた炭素材料の触媒活性として、アルカリ電解質を使用した場合における、電圧０Ｖでの電流密度（Ｉ０ｖ）と、酸素還元開始電位（ＥＯ２）とを評価した。
[Catalytic activity]
Further, as the catalytic activity of the carbon material obtained as described above, the current density (I 0v ) at a voltage of 0 V and the oxygen reduction starting potential (E O2 ) in the case of using an alkaline electrolyte were evaluated.
すなわち、まず触媒スラリーを調製した。具体的に、上述のようにして得られた炭素材料５ｍｇと、２５μＬのバインダー溶液（ナフィオン（商標登録）、デュポン株式会社）と、２００μＬの超純水と、１７５μＬのエタノールと、スパチュラで２杯（約１５粒）のガラスビーズ（直径１ｍｍ）とを混合し、２０分間超音波処理することにより、触媒スラリーを得た。 That is, first, a catalyst slurry was prepared. Specifically, 5 mg of the carbon material obtained as described above, 25 μL of binder solution (Nafion (registered trademark), DuPont), 200 μL of ultrapure water, 175 μL 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.
次いで、上述の触媒スラリー１．８μＬをピペットにより吸い取り、回転リングディスク電極装置（ＲＲＤＥ−３Ａ Ｖｅｒ．１．２Ｓ、ビー・エー・エス株式会社製）のディスク電極（０．１２５６ｃｍ２）に塗布し、乾燥させることにより、作用電極を作製した。また、リング電極としては、白金電極を用いた。参照電極として飽和塩化カリウム銀／塩化銀（Ａｇ／ＡｇＣｌ）電極を用いた。アルカリ電解質としては、酸素を常温で溶解させた、０．１Ｍ水酸化カリウム水溶液を用いた。 Next, 1.8 μL of the catalyst slurry described above was sucked up with a pipette and applied to the disk electrode (0.1256 cm 2 ) of a rotating ring disk electrode device (RRDE-3A Ver. 1.2S, manufactured by BAS Co., Ltd.). 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.
そして、電気化学アナライザー（ＣＨＩ７００Ｂ、株式会社ＡＬＳ社製）を用いてリニアスイープボルタンメトリーを行った。リニアスイープボルタンメトリーにおいて、電位は、飽和塩化カリウム銀／塩化銀電極を用いて測定した値を標準水素電極（ＮＨＥ）基準値に換算することにより算出した。 Then, linear sweep voltammetry was performed using an electrochemical analyzer (CHI700B, manufactured by ALS Co., Ltd.). In linear sweep voltammetry, the potential was calculated by converting a value measured using a saturated potassium silver chloride / silver chloride electrode into a standard hydrogen electrode (NHE) reference value.
まず、２５℃で酸素を２０分間バブリングすることにより電解質溶液を酸素飽和させた後、測定を開始した。次いで、初期電位を６００秒保持した後に、電極を回転速度１５００ｒｐｍで回転させ、２５℃にて、掃引速度１ｍＶ／秒で０．１Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）から−０．６Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）まで電位を掃引し、作用電極に流れる電流値を測定した。すなわち、標準水素電極（ＮＨＥ）基準値に換算すると、０．３Ｖ（ｖｓ．ＮＨＥ）から−０．４Ｖ（ｖｓ．ＮＨＥ）まで電位を掃引した。 First, the oxygen solution was saturated with oxygen by bubbling oxygen at 25 ° C. for 20 minutes, and then the measurement was started. Next, after maintaining the initial potential for 600 seconds, 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 current value flowing through the working electrode was measured. That is, when converted into a standard hydrogen electrode (NHE) reference value, the potential was swept from 0.3 V (vs. NHE) to -0.4 V (vs. NHE).
