JP2012164608A - ELECTRODE CATALYST CONTAINING Fe, Co, AND Ni, AND METHOD FOR MANUFACTURING THE SAME - Google Patents
ELECTRODE CATALYST CONTAINING Fe, Co, AND Ni, AND METHOD FOR MANUFACTURING THE SAME Download PDFInfo
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- JP2012164608A JP2012164608A JP2011026120A JP2011026120A JP2012164608A JP 2012164608 A JP2012164608 A JP 2012164608A JP 2011026120 A JP2011026120 A JP 2011026120A JP 2011026120 A JP2011026120 A JP 2011026120A JP 2012164608 A JP2012164608 A JP 2012164608A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 238000010304 firing Methods 0.000 claims description 40
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 239000010411 electrocatalyst Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 abstract description 46
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 36
- 229910021529 ammonia Inorganic materials 0.000 abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- 239000007784 solid electrolyte Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910020630 Co Ni Inorganic materials 0.000 description 8
- 229910002440 Co–Ni Inorganic materials 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 3
- 206010021143 Hypoxia Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
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- 229910002058 ternary alloy Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
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- 239000004809 Teflon Substances 0.000 description 1
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- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 102220318172 rs147648476 Human genes 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、Ｆｅ、Ｃｏ及びＮｉを含む電極触媒及びその製造方法に関する。 The present invention relates to an electrode catalyst containing Fe, Co and Ni and a method for producing the same.
燃料電池は、従来の発電技術と比較して高いエネルギー効率を達成し得ることから、環境負荷の少ない電力発生源としてその実用化が期待されている。これまでにも実用化に向けた様々な取り組みがなされ、特に燃料電池の電極に用いられる触媒の開発が注目されている。 Since fuel cells can achieve higher energy efficiency than conventional power generation technologies, their practical application is expected as a power generation source with a low environmental load. Various efforts have been made for practical use so far, and the development of a catalyst used for an electrode of a fuel cell has been attracting attention.
ここで、例えば特許文献１には、メタノールやエタノールを燃料とする燃料電池のアノード触媒として、鉄−コバルト−ニッケル触媒が用いられることが記載されている。 Here, for example, Patent Document 1 describes that an iron-cobalt-nickel catalyst is used as an anode catalyst of a fuel cell using methanol or ethanol as a fuel.
上述の燃料電池の一つとして、アンモニアを燃料とする燃料電池があり、アンモニアは容易に液化できるなどの利点を有している。しかし、アンモニアを燃料とする燃料電池（以下、「アンモニア燃料電池」という場合がある）に、例えば特許文献１に記載された鉄−コバルト−ニッケル触媒を電極触媒として用いると、十分な電流密度を得ることができないという問題があった。 As one of the fuel cells described above, there is a fuel cell using ammonia as a fuel, which has an advantage that ammonia can be easily liquefied. However, for example, when an iron-cobalt-nickel catalyst described in Patent Document 1 is used as an electrode catalyst in a fuel cell using ammonia as a fuel (hereinafter sometimes referred to as “ammonia fuel cell”), a sufficient current density can be obtained. There was a problem that could not be obtained.
そこで本発明は、アンモニアを燃料とする燃料電池に適用した場合に、高い起電力及び十分な電流密度を得ることができる電極触媒及びその製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide an electrode catalyst capable of obtaining a high electromotive force and a sufficient current density when applied to a fuel cell using ammonia as a fuel, and a method for producing the electrode catalyst.
本発明者らは、Ｆｅ、Ｃｏ及びＮｉを含む電極触媒について鋭意検討したところ、特定のＦｅ、Ｃｏ及びＮｉを含む電極触媒をアンモニア燃料電池に用いることによって、高い起電力及び十分な電流密度を得ることができることを見出した。また、この特定のＦｅ、Ｃｏ及びＮｉを含む電極触媒を製造する方法も見出し、以下の発明を完成させるに至った。 The present inventors diligently studied an electrode catalyst containing Fe, Co, and Ni. By using an electrode catalyst containing specific Fe, Co, and Ni in an ammonia fuel cell, a high electromotive force and a sufficient current density were obtained. Found that can be obtained. Also, a method for producing an electrode catalyst containing this specific Fe, Co, and Ni has been found, and the following invention has been completed.
本発明は、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒を提供する。このように、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒は、燃料電池に用いられた場合に、高い起電力及び十分な電流密度を得ることができる。 The present invention provides an electrocatalyst having an alloy material including an alloy part containing Fe, Co, and Ni and an Fe part that does not form the alloy part. Thus, an electrocatalyst having an alloy material containing an alloy part containing Fe, Co, and Ni and an Fe part not forming the alloy part has a high electromotive force and a high electromotive force when used in a fuel cell. A sufficient current density can be obtained.
本発明において、上記電極触媒はＸ線回折を行ったとき、回折角２θにおいて、Ｆｅ（上記合金部分におけるＦｅと、上記Ｆｅ部分）に由来する２つのピークを発現することが好ましい。このような特性を示す電極触媒は、燃料電池に用いられた場合に高い起電力及び十分な電流密度を得ることができる。 In the present invention, when the electrode catalyst performs X-ray diffraction, it preferably exhibits two peaks derived from Fe (Fe in the alloy part and Fe part) at a diffraction angle 2θ. An electrode catalyst exhibiting such characteristics can obtain a high electromotive force and a sufficient current density when used in a fuel cell.
また、本発明において、上記電極触媒は、炭素材料に上記合金材料を担持したものであることが好ましい。炭素材料に上記合金材料を担持させることによって、電極触媒として取り扱いが容易となる。 In the present invention, the electrode catalyst is preferably a carbon material carrying the alloy material. By supporting the above alloy material on the carbon material, handling as an electrode catalyst becomes easy.
本発明は、炭素材料を、Ｆｅ、Ｃｏ及びＮｉを含む水溶液に含侵させ、触媒前駆体を得る工程と、触媒前駆体を水素雰囲気下において焼成する第１の焼成工程と、第１の焼成工程後の触媒前駆体を水素雰囲気下において第１の焼成工程よりも低温で焼成する第２の焼成工程と、を備える電極触媒の製造方法を提供する。第１の焼成工程と、第１の焼成工程よりも低温で焼成する第２の焼成工程を備える上記製造方法により、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒を製造することができる。 The present invention includes impregnating a carbon material with an aqueous solution containing Fe, Co, and Ni to obtain a catalyst precursor, a first firing step of firing the catalyst precursor in a hydrogen atmosphere, and a first firing And a second firing step of firing the catalyst precursor after the step at a lower temperature than the first firing step in a hydrogen atmosphere. By the said manufacturing method provided with the 1st baking process and the 2nd baking process baked at low temperature rather than a 1st baking process, Fe part which has not formed the alloy part containing Fe, Co, and Ni And an electrode catalyst having an alloy material including the portion.