このときの流れた電流を電位の関数として記録した。そして、得られた分極曲線から、−１０μＡ／ｃｍ２の還元電流が流れたときの電圧を、“酸素還元開始電位（ＥＯ２）”（Ｖ ｖｓ． ＮＨＥ）として記録した。また、０Ｖ（ｖｓ． ＮＨＥ）の電位を印加したときの電流密度（ｍＡ／ｃｍ２）も“Ｉ０Ｖ”として記録した。 The current flowing at this time was recorded as a function of potential. Then, from the obtained polarization curve, a voltage when a reduction current of −10 μA / cm 2 flows was recorded as “oxygen reduction start 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 ”.
［結果］
図１には、各炭素材料について評価された、表面元素比と触媒活性とを示す。すなわち、図１には、各炭素材料の表面のＢ／Ｃ比、Ｎ／Ｃ比、Ｂ／Ｎ比及びＯ／Ｃ比と、電圧０Ｖでの電流密度（Ｉ０ｖ（ｍＡ／ｃｍ２））及び酸素還元開始電位（Ｅо２（Ｖ ｖｓ．ＮＨＥ））とを示す。
[result]
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 (Eо 2 (V vs. NHE)).
図１の「Ｂ／Ｃ比」に示すように、その製造過程でホウ素ドープ処理を行った実施例１〜３及び比較例４では、炭素材料にホウ素原子がドープされていることが確認された。特に、窒素ドープ処理後の炭素材料とホウ酸との混合物を加熱するホウ素ドープ処理を行った実施例１では、当該炭素材料にホウ素原子を効果的にドープすることができた。 As shown in “B / C ratio” in FIG. 1, in Examples 1 to 3 and Comparative Example 4 in which boron doping treatment was performed in the manufacturing process, it was confirmed that the carbon material was doped with boron atoms. . In particular, in 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.
また、図１の「Ｎ／Ｃ比」に示すように、その製造過程で窒素ドープ処理を行った実施例１〜３及び比較例２、３では、炭素材料に窒素原子がドープされていることが確認された。 Further, as shown in “N / C ratio” in FIG. 1, in Examples 1 to 3 and Comparative Examples 2 and 3 in which the nitrogen doping process was performed in the manufacturing process, the carbon material is doped with nitrogen atoms. Was confirmed.
また、図１の「Ｂ／Ｃ比」に示すように、実施例１で得られた炭素材料のＢ／Ｎ比は、実施例２、３のそれに比べて顕著に大きかった。また、図１の「Ｏ／Ｃ比」に示すように、実施例１〜３及び比較例２〜４では、炭素材料に酸素原子が導入されていることが確認された。 Further, as shown in “B / C ratio” in FIG. 1, the B / N ratio of the carbon material obtained in Example 1 was significantly larger than those in Examples 2 and 3. Moreover, as shown in the “O / C ratio” in FIG. 1, it was confirmed that oxygen atoms were introduced into the carbon material in Examples 1 to 3 and Comparative Examples 2 to 4.
そして、図１の「触媒活性」に示すように、実施例１〜３の炭素材料を使用して測定された電流密度（Ｉ０ｖ）及び酸素還元開始電位（ＥＯ２）は、比較例１〜４の炭素材料を使用して測定されたそれらに比べて顕著に大きかった。 As shown in “catalytic activity” of FIG. 1, the current density (I 0v ) and oxygen reduction initiation potential (E O2 ) measured using the carbon materials of Examples 1 to 3 It was significantly larger than those measured using 4 carbon materials.
すなわち、実施例１〜３の炭素材料は、比較例１〜４の炭素材料に比べて顕著に優れた触媒活性を示すことが確認された。さらに、実施例１、２の炭素材料は、実施例３の炭素材料に比べて大きな電流密度を示し、実施例１の炭素材料は特に大きな電流密度を示した。 That is, it was confirmed that 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.
Claims (7)
ことを特徴とするアルカリ型燃料電池用炭素触媒。 A carbon material containing a nitrogen atom, a boron atom and an oxygen atom, containing no metal inside, and having a boron atom / nitrogen atom ratio of 1.0 to 2.5 as measured by X-ray photoelectron spectroscopy. A carbon catalyst for alkaline fuel cells.
ことを特徴とする請求項１に記載のアルカリ型燃料電池用炭素触媒。 The carbon catalyst for alkaline fuel cells according to claim 1, wherein the carbon material has a boron atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.001 to 0.055.
ことを特徴とする請求項１又は２に記載のアルカリ型燃料電池用炭素触媒。 The carbon catalyst for alkaline fuel cells according to claim 1 or 2, wherein the carbon material has a nitrogen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.005 to 0.035.
ことを特徴とする請求項１乃至３のいずれかに記載のアルカリ型燃料電池用炭素触媒。 4. The alkaline fuel cell according to claim 1, wherein the carbon material has an oxygen atom / carbon atom ratio measured by X-ray photoelectron spectroscopy of 0.005 to 0.135. 5. Carbon catalyst.
ことを特徴とするアルカリ型燃料電池用電極。 An electrode for an alkaline fuel cell, comprising the carbon catalyst according to claim 1.
ことを特徴とするアルカリ型燃料電池。 An alkaline fuel cell comprising the electrode according to claim 5.
まず内部に金属を含まない炭素材料に窒素ドープ処理を施し、次いで、前記窒素ドープ処理後の前記炭素材料に、前記炭素材料とホウ酸との混合物を加熱する処理であるホウ素ドープ処理を施して、窒素原子及びホウ素原子を含む前記炭素材料を含むアルカリ型燃料電池用炭素触媒を得ることを含む
ことを特徴とするアルカリ型燃料電池用炭素触媒の製造方法。 A method for producing a carbon catalyst for an alkaline fuel cell according to any one of claims 1 to 4,
First, a carbon material containing no metal inside is subjected to nitrogen doping treatment, and then the carbon material after the nitrogen doping treatment is subjected to boron doping treatment which is a treatment of heating a mixture of the carbon material and boric acid. A method for producing a carbon catalyst for an alkaline fuel cell, comprising: obtaining a carbon catalyst for an alkaline fuel cell comprising the carbon material containing a nitrogen atom and a boron atom.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013248556A JP6254431B2 (en) | 2013-11-29 | 2013-11-29 | Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell |
| PCT/JP2014/080401 WO2015079956A1 (en) | 2013-11-29 | 2014-11-17 | Carbon catalyst for alkaline fuel cell and method for producing carbon catalyst, as well as electrode for alkaline fuel cell, and alkaline fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013248556A JP6254431B2 (en) | 2013-11-29 | 2013-11-29 | Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2015106512A JP2015106512A (en) | 2015-06-08 |
| JP2015106512A5 JP2015106512A5 (en) | 2017-01-12 |
| JP6254431B2 true JP6254431B2 (en) | 2017-12-27 |
Family
ID=53198901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013248556A Active JP6254431B2 (en) | 2013-11-29 | 2013-11-29 | Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6254431B2 (en) |
| WO (1) | WO2015079956A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6223798B2 (en) * | 2013-11-29 | 2017-11-01 | 日清紡ホールディングス株式会社 | Solid base catalyst and method and reaction apparatus related thereto |
| CN109311674B (en) * | 2016-06-15 | 2023-01-31 | 国立大学法人东北大学 | Carbon material and method for producing same |
| CN114497601B (en) * | 2020-10-26 | 2024-04-02 | 中国石油化工股份有限公司 | Carbon-doped material, platinum-carbon catalyst, and preparation methods and applications thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006331846A (en) * | 2005-05-26 | 2006-12-07 | Asahi Kasei Corp | Electrode catalyst for fuel cell |
| JP2009119423A (en) * | 2007-11-19 | 2009-06-04 | Asahi Kasei Corp | Active b-c-n material and method of manufacturing the same |
| JP5247129B2 (en) * | 2007-11-26 | 2013-07-24 | 日本カーリット株式会社 | Catalyst body and method for producing the same |
| JP5320579B2 (en) * | 2008-06-05 | 2013-10-23 | 清蔵 宮田 | Gas diffusion electrode and manufacturing method thereof, membrane electrode assembly and manufacturing method thereof, fuel cell member and manufacturing method thereof, fuel cell, power storage device and electrode material |
| WO2010064556A1 (en) * | 2008-12-02 | 2010-06-10 | 日清紡ホールディングス株式会社 | Carbon catalyst, method for manufacturing the carbon catalyst, and electrode and battery using the carbon catalyst |
-
2013
- 2013-11-29 JP JP2013248556A patent/JP6254431B2/en active Active
-
2014