上記製造方法において、第１の焼成工程における温度が９００〜１３００℃であり、第２の焼成工程における温度が４００〜６００℃であることが好ましい。焼成温度を当該範囲にすることによって、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒をより短時間で製造することができる。 In the said manufacturing method, it is preferable that the temperature in a 1st baking process is 900-1300 degreeC, and the temperature in a 2nd baking process is 400-600 degreeC. By making the firing temperature within this range, an electrode catalyst having an alloy material containing an alloy part containing Fe, Co, and Ni and an Fe part not forming the alloy part can be manufactured in a shorter time. it can.
本発明により、アンモニアを燃料とする燃料電池に適用した場合に、高い起電力及び十分な電流密度を得ることができる電極触媒及びその製造方法を提供することができる。 According to the present invention, when applied to a fuel cell using ammonia as a fuel, an electrode catalyst capable of obtaining a high electromotive force and a sufficient current density and a method for producing the same can be provided.
以下、場合により図面を参照しつつ本発明の好適な実施形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be.
＜Ｆｅ、Ｃｏ及びＮｉを含む電極触媒＞
本発明の電極触媒は、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する。Ｆｅ、Ｃｏ及びＮｉを含む合金部分とは、例えば、Ｆｅ、Ｃｏ及びＮｉが三元系の合金をなすものをいう。Ｆｅ、Ｃｏ及びＮｉを含む合金部分は、当該合金部分としての機能を害さない範囲で他の金属などの成分を含んでもよい。また、当該合金部分を形成していないＦｅ部分とは、Ｆｅ、Ｃｏ及びＮｉの三元系合金から一部のＦｅが析出したものをいう。この合金部分を形成していないＦｅ部分は、例えば、Ｆｅ、Ｃｏ及びＮｉを含む合金部分の領域外に存在しており、合金部分の領域の表面にＦｅ部分が析出したものも好ましい。合金材料は、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分を含むが、当該合金材料としての機能を害さない範囲で他の金属などの成分を含んでもよい。
<Electrocatalyst containing Fe, Co and Ni>
The electrode catalyst of the present invention has an alloy material including an alloy part containing Fe, Co, and Ni and an Fe part not forming the alloy part. The alloy part containing Fe, Co, and Ni refers to, for example, one in which Fe, Co, and Ni form a ternary alloy. The alloy part containing Fe, Co, and Ni may contain components such as other metals as long as the function as the alloy part is not impaired. Further, the Fe part not forming the alloy part means a part of Fe precipitated from a ternary alloy of Fe, Co and Ni. The Fe part that does not form this alloy part exists outside the region of the alloy part containing, for example, Fe, Co, and Ni, and it is also preferable that the Fe part is deposited on the surface of the alloy part region. The alloy material includes an alloy part containing Fe, Co, and Ni and an Fe part that does not form the alloy part, but may contain components such as other metals as long as the function as the alloy material is not impaired. .
合金材料が、Ｆｅを含む合金部分と、当該合金を形成していないＦｅ部分を含むことは、合金材料をＸ線回折（回折角２θ）を用いて構造解析したときに、Ｆｅに由来する２つのピークが発現することで確認できる。すなわち、本発明の電極触媒は、Ｘ線回折（回折角２θ）を用いて構造解析すると、４３〜４５°の範囲において、Ｆｅに由来する２つのピークを発現する。２つのピークは、合金部分に含まれるＦｅを示す第１のピークと、当該合金部分を形成していないＦｅ部分を示す第２のピークとからなる。第１のピークと第２のピークとは、それらの裾部において必ずしも明確に２つに分離していない場合もあるが、両ピークの最も高い部分同士が、少なくとも０．５〜１°、好ましくは０．８〜１°、より好ましくは０．９〜１°離れていれば、Ｆｅに由来する２つのピークが発現していると見なすことができる。また、第２のピークの強度は、第１のピークの強度の３０〜５０％であればよい。この割合は、好ましくは３５〜５０％であり、より好ましくは４０〜５０％である。本発明者らは本電極触媒の上記構造が、アンモニア燃料電池に適用された場合に、高い起電力と十分な電流密度を可能としているものと推察している。 The fact that the alloy material includes an alloy portion containing Fe and an Fe portion not forming the alloy is derived from Fe when the alloy material is structurally analyzed using X-ray diffraction (diffraction angle 2θ). This can be confirmed by the appearance of two peaks. That is, the structure of the electrode catalyst of the present invention using X-ray diffraction (diffraction angle 2θ) reveals two peaks derived from Fe in the range of 43 to 45 °. The two peaks are composed of a first peak indicating Fe contained in the alloy part and a second peak indicating Fe part not forming the alloy part. The first peak and the second peak may not necessarily be clearly separated into two at their skirts, but the highest portions of both peaks are at least 0.5 to 1 °, preferably Is 0.8 to 1 °, more preferably 0.9 to 1 °, it can be considered that two peaks derived from Fe are expressed. The intensity of the second peak may be 30 to 50% of the intensity of the first peak. This proportion is preferably 35 to 50%, more preferably 40 to 50%. The present inventors presume that the above-described structure of the electrode catalyst enables a high electromotive force and a sufficient current density when applied to an ammonia fuel cell.
上記電極触媒は炭素材料に、上記合金材料を担持したものであることが好ましい。ここで、炭素材料としては炭素の含有割合が高い材料が好ましく、例えばカーボンブラックを用いることができる。 The electrode catalyst is preferably a carbon material carrying the alloy material. Here, as the carbon material, a material having a high carbon content is preferable. For example, carbon black can be used.
＜Ｆｅ、Ｃｏ及びＮｉを含む電極触媒の製造方法＞
本発明の電極触媒は、触媒前駆体を得る工程、第１の焼成工程及び第２の焼成工程により製造することができる。
<Method for Producing Electrocatalyst Containing Fe, Co and Ni>
The electrode catalyst of the present invention can be produced by a step of obtaining a catalyst precursor, a first firing step, and a second firing step.
［触媒前駆体を得る工程］
本工程においては、Ｆｅ、Ｃｏ及びＮｉを含む水溶液に炭素材料を含侵させ、触媒前駆体を得る。Ｆｅ、Ｃｏ及びＮｉを含む水溶液とは、Ｆｅ、Ｃｏ及びＮｉを所定の割合で含有している水溶液であればよく、Ｆｅ、Ｃｏ及びＮｉの塩を水に溶解させた水溶液が好ましい。Ｆｅの塩としては例えばＦｅ（ＮＯ３）３・９Ｈ２Ｏ、Ｃｏの塩としては例えばＣｏ（ＮＯ３）２・６Ｈ２Ｏ、Ｎｉの塩としては例えばＮｉ（ＮＯ３）２・６Ｈ２Ｏが挙げられる。
[Step of obtaining catalyst precursor]
In this step, a carbon precursor is impregnated in an aqueous solution containing Fe, Co and Ni to obtain a catalyst precursor. The aqueous solution containing Fe, Co, and Ni may be an aqueous solution containing Fe, Co, and Ni at a predetermined ratio, and an aqueous solution in which a salt of Fe, Co, and Ni is dissolved in water is preferable. Examples of the Fe salt include Fe (NO 3 ) 3 · 9H 2 O, examples of the Co salt include Co (NO 3 ) 2 · 6H 2 O, and examples of the Ni salt include Ni (NO 3 ) 2 · 6H 2 O Is mentioned.
Ｆｅ、Ｃｏ及びＮｉを含む水溶液におけるＦｅ、Ｃｏ及びＮｉの割合は、Ｆｅを１としたときに、Ｃｏが０．３〜３、Ｎｉが０．３〜３であることが好ましく、Ｃｏが０．５〜２、Ｎｉが０．５〜２であることがより好ましく、Ｃｏが０．８〜１．２、Ｎｉが０．８〜１．２であることがさらに好ましく、Ｃｏが０．９〜１．１、Ｎｉが０．９〜１．１であることが特に好ましい。最も好ましくは、Ｆｅ：Ｃｏ：Ｎｉが１：１：１の割合である。 The ratio of Fe, Co, and Ni in the aqueous solution containing Fe, Co, and Ni is preferably 0.3 to 3 for Co and 0.3 to 3 for Ni when Fe is 1, and 0 to Co. More preferably, Ni is 0.5-2, Co is 0.8-1.2, Ni is 0.8-1.2, and Co is 0.9. -1.1 and Ni are particularly preferably 0.9 to 1.1. Most preferably, the ratio of Fe: Co: Ni is 1: 1: 1.
Ｆｅ、Ｃｏ及びＮｉを含む水溶液に含侵させる炭素材料としては、炭素の含有割合が高い材料が好ましく、例えばカーボンブラックを用いることができる。カーボンブラックの重量は触媒量が３０〜８０重量％になるように調製することが好ましく、より好ましくは４０〜７０重量％であり、さらに好ましくは５０〜６０重量％である。また、Ｆｅ、Ｃｏ及びＮｉを含む水溶液に含侵させた炭素材料（触媒前駆体）の水分を蒸発させ、乾燥させる工程を有することが好ましい。 As the carbon material impregnated with the aqueous solution containing Fe, Co, and Ni, a material having a high carbon content is preferable, and for example, carbon black can be used. The weight of the carbon black is preferably adjusted so that the catalyst amount is 30 to 80% by weight, more preferably 40 to 70% by weight, and still more preferably 50 to 60% by weight. Moreover, it is preferable to have the process of evaporating the water | moisture content of the carbon material (catalyst precursor) impregnated with the aqueous solution containing Fe, Co, and Ni, and drying it.
［第１の焼成工程］
第１の焼成工程においては、上記工程で得られた触媒前駆体を水素雰囲気下において焼成する。第１の焼成工程における温度は、９００〜１３００℃であることが好ましい。９００〜１３００℃で焼成することによって、Ｆｅ、Ｃｏ及びＮｉを含む合金を生成し易くなる。焼成温度は、より好ましくは１０５０〜１３００℃であり、特に好ましくは１２００〜１３００℃である。急速に１２００〜１３００oＣ程度の高温にすることで、高分散で粒子径の小さい合金を形成することができる。
[First firing step]
In the first firing step, the catalyst precursor obtained in the above step is fired in a hydrogen atmosphere. The temperature in the first baking step is preferably 900 to 1300 ° C. By firing at 900 to 1300 ° C., an alloy containing Fe, Co, and Ni is easily generated. The firing temperature is more preferably 1050 to 1300 ° C, particularly preferably 1200 to 1300 ° C. By rapidly raising the temperature to about 1200 to 1300 ° C., an alloy having a high dispersion and a small particle size can be formed.
第１の焼成工程における焼成時間は、１〜１２０分であることが好ましく、より好ましくは１〜６０分であり、さらに好ましくは１〜３０分であり、特に好ましくは１〜１０分であり、最も好ましくは１〜３分である。 The firing time in the first firing step is preferably 1 to 120 minutes, more preferably 1 to 60 minutes, still more preferably 1 to 30 minutes, and particularly preferably 1 to 10 minutes, Most preferably, it is 1 to 3 minutes.
［第２の焼成工程］
第２の焼成工程においては、上記第１の焼成工程後の触媒前駆体（Ｆｅ、Ｃｏ及びＮｉを含む合金）を水素雰囲気下においてさらに焼成する。ここで、第２の焼成工程における温度は、上記第１の焼成工程よりも低温であり、第１の焼成温度よりも４００〜８００℃低温であると好ましく、６００〜７００℃低温であることがより好ましい。さらに好ましくは５００℃程度であるとよい。第１の焼成温度よりも低温でＦｅ、Ｃｏ及びＮｉを含む合金（第１の焼成工程後の触媒前駆体）を焼成することによって、合金部分からＦｅを析出させ、当該合金部分を形成していないＦｅ部分を含む合金材料が得られ易くなる。より具体的には、第２の焼成工程における温度は、４００〜６００℃であることが好ましい。この焼成温度は、より好ましくは４５０〜５５０℃であり、さらに好ましくは４８０〜５２０℃である。特に５００℃前後で焼成することにより、合金部分からＦｅがより析出しやすくなる。
[Second firing step]
In the second firing step, the catalyst precursor (an alloy containing Fe, Co, and Ni) after the first firing step is further fired in a hydrogen atmosphere. Here, the temperature in the second baking step is lower than that in the first baking step, preferably 400 to 800 ° C. lower than the first baking temperature, and 600 to 700 ° C. lower. More preferred. More preferably, it is good about 500 degreeC. By firing an alloy containing Fe, Co and Ni (catalyst precursor after the first firing step) at a temperature lower than the first firing temperature, Fe is precipitated from the alloy portion to form the alloy portion. It becomes easy to obtain an alloy material containing no Fe part. More specifically, the temperature in the second baking step is preferably 400 to 600 ° C. This firing temperature is more preferably 450 to 550 ° C, and further preferably 480 to 520 ° C. In particular, by firing at around 500 ° C., Fe is more likely to precipitate from the alloy part.
第２の焼成工程における焼成時間は、０．１〜１０時間であることが好ましく、より好ましくは０．５〜５時間であり、さらに好ましくは１〜５時間であり、特に好ましくは１〜４時間であり、最も好ましくは１〜３時間である。 The firing time in the second firing step is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, still more preferably 1 to 5 hours, and particularly preferably 1 to 4 hours. Hours, most preferably 1 to 3 hours.
このように触媒前駆体を２回の工程に分けて焼成し、特に第２の焼成工程における温度を第１の焼成工程よりも低温で焼成することによって、Ｆｅ、Ｃｏ及びＮｉを含む合金部分から一部のＦｅ（当該合金部分を形成していないＦｅ）が析出した、従来のＦｅ−Ｃｏ−Ｎｉ触媒には見られない構造を容易に発現させることができる。 In this way, the catalyst precursor is fired in two steps, and in particular, by firing the temperature in the second firing step at a lower temperature than the first firing step, from the alloy portion containing Fe, Co and Ni A structure which is not found in the conventional Fe—Co—Ni catalyst in which a part of Fe (Fe not forming the alloy part) is precipitated can be easily developed.
なお、上記第１の焼成工程又は第２の焼成工程においては、例えば、第１の焼成工程における合金部分の形成後に、Ｆｅをさらに添加し焼成することによっても、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を製造することも可能である。 In the first firing step or the second firing step, for example, an alloy containing Fe, Co, and Ni can be obtained by further adding Fe and firing after the formation of the alloy portion in the first firing step. It is also possible to produce an alloy material that includes a portion and an Fe portion that does not form the alloy portion.
＜燃料電池＞
本発明の電極触媒をアノード電極に用い、このアノード電極を固体電解質層の一方面に、もう一方の面にカソード電極を備えることによって、アンモニア燃料電池を構成することが可能である。
<Fuel cell>
An ammonia fuel cell can be constructed by using the electrode catalyst of the present invention as an anode electrode and providing the anode electrode on one side of the solid electrolyte layer and the cathode electrode on the other side.
アノード電極は、本電極触媒を含み、アンモニア燃料電池に用いることができるものであれば特に制限されないが、本電極触媒と層状金属酸化物を含むものが好ましく、本発明のＦｅ−Ｃｏ−Ｎｉ電極触媒と例えばＮａＣｏ２Ｏ４焼結体を所定の割合で混合し、ペースト状にして発泡Ｎｉ上に塗布したものを使用することがより好ましい。 The anode electrode is not particularly limited as long as it includes the present electrode catalyst and can be used for an ammonia fuel cell, but preferably includes the present electrode catalyst and a layered metal oxide, and the Fe—Co—Ni electrode of the present invention. More preferably, a catalyst and, for example, a NaCo 2 O 4 sintered body are mixed at a predetermined ratio, pasted into a paste, and applied onto foamed Ni.
ＮａＣｏ２Ｏ４焼結体は、上記国際公開第２０１０／００７９４９号に記載されているように、酢酸ナトリウムと酢酸コバルト四水和物を所定の比率で溶解させた溶液を乾燥させ、得られた試料の粉砕・仮焼成を行い、仮焼成後の試料を粉砕した後、ペレットに成型した状態で７５０〜８５０℃程度の温度で再度焼成を行い、その後、焼成後のペレットの粉砕・ペレット化を行って、９００〜１０００℃程度の温度で焼結させることにより、層状の結晶構造を有するＮａＣｏ２Ｏ４を得ることができる。 The NaCo 2 O 4 sintered body was obtained by drying a solution in which sodium acetate and cobalt acetate tetrahydrate were dissolved in a predetermined ratio as described in the above-mentioned International Publication No. 2010/007949. After crushing and pre-baking the sample, crushing the pre-baked sample and then baking again at a temperature of about 750 to 850 ° C. in a state of being molded into pellets, and then crushing and pelletizing the pellets after baking By performing the sintering at a temperature of about 900 to 1000 ° C., NaCo 2 O 4 having a layered crystal structure can be obtained.
固体電解質層は、ＯＨ−イオンが伝導できるものであれば特に制限されないが、下記一般式（１）で表される層状金属酸化物、又はＮａＣｏ２Ｏ４を含む固体電解質をペレット状に成型したものを使用することが好ましい。
（Ｌａ１−ｘＡｘ）（Ｓｒ１−ｙＢｙ）３（Ｃｏ１−ｚＣｚ）３Ｏ１０−δ （１）
［式中、ＡはＬａ以外の希土類元素であり、ＢはＭｇ、Ｃａ又はＢａであり、ＣはＴｉ、Ｖ、Ｃｒ又はＭｎであり、０≦ｘ＜１、０≦ｙ＜１、０≦ｚ＜１、δは酸素欠損量である。］
The solid electrolyte layer is not particularly limited as long as it can conduct OH − ions, but a layered metal oxide represented by the following general formula (1) or a solid electrolyte containing NaCo 2 O 4 is molded into a pellet shape. It is preferable to use one.
(La 1-x A x) (Sr 1-y B y) 3 (Co 1-z C z) 3 O 10-δ (1)
[In the formula, A is a rare earth element other than La, B is Mg, Ca, or Ba, C is Ti, V, Cr, or Mn, and 0 ≦ x <1, 0 ≦ y <1, 0 ≦ z <1, δ is the amount of oxygen deficiency. ]
上記一般式（１）中、ＡはＬａサイトに含まれる元素であり、Ｌａ（ランタン）以外の希土類元素である。例えば、Ｓｃ（スカンジウム）、Ｙ（イットリア）、Ｃｅ（セリウム）、Ｐｒ（プラセオジウム）、Ｎｄ（ネオジム）、Ｐｍ（プロメチウム）、Ｓｍ（サマリウム）、Ｅｕ（ユーロピウム）、Ｇｄ（ガドリニウム）、Ｔｂ（テルビウム）、Ｄｙ（ジスプロシウム）、Ｈｏ（ホルミウム）、Ｅｒ（エルビウム）、Ｔｍ（ツリウム）、Ｙｂ（イッテルビウム）又はＬｕ（ルテチウム）である。この中でもＡは、好ましくはＹ、Ｓｃ、Ｃｅ、Ｅｕ、Ｓｍ、Ｇｄ、Ｐｒ、Ｎｄであり、より好ましくはＹ、Ｅｕ、Ｓｍ、Ｇｄ、Ｎｄである。また、ｘは０以上１未満であり、好ましくは０以上０．５以下であり、より好ましくは０以上０．１以下である。 In the general formula (1), A is an element contained in the La site and is a rare earth element other than La (lanthanum). For example, Sc (scandium), Y (yttria), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium) ), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium) or Lu (lutetium). Among these, A is preferably Y, Sc, Ce, Eu, Sm, Gd, Pr, or Nd, and more preferably Y, Eu, Sm, Gd, or Nd. X is 0 or more and less than 1, preferably 0 or more and 0.5 or less, more preferably 0 or more and 0.1 or less.
ＢはＳｒサイトに含まれる元素であり、Ｍｇ、Ｃａ又はＢａである。好ましくはＢは、Ｃａ又はＢａである。また、ｙは０以上１未満であり、好ましくは０以上０．５以下であり、より好ましくは０以上０．１以下である。 B is an element contained in the Sr site and is Mg, Ca, or Ba. Preferably B is Ca or Ba. Moreover, y is 0 or more and less than 1, preferably 0 or more and 0.5 or less, more preferably 0 or more and 0.1 or less.
ＣはＣｏサイトに含まれる元素であり、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ又はＭｎである。好ましくはＣは、Ｍｎ、Ｆｅ又はＣｒであり、より好ましくはＭｎ又はＦｅである。また、ｚは０以上１未満であり、好ましくは０以上０．５以下であり、より好ましくは０以上０．１以下である。 C is an element contained in the Co site, and is Ti, V, Cr, Fe, or Mn. Preferably C is Mn, Fe or Cr, more preferably Mn or Fe. Z is 0 or more and less than 1, preferably 0 or more and 0.5 or less, more preferably 0 or more and 0.1 or less.
また、δは酸素欠損量を示し、−０．２以上１．５以下の酸素欠損が生じる。すなわち、式（１）中の酸素の価数（原子価）は、８．５以上１０．２以下となる。 Further, δ represents the amount of oxygen deficiency, and oxygen deficiency of −0.2 or more and 1.5 or less occurs. That is, the valence (valence) of oxygen in formula (1) is 8.5 or more and 10.2 or less.
上記一般式（１）で示される層状金属酸化物は、水蒸気処理が施されると当該層状金属酸化物中の酸素欠陥に水分子が水和し、水酸化物イオンの伝導性が発現すると推察される。この層状金属酸化物を含有する電解質層を採用することで、室温であっても十分に高い起電力が得ることができる。水蒸気処理は、例えば、後述する固体電解質を作成した後に、当該固体電解質を、所定の温度、相対湿度及び圧力の条件にさらすことによって実施することができる。その条件は、水酸化物イオンの伝導性が発現する範囲で適宜設定することが好ましい。例えば、温度を５０〜１２０℃の範囲とし、相対湿度を５０〜９０％の範囲とし、圧力を０．１〜１ＭＰａの範囲とし、処理時間を２〜４８時間の範囲とすることが好ましい。 The layered metal oxide represented by the general formula (1) is presumed that when water vapor treatment is performed, water molecules are hydrated by oxygen defects in the layered metal oxide, and the conductivity of hydroxide ions is expressed. Is done. By adopting an electrolyte layer containing this layered metal oxide, a sufficiently high electromotive force can be obtained even at room temperature. The steam treatment can be performed, for example, by preparing a solid electrolyte described later and then exposing the solid electrolyte to conditions of a predetermined temperature, relative humidity, and pressure. The conditions are preferably set as appropriate as long as the conductivity of hydroxide ions is expressed. For example, it is preferable that the temperature is in the range of 50 to 120 ° C., the relative humidity is in the range of 50 to 90%, the pressure is in the range of 0.1 to 1 MPa, and the treatment time is in the range of 2 to 48 hours.
カソード電極としては、アンモニア燃料電池に用いることができるものであれば特に制限されないが、カーボン材料と層状金属酸化物を含むものが好ましく、例えばＮａＣｏ２Ｏ４焼結体と、カーボンブラックを所定の割合で混合させカーボンペーパー上に塗布したものを使用することができる。 The cathode electrode is not particularly limited as long as it can be used for an ammonia fuel cell. However, the cathode electrode preferably includes a carbon material and a layered metal oxide. For example, a NaCo 2 O 4 sintered body and carbon black are used as a predetermined material. What was mixed in the ratio and apply | coated on carbon paper can be used.
上記燃料電池においては、発電する前に固体電解質層を２５０〜３００℃に昇温させ、室温で加湿した水素を５〜１０ｍｌ／分で１５〜６０分流し、前処理することが好ましい。これにより、固体電解質層内をＯＨ−イオンが伝導しやすくなる。また、アノード電極も同様に前処理することが好ましいが、カソード電極は同様の前処理を施さないことが好ましい。 In the fuel cell, it is preferable that the solid electrolyte layer is heated to 250 to 300 ° C. before power generation, and pretreated by flowing hydrogen humidified at room temperature at 5 to 10 ml / min for 15 to 60 minutes. Thereby, OH − ions are easily conducted in the solid electrolyte layer. The anode electrode is preferably pretreated in the same manner, but the cathode electrode is preferably not subjected to the same pretreatment.
上記燃料電池で発電するには、アノード電極にアンモニアを含むガスを供給し、カソード電極に加湿した酸素を含むガスを供給することが好ましい。これにより、アンモニア燃料電池内において以下の反応が生じ、発電する。
アノード電極：ＮＨ３＋３ＯＨ− → １／２Ｎ２＋３Ｈ２Ｏ＋３ｅ−
カソード電極：３／４Ｏ２＋３／２Ｈ２Ｏ＋３ｅ− → ３ＯＨ−
アンモニア燃料電池全体：ＮＨ３＋３／４Ｏ２ → １／２Ｎ２＋３／２Ｈ２Ｏ
In order to generate electricity with the fuel cell, it is preferable to supply a gas containing ammonia to the anode electrode and a gas containing humidified oxygen to the cathode electrode. As a result, the following reaction occurs in the ammonia fuel cell to generate power.
Anode electrode: NH 3 + 3OH − → 1 / 2N 2 + 3H 2 O + 3e −
Cathode electrode: 3 / 4O 2 + 3 / 2H 2 O + 3e − → 3OH −
Whole ammonia fuel cell: NH 3 + 3 / 4O 2 → 1 / 2N 2 + 3 / 2H 2 O
以上のとおり、本発明により、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒及びその製造方法を提供することができる。また、当該電極触媒を燃料電池のアノード電極に用いることによって、アンモニアを燃料する燃料電池を高い起電力及び十分な電流密度で作動させることが可能となる。 As described above, according to the present invention, it is possible to provide an electrode catalyst having an alloy material including an alloy part containing Fe, Co, and Ni and an Fe part not forming the alloy part, and a method for manufacturing the electrode catalyst. Further, by using the electrode catalyst as an anode electrode of a fuel cell, a fuel cell fueled with ammonia can be operated with a high electromotive force and a sufficient current density.
以上、本発明の実施形態について詳細に説明したが、本発明は上記実施形態に限定されるものではない。例えば、本発明に係るＦｅ、Ｃｏ及びＮｉを含む電極触媒は、燃料電池用触媒としてだけでなく、他の反応や合成等に使用することができ、例えば、アンモニア合成に用いることも可能である。 As mentioned above, although embodiment of this invention was described in detail, this invention is not limited to the said embodiment. For example, the electrode catalyst containing Fe, Co and Ni according to the present invention can be used not only as a catalyst for a fuel cell but also for other reactions and synthesis, for example, for ammonia synthesis. .
以下、実施例により本発明を説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
＜Ｆｅ−Ｃｏ−Ｎｉ電極触媒の調製＞
（実施例１）
まず、Ｆｅ：Ｃｏ：Ｎｉが１：１：１になるように、Ｆｅ（ＮＯ３）３・９Ｈ２Ｏを２．８６ｇ、Ｃｏ（ＮＯ３）２・６Ｈ２Ｏを２．０８ｇ、Ｎｉ（ＮＯ３）２・６Ｈ２Ｏを２．０８ｇ、蒸留水１０ｍｌ中に溶解させ、Ｆｅ、Ｃｏ及びＮｉの硝酸塩水溶液を用意した。この硝酸塩水溶液に、カーボンブラック（Ｖｕｌｃａｎ ＸＣ７２）を、得られる合金材料が５５重量％になるように１．００ｇ、蒸留水１０ｍｌを攪拌しながら加え、水浴上で水分を蒸発させ、８０℃のオーブンで一晩乾燥させた。
<Preparation of Fe-Co-Ni Electrocatalyst>
Example 1
First, 2.86 g of Fe (NO 3 ) 3 .9H 2 O, 2.08 g of Co (NO 3 ) 2 .6H 2 O, and Ni (NO) so that Fe: Co: Ni is 1: 1: 1. NO 3 ) 2 · 6H 2 O was dissolved in 2.08 g of distilled water 10 ml to prepare a nitrate aqueous solution of Fe, Co, and Ni. To this aqueous nitrate solution, carbon black (Vulcan XC72) is added with stirring to 1.00 g and distilled water 10 ml so that the obtained alloy material is 55% by weight, and the water is evaporated on a water bath. And dried overnight.
乾燥させた粉末を水素雰囲気下（Ｈ２／Ａｒ ６０ｍｌ／ｍｉｎ）、１２００℃（昇温速度：１００Ｋ／ｍｉｎ）で３分間焼成した。その後、自然冷却し、焼成した粉末をさらに同様の水素雰囲気下５００℃で保持し２時間焼成した。 The dried powder was fired at 1200 ° C. (temperature increase rate: 100 K / min) for 3 minutes in a hydrogen atmosphere (H 2 / Ar 60 ml / min). Thereafter, the powder was naturally cooled and fired, and the powder was further fired for 2 hours while being held at 500 ° C. in a similar hydrogen atmosphere.
（比較例１）
乾燥させた粉末を１２００℃で１回焼成しただけであり、５００℃での２回目の焼成を行わなかったこと以外は、実施例１と同様にして、Ｆｅ−Ｃｏ−Ｎｉ電極触媒を調製した。
(Comparative Example 1)
An Fe—Co—Ni electrode catalyst was prepared in the same manner as in Example 1 except that the dried powder was only fired once at 1200 ° C., and the second firing was not performed at 500 ° C. .
＜電極触媒の構造解析＞
粉末Ｘ線回折装置（Ｒｉｇａｋｕ、ＲＩＮＴ−Ｕｌｉｔｉｍａ＋）を用いて実施例１及び比較例１の電極触媒の構造解析を行った。測定条件は以下のとおりである。
線源：ＣｕＫα、
波長λ：０．１５４０５６ｎｍ、
管電圧：４０ｋＶ、
電流：２０ｍＡ、
測定範囲２θ：２〜８０°、
走査軸：２θ／θ、
スキャンステップ：０．０２°、
スキャンスピード：２°／分、
発散スリット：１／２°、
散乱スリット：１／２°、
受光スリット：０．１５ｍｍ。
<Structural analysis of electrode catalyst>
Structural analysis of the electrode catalysts of Example 1 and Comparative Example 1 was performed using a powder X-ray diffractometer (Rigaku, RINT-Ultima +). The measurement conditions are as follows.
Radiation source: CuKα
Wavelength λ: 0.154056 nm,
Tube voltage: 40 kV,
Current: 20 mA
Measurement range 2θ: 2 to 80 °,
Scanning axis: 2θ / θ,
Scan step: 0.02 °
Scanning speed: 2 ° / min,
Divergent slit: 1/2 °
Scattering slit: 1/2 °,
Light receiving slit: 0.15 mm.
実施例１及び比較例１の電極触媒のＸＲＤパターン（２〜８０°）を図１に、図１の一部を拡大したＸＲＤパターン（４０〜５０°）を図２に示す。図１及び図２のとおり、１２００℃で焼成し、さらに５００℃で焼成した実施例１に係る回折線（ａ）は、４３〜４５°に２つのピークが発現しており、これにより、Ｆｅ、Ｃｏ及びＮｉを含む合金部分と、当該合金部分を形成していないＦｅ部分と、を含む合金材料を有する電極触媒であることが確認された。 FIG. 1 shows an XRD pattern (2 to 80 °) of the electrode catalyst of Example 1 and Comparative Example 1, and FIG. 2 shows an XRD pattern (40 to 50 °) obtained by enlarging a part of FIG. As shown in FIG. 1 and FIG. 2, the diffraction line (a) according to Example 1 baked at 1200 ° C. and further baked at 500 ° C. has two peaks at 43 to 45 °. It was confirmed that the electrode catalyst had an alloy material containing an alloy part containing Co, Ni, and an Fe part not forming the alloy part.
一方、１２００℃で１回焼成しただけの比較例１に係る回折線（ｂ）は、４３〜４５°に１つしかピークが発現しておらず、Ｆｅ、Ｃｏ及びＮｉを含む合金部分はあるが、当該合金部分を形成していないＦｅ部分を含まない合金材料を有する電極触媒であることが確認された。 On the other hand, the diffraction line (b) according to Comparative Example 1 which has only been fired once at 1200 ° C. has only one peak at 43 to 45 °, and there is an alloy portion containing Fe, Co and Ni. However, it was confirmed that this is an electrode catalyst having an alloy material that does not include an Fe portion that does not form the alloy portion.
（実施例２）
＜発電試験＞
実施例１で得たＦｅ−Ｃｏ−Ｎｉ電極触媒の燃料電池用電極触媒としての性能を評価するために、図３の評価装置（燃料電池）を準備した。燃料電池１０は、ＮａＣｏ２Ｏ４ペレットを固体電解質層１とし、一方の面上にアノード電極２を、もう一方の面上にカソード電極３を配置した。また、上記燃料電池１０においては、アノード電極２及びカソード電極３の面上にＰｔ網４を配置し、これに接続された導線５（Ｐｔ線）からの出力を測定した。また、アノード電極２側には燃料ガス供給口７、カソード電極３側には酸素ガス供給口８を設け、さらに、ガスが燃料電池１０から漏れないように、それらの外側にセル本体部９を配置するとともに、セル本体部９と固体電解質層１との間にガスケット６を配置した。
(Example 2)
<Power generation test>
In order to evaluate the performance of the Fe—Co—Ni electrode catalyst obtained in Example 1 as a fuel cell electrode catalyst, the evaluation apparatus (fuel cell) shown in FIG. 3 was prepared. In the fuel cell 10, NaCo 2 O 4 pellets were used as the solid electrolyte layer 1, the anode electrode 2 was disposed on one surface, and the cathode electrode 3 was disposed on the other surface. In the fuel cell 10, the Pt net 4 was disposed on the surfaces of the anode electrode 2 and the cathode electrode 3, and the output from the conducting wire 5 (Pt line) connected thereto was measured. In addition, a fuel gas supply port 7 is provided on the anode electrode 2 side, an oxygen gas supply port 8 is provided on the cathode electrode 3 side, and a cell main body 9 is provided outside them so that gas does not leak from the fuel cell 10. While arranging, the gasket 6 was arrange | positioned between the cell main-body part 9 and the solid electrolyte layer 1. FIG.
ここで、ＮａＣｏ２Ｏ４ペレットの調製について述べる。本調製においては、以下の試薬を使用したが、他のものを適宜使用してもよい。
酢酸ナトリウム（ＣＨ３ＣＯＯＮａ、関東化学 特級）
酢酸コバルト四水和物（（ＣＨ３ＣＯＯ）２Ｃｏ・４Ｈ２Ｏ、和光純薬 鹿特級）
ジニトロジアンミンパラジウム（Ｐｄ（ＮＯ２）２（ＮＨ３）２、田中貴金属）
エチレングリコール（ＨＯＣＨ２ＣＨ２ＯＨ、和光純薬 特級）
Here, preparation of NaCo 2 O 4 pellet will be described. In this preparation, the following reagents were used, but other reagents may be used as appropriate.
Sodium acetate (CH 3 COONa, Kanto Chemical Special Grade)
Cobalt acetate tetrahydrate ((CH 3 COO) 2 Co.4H 2 O, Wako Pure Chemicals Shika Special Grade)
Dinitrodiammine palladium (Pd (NO 2 ) 2 (NH 3 ) 2 , Tanaka Kikinzoku)
Ethylene glycol (HOCH 2 CH 2 OH, Wako Pure Chemical)
ＮａＣｏ２Ｏ４ペレットを以下の（１）〜（５）の手順に従って調製した。なお、本実施例においては、ＮａＣｏ２Ｏ４ペレットは、後述の通り、温度９００℃程度の焼成過程を経て作製されるものであり、このような高温条件にあっては、Ｎａが蒸発する。したがって、理論量のモル比（Ｎａ：Ｃｏ＝１：２）で原料を調製すると、生成物中に不純物（Ｃｏ３Ｏ４）が生じてしまうため、ここでは、原料中のＮａとＣｏのモル比をＮａ：Ｃｏ＝１．６：２とした。
（１）酢酸ナトリウム５．００ｇ（６０．９５ｍｍｏｌ）と酢酸コバルト四水和物１９．００ｇ（７６．２８ｍｍｏｌ）を内容積２００ｍＬのテフロン（登録商標）製のビーカーに秤取し、蒸留水４０ｍＬを用いて溶解した。
（２）上記（１）で得た溶液を８０℃で撹拌しながら水分を蒸発させ、乾燥機（温度条件：８０℃）に入れて、一晩乾燥させた。
（３）乾燥させた試料をメノウ乳鉢でよく粉砕し、これをアルミナるつぼに入れた。このるつぼをＭｕｆｆｌｅ炉に入れ、試料を空気中にて温度７５０℃、保持時間５時間の条件で仮焼きした。
（４）仮焼きした試料をメノウ乳鉢で粉砕し、錠剤成型器を用いてペレット(直径：２０ｍｍ、厚さ：〜３ｍｍ)に成型した（圧力：３０ＭＰａ、保持時間：５分）。得られた成型体をＭｕｆｆｌｅ炉内に入れ、空気中にて温度７９０℃、保持時間３時間の条件で本焼きした。
（５）本焼きした試料を遊星型ボールミル（ＦＲＩＴＳＣＨ ｐｕｌｖｅｒｉｓｅｔｔｅ）に収容し、回転速度３００ｒｐｍ、処理時間２０分の条件で粉砕した。得られた粉体を錠剤成型器に入れてペレット(直径：１０ｍｍ、厚さ：１．７〜１２ｍｍ）に成型した。なお、ペレットの厚さが６ｍｍ以下の場合は、圧力３０ＭＰａ、保持時間５分、ペレットの厚さが１２ｍｍ程度の場合は、圧力４０ＭＰａ、保持時間５分の条件で成型した。得られた成型体をＭｕｆｆｌｅ炉内に入れ、空気中にて温度９００℃、保持時間３２時間の条件で焼結させ、ＮａＣｏ２Ｏ４の焼結体を得た。
NaCo 2 O 4 pellets were prepared according to the following procedures (1) to (5). In this embodiment, the NaCo 2 O 4 pellet is produced through a firing process at a temperature of about 900 ° C. as will be described later, and Na evaporates under such a high temperature condition. Therefore, when the raw material is prepared at a theoretical molar ratio (Na: Co = 1: 2), impurities (Co 3 O 4 ) are generated in the product. Here, the moles of Na and Co in the raw material are here. The ratio was Na: Co = 1.6: 2.
(1) Weigh 5.00 g (60.95 mmol) of sodium acetate and 19.00 g (76.28 mmol) of cobalt acetate tetrahydrate in a 200 mL Teflon (registered trademark) beaker, and add 40 mL of distilled water. Used to dissolve.
(2) While stirring the solution obtained in the above (1) at 80 ° C., water was evaporated, put into a dryer (temperature condition: 80 ° C.) and dried overnight.
(3) The dried sample was pulverized well in an agate mortar and placed in an alumina crucible. The crucible was placed in a Muffle furnace, and the sample was calcined in air at a temperature of 750 ° C. and a holding time of 5 hours.
(4) The calcined sample was pulverized in an agate mortar and formed into pellets (diameter: 20 mm, thickness: ˜3 mm) using a tablet molding machine (pressure: 30 MPa, holding time: 5 minutes). The obtained molded body was placed in a Muffle furnace and baked in air at a temperature of 790 ° C. and a holding time of 3 hours.
(5) The main-baked sample was placed in a planetary ball mill (FRITSCH pulverisete) and pulverized under conditions of a rotation speed of 300 rpm and a processing time of 20 minutes. The obtained powder was put into a tablet molding machine and molded into pellets (diameter: 10 mm, thickness: 1.7-12 mm). In addition, when the thickness of the pellet was 6 mm or less, it was molded under the conditions of a pressure of 30 MPa and a holding time of 5 minutes, and when the thickness of the pellet was about 12 mm, the pressure was 40 MPa and the holding time was 5 minutes. The obtained molded body was put in a Muffle furnace and sintered in air at a temperature of 900 ° C. and a holding time of 32 hours to obtain a NaCo 2 O 4 sintered body.
また、アノード電極２としては、実施例１で調製したＦｅ−Ｃｏ−Ｎｉ／Ｃ触媒０．０１ｇとＮａＣｏ２Ｏ４０．０１ｇとを粉砕・混合し、ペースト状に塗布したものを使用した。また、カソード電極３としては、カーボンペーパー（製品名：Ｐ５０Ｔ、バラードマテリアルプロダクツ社製）上にカーボンブラック１０ｍｇとＮａＣｏ２Ｏ４２０ｍｇとを塗布したものを使用した。 As the anode 2, it was used for the Fe-Co-Ni / C catalyst 0.01g and NaCo 2 O 4 0.01g prepared in Example 1 pulverized and mixed, was applied to the paste. As the cathode electrode 3, carbon paper (product name: P50T, Ballard Material Products Inc.) was used coated with carbon black 10mg and NaCo 2 O 4 20 mg on.
図３の評価装置（燃料電池）における測定は、以下の手順に従って行った。
（１）ＮａＣｏ２Ｏ４ペレットを２８０℃に昇温させ、室温で加湿した水素を５ｍｌ／分で３０分流し、前処理した。
（２）Ｆｅ−Ｃｏ−Ｎｉ／Ｃ触媒とＮａＣｏ２Ｏ４を面上に有する発泡Ｎｉ（アノード）を２８０℃に昇温させ、室温で加湿した水素を５ｍｌ／分で３０分流し、前処理した。
（３）アノードにアンモニアとＨｅの混合ガスを２０ｍｌ／分で供給するとともに、カソードに酸素を２０ｍｌ／分で８５℃加湿されたものを供給した。
（４）セル温度は８０℃とした。
The measurement in the evaluation apparatus (fuel cell) in FIG. 3 was performed according to the following procedure.
(1) The NaCo 2 O 4 pellet was heated to 280 ° C., and pretreated by flowing hydrogen humidified at room temperature at 5 ml / min for 30 minutes.
(2) Ni (anode) foamed with Fe—Co—Ni / C catalyst and NaCo 2 O 4 on the surface is heated to 280 ° C., and humidified hydrogen at room temperature is allowed to flow at 5 ml / min for 30 minutes for pretreatment did.
(3) A mixed gas of ammonia and He was supplied to the anode at 20 ml / min, and oxygen that was humidified at 85 ° C. at 20 ml / min was supplied to the cathode.
(4) The cell temperature was 80 ° C.
（比較例２）
アノード電極２に用いるＦｅ−Ｃｏ−Ｎｉ／Ｃ触媒として比較例１の触媒を用いた以外は、実施例２と同様にして燃料電池を構成し、発電試験を実施した。
(Comparative Example 2)
A fuel cell was constructed in the same manner as in Example 2 except that the catalyst of Comparative Example 1 was used as the Fe—Co—Ni / C catalyst used for the anode electrode 2, and a power generation test was performed.
実施例２及び比較例２の測定結果を図４に示す。図４は、上記の測定条件で実施例２及び比較例２の燃料電池を動作させたときの、得られる電流密度（ｍＡｃｍ−２）の値に対する、そのときのセル電圧（Ｖ）及び電力密度（ｍＡｃｍ−２）の値を示すグラフである。図４中、ａ１及びａ２はそれぞれ実施例２の燃料電池で得られたセル電圧及び電流密度の値を示し、ｂ１及びｂ２はそれぞれ比較例２の燃料電池で得られたセル電圧及び電流密度の値を示す。図４のａ１及びａ２のとおり、本発明の電極触媒（実施例１）を用いた実施例２の燃料電池は、ＯＣＶは０．８Ｖ、電流密度は２８０ｍＡ／ｃｍ２と高い性能を示した。一方、比較例１の電極触媒を用いた比較例２の燃料電池については、図４のｂ１及びｂ２のとおり、ＯＣＶは０．７６Ｖ、電流密度は１７５ｍＡ／ｃｍ２と実施例２に比べて低い性能を示した。 The measurement results of Example 2 and Comparative Example 2 are shown in FIG. FIG. 4 shows the cell voltage (V) and power density at that time with respect to the value of current density (mAcm −2 ) obtained when the fuel cells of Example 2 and Comparative Example 2 were operated under the above measurement conditions. It is a graph which shows the value of (mAcm <-2 >). In FIG. 4, a1 and a2 indicate the cell voltage and current density values obtained with the fuel cell of Example 2, respectively, and b1 and b2 indicate the cell voltage and current density obtained with the fuel cell of Comparative Example 2, respectively. Indicates the value. As shown in a1 and a2 of FIG. 4, the fuel cell of Example 2 using the electrode catalyst (Example 1) of the present invention exhibited high performance with an OCV of 0.8 V and a current density of 280 mA / cm 2 . On the other hand, the fuel cell of Comparative Example 2 using an electrode catalyst of Comparative Example 1, as b1 and b2 in FIG. 4, OCV is 0.76 V, the current density is lower than that of 175 mA / cm 2 Example 2 Showed performance.
（実施例３）
第１の焼成温度を９００℃とした以外は実施例１と同様にして調製した電極触媒のＳＥＭ画像を図５に、ＴＥＭ画像を図６に示す。
(Example 3)
FIG. 5 shows an SEM image of the electrode catalyst prepared in the same manner as in Example 1 except that the first baking temperature was 900 ° C., and FIG. 6 shows a TEM image.
１…固体電解質層、２…アノード電極、３…カソード電極、１０…燃料電池。 DESCRIPTION OF SYMBOLS 1 ... Solid electrolyte layer, 2 ... Anode electrode, 3 ... Cathode electrode, 10 ... Fuel cell.
Claims (5)
前記触媒前駆体を水素雰囲気下において焼成する第１の焼成工程と、
前記第１の焼成工程後の前記触媒前駆体を水素雰囲気下において前記第１の焼成工程よりも低温で焼成する第２の焼成工程と、を備える電極触媒の製造方法。 Impregnating a carbon material with an aqueous solution containing Fe, Co and Ni to obtain a catalyst precursor;
A first firing step of firing the catalyst precursor in a hydrogen atmosphere;
And a second firing step of firing the catalyst precursor after the first firing step at a lower temperature than the first firing step in a hydrogen atmosphere.
The manufacturing method of Claim 4 whose temperature in a said 1st baking process is 900-1300 degreeC, and whose temperature in a said 2nd baking process is 400-600 degreeC.
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