- 2014-11-17 WO PCT/JP2014/080401 patent/WO2015079956A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015079956A1 (en) | 2015-06-04 |
| JP2015106512A (en) | 2015-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Deng et al. | Metal–organic framework‐derived carbon nanorods encapsulating bismuth oxides for rapid and selective CO2 electroreduction to formate | |
| Rao et al. | Borocarbonitrides as metal‐free catalysts for the hydrogen evolution reaction | |
| Alia et al. | Porous platinum nanotubes for oxygen reduction and methanol oxidation reactions | |
| Sahraie et al. | Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts | |
| Hosseini et al. | Highly active nickel nanoparticles supported on TiO2 nanotube electrodes for methanol electrooxidation | |
| Moon et al. | Highly active cobalt‐based electrocatalysts with facile incorporation of dopants for the oxygen evolution reaction | |
| Pillai et al. | New insights into electrochemical ammonia oxidation on Pt (100) from first principles | |
| Kundu et al. | Platinum nanostructure/nitrogen‐doped carbon hybrid: enhancing its base media HER/HOR activity through bi‐functionality of the catalyst | |
| Watanabe et al. | Tailored design of boron‐doped diamond electrodes for various electrochemical applications with boron‐doping level and sp2‐bonded carbon impurities | |
| Meng et al. | Electrodeposition of cobalt oxide nanoparticles on carbon nanotubes, and their electrocatalytic properties for nitrite electrooxidation | |
| Yi et al. | Electrochemical Activity of Novel Titanium‐Supported Porous Binary Pd‐Ru Particles for Ethanol Oxidation in Alkaline Media | |
| Mecheri et al. | Carbon‐supported zirconium oxide as a cathode for microbial fuel cell applications | |
| Li et al. | Chemically heterogeneous nitrogen sites of various reactivity in porous carbons provide high stability of CO2 electroreduction catalysts | |
| Ojani et al. | Electrochemical behavior of Ni (II) incorporated in zeolite Y-modified carbon electrode: application for electrocatalytic oxidation of methanol in alkaline solution | |
| JP6254431B2 (en) | Carbon catalyst for alkaline fuel cell and method for producing the same, electrode for alkaline fuel cell, and alkaline fuel cell | |
| Yu et al. | Amorphous FeOOH decorated CoSe2 nanorod heterostructured arrays for efficient water oxidation | |
| WO2017199653A1 (en) | Cell electrode, composition for cell electrode catalyst layer, and cell | |
| Janicek et al. | High performance activated carbon/carbon cloth cathodes for microbial fuel cells | |
| Wang et al. | Polyaniline synthesis by cyclic voltammetry for anodic modification in microbial fuel cells | |
| Kübler et al. | Impact of surface functionalization on the intrinsic properties of the resulting Fe–N–C catalysts for fuel cell applications | |
| CN110273162B (en) | Iron/cobalt/nickel-nitrogen coupled carbon-based composite material and application thereof | |
| Li et al. | Dopamine-derived nitrogen-doped carboxyl multiwalled carbon nanotube-modified graphite felt with improved electrochemical activity for vanadium redox flow batteries | |
| Srinivas et al. | Co/Co‐N@ Nanoporous Carbon Derived from ZIF‐67: A Highly Sensitive and Selective Electrochemical Dopamine Sensor | |
| Daniele et al. | Bismuth‐Coated Mesoporous Platinum Microelectrodes as Sensors for Formic Acid Detection | |
| Wang et al. | Oxygen evolution reaction on nanoporous gold modified with Ir and Pt: Synergistic electrocatalysis between structure and composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20161125 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161125 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20161125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170718 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170901 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20171107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20171130 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6254431 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |