JP2007207662A - Electrode catalyst for fuel cell, its manufacturing method, and fuel cell using the catalyst - Google Patents
Electrode catalyst for fuel cell, its manufacturing method, and fuel cell using the catalyst Download PDFInfo
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- JP2007207662A JP2007207662A JP2006027005A JP2006027005A JP2007207662A JP 2007207662 A JP2007207662 A JP 2007207662A JP 2006027005 A JP2006027005 A JP 2006027005A JP 2006027005 A JP2006027005 A JP 2006027005A JP 2007207662 A JP2007207662 A JP 2007207662A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000000446 fuel Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 177
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 172
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 167
- 239000002245 particle Substances 0.000 claims abstract description 130
- 239000005539 carbonized material Substances 0.000 claims abstract description 117
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 88
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 45
- 150000003624 transition metals Chemical class 0.000 claims abstract description 45
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 238000010586 diagram Methods 0.000 claims abstract description 10
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 45
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- 238000000034 method Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 30
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- 239000012528 membrane Substances 0.000 claims description 17
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- 239000001301 oxygen Substances 0.000 abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 36
- 230000010757 Reduction Activity Effects 0.000 abstract description 26
- 229910052697 platinum Inorganic materials 0.000 abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
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- 229910017052 cobalt Inorganic materials 0.000 description 45
- 239000010941 cobalt Substances 0.000 description 45
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- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
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- 229920000557 Nafion® Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- FLESAADTDNKLFJ-UHFFFAOYSA-N nickel;pentane-2,4-dione Chemical compound [Ni].CC(=O)CC(C)=O FLESAADTDNKLFJ-UHFFFAOYSA-N 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- 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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- Catalysts (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は、白金や白金合金等の貴金属を全く担持しないか、或いはその使用量を極力抑えた燃料電池用電極触媒と、この触媒を製造する方法と、この触媒を用いた燃料電池に関するものである。 The present invention relates to an electrode catalyst for a fuel cell in which no noble metal such as platinum or a platinum alloy is supported at all, or a use amount thereof being suppressed as much as possible, a method for producing the catalyst, and a fuel cell using the catalyst. is there.
高効率、無公害の燃料電池の実用化は、地球温暖化、環境汚染問題に対する重要な対処手段である。とくに昨今、電気自動車（ＦＣＥＶ）や定置用電熱併供システム（ＣＧ−ＦＣ）に用いられる固体高分子型燃料電池は、低コスト化の可能性が大きく、広く研究、開発競争が展開されている。
こうした固体高分子型燃料電池において、その反応は多孔質ガス拡散電極内で起こる。十分な電流密度Ｉ（Ａ／投影電極面積）を得るために、その電極としては、比表面積が大きくかつ導電性のあるカーボンブラックを多孔質構造体兼触媒担体としたものが一般に使用されている。また、その触媒としては白金（Ｐｔ）あるいは白金合金系触媒（Ｐｔ−Ｆｅ，Ｐｔ−Ｃｒ，Ｐｔ−Ｒｕ）が使用され、これら貴金属触媒が担体に高分散担持（粒径２〜数十ｎｍ）されている。
Practical application of high-efficiency, pollution-free fuel cells is an important countermeasure for global warming and environmental pollution problems. In particular, recently, polymer electrolyte fuel cells used in electric vehicles (FCEV) and stationary combined heat and power systems (CG-FC) have a great potential for cost reduction, and research and development competition are widely deployed. .
In such a polymer electrolyte fuel cell, the reaction occurs in the porous gas diffusion electrode. In order to obtain a sufficient current density I (A / projection electrode area), an electrode having a large specific surface area and conductive carbon black as a porous structure / catalyst support is generally used as the electrode. . As the catalyst, platinum (Pt) or a platinum alloy catalyst (Pt—Fe, Pt—Cr, Pt—Ru) is used, and these noble metal catalysts are supported in a highly dispersed state (particle diameter 2 to several tens of nm). Has been.
固体高分子型燃料電池では、これまで特に、カソード極で起こる酸素の還元反応が非常に起こりにくいため、標準的担体材料としてのある決まった銘柄の炭素担体に、触媒である白金が、例えば、１ｍｇ／ｃｍ2の割合で多量に投入されてきた。即ち、白金の標準的担体材料としては、(1)カーボンブラック、例えばカーボンブラック(Carbon Black)Ｂ１ Ｄｅｇｕｓｓａ−Ｈｕｅｌｓ社(フランクフルト)、(2)ファーネスブラック、例えばバルカン(Vulcan)ＸＣ−７２ Ｃａｂｏｔ社(マサチューセッツ)、(3)アセチレンブラック、例えばシャウイニガンブラック(Shawinigan Black)Ｃｈｅｖｒｏｎ Ｃｈｅｍｉｃａｌｓ社(ヒューストン、テキサス)などが挙げられる。
しかしながら、従来の標準的担体材料であるカーボンブラック、ファーネスブラック、アセチレンブラックへの白金の担持の仕方は、白金をできるだけ微分散させることに多くの努力が傾注されてきた。そこでは、カーボンブラック等の標準的担体材料は、単に白金を分散させ易くするとともに、担体自体が導電性を与える媒体に過ぎず、担持された白金の活性化を十分に図ることができなかった。
In the polymer electrolyte fuel cell, since the reduction reaction of oxygen that has occurred at the cathode electrode is very unlikely to occur so far, platinum as a catalyst is, for example, a certain brand of carbon support as a standard support material. A large amount has been introduced at a rate of 1 mg / cm 2 . That is, standard support materials for platinum include: (1) carbon black, such as Carbon Black B1 Degussa-Huels (Frankfurt), (2) furnace black, such as Vulcan XC-72 Cabot ( Massachusetts), (3) acetylene black, such as Shawinigan Black Chevron Chemicals (Houston, Texas).
However, with respect to the manner in which platinum is supported on carbon black, furnace black, and acetylene black, which are conventional standard support materials, much effort has been devoted to finely dispersing platinum as much as possible. In this case, standard carrier materials such as carbon black merely facilitate the dispersion of platinum, and the carrier itself is merely a medium that imparts conductivity, and it was not possible to sufficiently activate the supported platinum. .
この点を改良するために、難黒鉛化性炭素を主成分とする炭素材料であって、その構造の少なくとも一部に乱層構造を有するものを電極触媒として用いる燃料電池用電極触媒が開示されている（例えば、特許文献１参照。）。この燃料電池用電極触媒では、難黒鉛化性炭素を生成する原材料に金属化合物を添加混合した後、焼成による炭素化処理により得られかつその構造の少なくとも一部に乱層構造を有するものが電極触媒として用いられる。
このように構成された燃料電池用電極触媒では、白金又は白金系合金等の貴金属触媒の代替として廉価で触媒活性の高い電極触媒が得られ、容易に製造することができるとともに、炭素化過程を制御することにより望み通りの触媒機能を備える炭素材料が得られるようになっている。
また白金又は白金合金を担持した炭素基材が窒素原子又はホウ素原子がドープされた平均粒径４５μｍ以下のカーボンアロイ微粒子であって、炭素基材が含窒素化合物又は含ホウ素化合物と熱硬化性樹脂の前駆体とを加熱反応させて重合し、これにより得られた窒素化合物含有熱硬化性樹脂又はホウ素化合物含有硬化性樹脂を熱処理して炭素化し、炭素化された窒素化合物含有熱硬化性樹脂又はホウ素化合物含有硬化性樹脂を微粉砕してなるカーボンアロイ微粒子である燃料電池用電極触媒が開示されている（例えば、特許文献２参照。）。
このように構成された燃料電池用電極触媒では、炭素中に窒素又はホウ素のいずれか一方又は双方が導入された場合、導入した元素は炭素構造の発達を妨げる。これに伴い、基底面とは垂直方向のエッジ面の割合が増加する。エッジ面は基底面に比べて電子的、化学的に活性であり、このため、これと接触した白金は活性化される。また、同時に電極触媒では電子が増加し、炭素基材中にホウ素原子がドープされた場合、電極触媒では電子が減少する。これにより窒素原子又はホウ素原子がドープされない場合と比較して、窒素原子又はホウ素原子がドープされた炭素基材は導電性材料としての機能だけでなく、酸素還元の機能が付加され、担持された白金の活性化がより高まるようになっている。
In the fuel cell electrode catalyst thus configured, an inexpensive and highly active electrode catalyst can be obtained as an alternative to a noble metal catalyst such as platinum or a platinum-based alloy, and the carbonization process can be easily manufactured. By controlling the carbon material, a carbon material having a desired catalytic function can be obtained.
The carbon base material carrying platinum or a platinum alloy is carbon alloy fine particles having an average particle size of 45 μm or less doped with nitrogen atoms or boron atoms, and the carbon base material is a nitrogen-containing compound or a boron-containing compound and a thermosetting resin. The precursor of the above is polymerized by heating reaction, and the resulting nitrogen compound-containing thermosetting resin or boron compound-containing curable resin is carbonized by heat treatment, or the carbonized nitrogen compound-containing thermosetting resin or A fuel cell electrode catalyst, which is carbon alloy fine particles obtained by finely pulverizing a boron compound-containing curable resin, is disclosed (for example, see Patent Document 2).
In the fuel cell electrode catalyst configured as described above, when one or both of nitrogen and boron is introduced into carbon, the introduced element hinders the development of the carbon structure. Accordingly, the ratio of the edge surface in the direction perpendicular to the base surface increases. The edge surface is more electronically and chemically active than the basal surface, so that platinum in contact with it is activated. At the same time, electrons increase in the electrode catalyst, and when boron atoms are doped in the carbon substrate, electrons decrease in the electrode catalyst. As a result, the carbon base material doped with nitrogen atoms or boron atoms was supported not only as a conductive material but also as an oxygen reduction function as compared with the case where nitrogen atoms or boron atoms were not doped. The activation of platinum is increasing.
しかし、上記従来の特許文献１に示された燃料電池用電極触媒では、構造の少なくとも一部に乱層構造を有する炭素材料を用いることにより、また上記従来の特許文献２に示された燃料電池用電極触媒では、炭素中に窒素又はホウ素を導入して炭素構造の発達を妨げ、基底面に対して垂直方向のエッジ面の割合を増加させることにより、それぞれ電極触媒の酸素還元活性を向上させているけれども、その電極触媒の酸素還元活性は未だ不十分であった。
本発明の目的は、酸素還元活性を炭素化材自体にもたせることができ、これにより炭素化材の酸素還元活性を向上できる、燃料電池用電極触媒及びその製造方法並びに該触媒を用いた燃料電池を提供することにある。
本発明の別の目的は、高価な白金や白金合金等の貴金属を担持せずに、或いは僅かな貴金属の使用で、高い酸素還元活性を発現できる、燃料電池用電極触媒の製造方法及びその方法で製造された電極触媒を提供することにある。
本発明の更に別の目的は、高価な白金や白金合金等の貴金属を担持せずに、或いは僅かな貴金属の使用で、極めて高い電流密度を得ることができる、燃料電池を提供することにある。
However, the fuel cell electrode catalyst disclosed in the above-mentioned conventional patent document 1 uses a carbon material having a turbulent layer structure in at least a part of the structure, and also the fuel cell disclosed in the above-mentioned conventional patent document 2. In the electrode catalyst, nitrogen or boron is introduced into the carbon to prevent the development of the carbon structure, and the ratio of the edge surface perpendicular to the basal plane is increased, thereby improving the oxygen reduction activity of the electrode catalyst. However, the oxygen reduction activity of the electrocatalyst was still insufficient.
An object of the present invention is to provide an electrode catalyst for a fuel cell, a method for producing the same, and a fuel cell using the catalyst, in which the oxygen reduction activity can be imparted to the carbonization material itself, thereby improving the oxygen reduction activity of the carbonization material. Is to provide.
Another object of the present invention is to provide a method for producing an electrode catalyst for a fuel cell, which can exhibit high oxygen reduction activity without carrying a noble metal such as expensive platinum or platinum alloy, or by using a small amount of noble metal, and the method thereof. It is to provide an electrocatalyst manufactured in
Still another object of the present invention is to provide a fuel cell capable of obtaining an extremely high current density without carrying a noble metal such as expensive platinum or platinum alloy or using a small amount of noble metal. .
請求項１に係る発明は、遷移金属共存下で炭素化調製して得られた炭素化材からなる燃料電池用電極触媒の改良である。
その特徴ある構成は、炭素化材が、多数の平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子が非凝集状態で集合して形成されたところにある。
請求項２に係る発明は、請求項１に係る発明であって、更にシェル状構造の炭素粒子の（００２）面反射に対応するＸ線回折線図における先鋭成分面積と略平坦成分面積との合計面積に対する先鋭成分面積の割合が０．１以上であることを特徴とする。
請求項３に係る発明は、請求項１又は２に係る発明であって、更にシェル状構造の炭素粒子の炭素網面のエッジ面に、シェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２の窒素を含むことを特徴とする。
請求項４に係る発明は、請求項１又は２に係る発明であって、更にシェル状構造の炭素粒子の炭素網面のエッジ面に、シェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２の窒素を含み、かつシェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．７のホウ素を含むことを特徴とする。
The invention according to claim 1 is an improvement of an electrode catalyst for a fuel cell comprising a carbonized material obtained by carbonization in the presence of a transition metal.
The characteristic structure is that the carbonized material is formed by aggregating a large number of carbon particles having a shell-like structure having an average particle diameter of 10 to 20 nm in a non-aggregated state.
The invention according to claim 2 is the invention according to claim 1, further comprising a sharp component area and a substantially flat component area in an X-ray diffraction diagram corresponding to (002) plane reflection of shell-structured carbon particles. The ratio of the sharp component area to the total area is 0.1 or more.
The invention according to claim 3 is the invention according to claim 1 or 2, wherein the atomic ratio relative to the carbon on the surface of the carbon particles of the shell-like structure on the edge surface of the carbon network surface of the carbon particles of the shell-like structure. And 0.01 to 0.2 nitrogen.
The invention according to claim 4 is the invention according to claim 1 or 2, wherein the atomic ratio relative to the carbon on the surface of the carbon particles of the shell-like structure on the edge surface of the carbon network surface of the carbon particles of the shell-like structure. And 0.01 to 0.2 nitrogen, and boron in an atomic ratio of 0.01 to 0.7 with respect to the carbon on the surface of the shell-like carbon particles.
請求項５に係る発明は、遷移金属をイオン交換樹脂に導入して遷移金属含有イオン交換樹脂を調製する工程と、この遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入する工程とを含む燃料電池用電極触媒の製造方法である。
請求項６に係る発明は、遷移金属をイオン交換樹脂に導入して遷移金属含有イオン交換樹脂を調製する工程と、この遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入する工程とを含む燃料電池用電極触媒の製造方法である。
請求項７に係る発明は、遷移金属をイオン交換樹脂に導入して遷移金属含有イオン交換樹脂を調製する工程と、この遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製する工程と、このポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入する工程とを含む燃料電池用電極触媒の製造方法である。
請求項８に係る発明は、遷移金属をイオン交換樹脂に導入して遷移金属含有イオン交換樹脂を調製する工程と、この遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製する工程と、このポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入する工程とを含む燃料電池用電極触媒の製造方法である。
The invention according to claim 5 includes a step of preparing a transition metal-containing ion exchange resin by introducing a transition metal into the ion exchange resin, and heat-treating the transition metal-containing ion exchange resin at a temperature of 600 to 2000 ° C. A step of preparing a carbonized material that is an aggregate of carbon particles having a shell-like structure having a diameter of 10 to 20 nm, a step of introducing nitrogen or nitrogen and boron into the edge surface of the carbon network surface of the carbon particles by a liquid phase doping method; Is a method for producing a fuel cell electrode catalyst.
The invention according to claim 6 includes a step of preparing a transition metal-containing ion exchange resin by introducing a transition metal into the ion exchange resin, and heat-treating the transition metal-containing ion exchange resin at a temperature of 600 to 2000 ° C. A step of preparing a carbonized material that is an aggregate of carbon particles having a shell-like structure having a diameter of 10 to 20 nm, a step of introducing nitrogen or nitrogen and boron into the edge surface of the carbon network surface of the carbon particles by a vapor phase doping method, Is a method for producing a fuel cell electrode catalyst.
The invention according to claim 7 is a process for preparing a transition metal-containing ion exchange resin by introducing a transition metal into an ion exchange resin, and preparing a polymer mixture by introducing the transition metal-containing ion exchange resin into a carbon precursor. A step of preparing the carbonized material which is an aggregate of carbon particles having an average particle size of 10 to 20 nm by heat-treating the polymer mixture at a temperature of 600 to 2000 ° C., and a carbon network of the carbon particles. And a step of introducing nitrogen or nitrogen and boron into the edge surface of the surface by a liquid phase doping method.
The invention according to claim 8 is a step of preparing a transition metal-containing ion exchange resin by introducing a transition metal into an ion exchange resin, and preparing a polymer mixture by introducing the transition metal-containing ion exchange resin into a carbon precursor. A step of preparing the carbonized material which is an aggregate of carbon particles having an average particle size of 10 to 20 nm by heat-treating the polymer mixture at a temperature of 600 to 2000 ° C., and a carbon network of the carbon particles. And a step of introducing nitrogen or nitrogen and boron into the edge surface of the surface by a vapor phase doping method.
請求項９に係る発明は、請求項１ないし４いずれか１項に記載の燃料電池用電極触媒を固体高分子電解質膜の一方又は双方の面に層状に形成した電解反応層を有する燃料電池である。
請求項１０に係る発明は、請求項５ないし８いずれか１項に記載の方法で製造された燃料電池用電極触媒を固体高分子電解質膜の一方又は双方の面に層状に形成した電解反応層を有する燃料電池である。
The invention according to claim 9 is a fuel cell having an electrolytic reaction layer in which the electrode catalyst for fuel cell according to any one of claims 1 to 4 is formed in a layer form on one or both sides of a solid polymer electrolyte membrane. is there.
The invention according to claim 10 is an electrolytic reaction layer in which the electrode catalyst for a fuel cell produced by the method according to any one of claims 5 to 8 is formed in a layer on one or both surfaces of the solid polymer electrolyte membrane. A fuel cell having
請求項１に係る発明では、多数の平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子を非凝集状態で集合させることにより炭素化材を形成したので、ナノオーダーの均一なシェル構造の各炭素化材の表面に、カソード電極の触媒活性、即ち酸素還元活性をもたらす欠陥が多く存在する。この結果、酸素還元活性を炭素化材自体にもたせることができる。
請求項２に係る発明では、シェル状構造の炭素粒子の（００２）面反射に対応するＸ線回折線図における先鋭成分面積と略平坦成分面積との合計面積に対する先鋭成分面積の割合が０．１以上であるので、即ちシェル構造の発達程度を表すパラメータが０．１以上と大きくなる。この結果、シェル状構造の炭素粒子の平均粒径を１０〜２０ｎｍの範囲内に揃えることができるので、酸素還元活性を炭素化材自体にもたせることができる。
請求項３に係る発明では、シェル状構造の炭素粒子の炭素網面のエッジ面に、シェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２の窒素を含むので、欠陥の一つである炭素粒子の炭素網面のエッジ面に窒素を導入することにより、炭素化材にカソード電極の触媒活性、即ち酸素還元活性が発現させることができる。
請求項４に係る発明では、シェル状構造の炭素粒子の炭素網面のエッジ面に、シェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２の窒素を含み、かつシェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．７のホウ素を含むので、欠陥の一つである炭素粒子の炭素網面のエッジ面に窒素及びホウ素を導入することにより、炭素化材のカソード電極の触媒活性、即ち酸素還元活性が更に向上できる。
In the invention according to claim 1, since the carbonized material is formed by aggregating a large number of shell-like carbon particles having an average particle diameter of 10 to 20 nm in a non-aggregated state, each carbon having a uniform shell structure of nano-order. There are many defects on the surface of the chemical material that cause catalytic activity of the cathode electrode, that is, oxygen reduction activity. As a result, the oxygen reduction activity can be imparted to the carbonized material itself.
In the invention according to claim 2, the ratio of the sharp component area to the total area of the sharp component area and the substantially flat component area in the X-ray diffraction diagram corresponding to the (002) plane reflection of the shell-shaped carbon particles is 0.00. Since it is 1 or more, that is, the parameter representing the degree of development of the shell structure becomes as large as 0.1 or more. As a result, since the average particle diameter of the carbon particles having a shell-like structure can be made within the range of 10 to 20 nm, the oxygen reduction activity can be imparted to the carbonized material itself.
In the invention according to claim 3, since the edge surface of the carbon network surface of the shell-like structure carbon particles contains nitrogen having an atomic ratio of 0.01 to 0.2 with respect to the carbon on the surface of the shell-like structure carbon particles. By introducing nitrogen into the edge surface of the carbon network surface of the carbon particles, which is one of the defects, the catalytic activity of the cathode electrode, that is, the oxygen reduction activity can be expressed in the carbonized material.
In the invention according to claim 4, the edge surface of the carbon network surface of the shell-like structure carbon particles contains nitrogen having an atomic ratio of 0.01 to 0.2 with respect to the carbon on the surface of the shell-like structure carbon particles, In addition, since boron is included in an atomic ratio of 0.01 to 0.7 with respect to the carbon on the surface of the shell-shaped carbon particles, nitrogen and boron are introduced into the edge surface of the carbon network surface of the carbon particles, which is one of the defects. By doing so, the catalytic activity of the cathode of the carbonized material, that is, the oxygen reduction activity can be further improved.
請求項５に係る発明では、遷移金属をイオン交換樹脂に導入して調製した遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製し、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入したので、シェル状構造の炭素粒子の凝集を抑制でき、炭素網面のエッジ面に窒素又は窒素及びホウ素が導入されたシェル状構造の炭素化材を得ることができる。この結果、炭素化材自体に酸素還元活性をもたせることができる。
請求項６に係る発明では、遷移金属をイオン交換樹脂に導入して調製した遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製し、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入したので、液相ドープ法では炭素化材と窒素源等の混合工程とこの混合後の熱処理工程の２つの工程を必要とするのに対し、１つの工程で炭素化材に窒素等を導入することができ、液相ドープ法より製造工数を低減できる。
請求項７に係る発明では、遷移金属をイオン交換樹脂に導入して調製した遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製し、このポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製し、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入したので、炭素前駆体中への遷移金属含有イオン交換樹脂の導入により、シェル状構造の炭素粒子の凝集を更に抑制でき、効率良くシェル状構造の炭素粒子を形成できるとともに、炭素網面のエッジ面に窒素又は窒素及びホウ素が導入されたシェル状構造の炭素化材を得ることができる。この結果、炭素化材自体に酸素還元活性をもたせることができる。
請求項８に係る発明では、遷移金属をイオン交換樹脂に導入して調製した遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製し、このポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製し、炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入したので、液相ドープ法では炭素化材と窒素源等の混合工程とこの混合後の熱処理工程の２つの工程を必要とするのに対し、１つの工程で炭素化材に窒素等を導入することができ、液相ドープ法より製造工数を低減できる。
In the invention according to claim 5, shell-structured carbon particles having an average particle size of 10 to 20 nm are obtained by heat-treating a transition metal-containing ion exchange resin prepared by introducing a transition metal into an ion exchange resin at a temperature of 600 to 2000 ° C. A carbonized material that is an aggregate of the carbon particles was prepared, and nitrogen or nitrogen and boron were introduced into the edge surface of the carbon network surface of the carbon particles by a liquid phase doping method. A carbonized material having a shell-like structure in which nitrogen or nitrogen and boron are introduced into the edge surface of the mesh surface can be obtained. As a result, the carbonized material itself can have oxygen reduction activity.
In the invention according to claim 6, the transition metal-containing ion exchange resin prepared by introducing the transition metal into the ion exchange resin is heat-treated at a temperature of 600 to 2000 ° C., so that the carbon particles having a shell-like structure with an average particle diameter of 10 to 20 nm are obtained. A carbonized material that is an aggregate of the above is prepared, and nitrogen or nitrogen and boron are introduced into the edge surface of the carbon network surface of the carbon particles by a vapor phase doping method. While two steps, a mixing step and a heat treatment step after mixing, are required, nitrogen and the like can be introduced into the carbonized material in one step, and the number of manufacturing steps can be reduced compared to the liquid phase doping method.
In the invention which concerns on Claim 7, the transition metal containing ion exchange resin prepared by introduce | transducing a transition metal into an ion exchange resin is introduce | transduced in a carbon precursor, a polymer mixture is prepared, and this polymer mixture is 600-2000 degreeC. A carbonized material that is an aggregate of shell-shaped carbon particles having an average particle diameter of 10 to 20 nm is prepared by heat treatment at a temperature, and liquid phase doping is performed with nitrogen or nitrogen and boron on the edge surface of the carbon network surface of the carbon particles. Therefore, the introduction of the transition metal-containing ion exchange resin into the carbon precursor can further suppress the aggregation of the shell-like carbon particles, can efficiently form the shell-like carbon particles, and the carbon network surface. A carbonized material having a shell-like structure in which nitrogen or nitrogen and boron are introduced into the edge surface of the substrate can be obtained. As a result, the carbonized material itself can have oxygen reduction activity.
In the invention which concerns on Claim 8, the transition metal containing ion exchange resin prepared by introduce | transducing a transition metal into an ion exchange resin is introduce | transduced in a carbon precursor, a polymer mixture is prepared, and this polymer mixture is 600-2000 degreeC. A carbonized material that is an aggregate of shell-like carbon particles having an average particle diameter of 10 to 20 nm is prepared by heat treatment at a temperature, and nitrogen or nitrogen and boron are vapor-phase doped on the edge surface of the carbon network surface of the carbon particles In the liquid phase doping method, two steps of mixing the carbonized material and the nitrogen source and the heat treatment step after the mixing are necessary, whereas nitrogen or the like is added to the carbonized material in one step. The number of manufacturing steps can be reduced as compared with the liquid phase doping method.
請求項９に係る発明では、上記請求項１ないし４いずれか１項に記載の燃料電池用電極触媒を固体高分子電解質膜の一方又は双方の面に層状に形成した電解反応層を有するので、電極触媒で高い酸化還元能力が発現され、燃料電池の電流密度が極めて高く又は比較的高くなる。
請求項１０に係る発明では、上記請求項５ないし８いずれか１項に記載の方法で製造された燃料電池用電極触媒を固体高分子電解質膜の一方又は双方の面に層状に形成した電解反応層を有するので、電極触媒で高い酸化還元能力が発現され、燃料電池の電流密度が極めて高く又は比較的高くなる。
The invention according to claim 9 has an electrolytic reaction layer in which the electrode catalyst for fuel cells according to any one of claims 1 to 4 is formed in layers on one or both surfaces of the solid polymer electrolyte membrane. The electrode catalyst exhibits a high redox capacity, and the current density of the fuel cell is extremely high or relatively high.
The invention according to claim 10 is an electrolytic reaction in which a fuel cell electrode catalyst produced by the method according to any one of claims 5 to 8 is formed in a layered manner on one or both surfaces of a solid polymer electrolyte membrane. Since it has a layer, a high oxidation-reduction capability is exhibited in the electrode catalyst, and the current density of the fuel cell becomes extremely high or relatively high.
次に本発明を実施するための最良の形態を図面に基づいて説明する。
燃料電池用電極触媒は、遷移金属共存下で炭素化調製して得られた炭素化材からなる。この炭素化材は、多数の平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子が非凝集状態で集合して形成される。ここでシェル状構造の炭素粒子の平均粒径を１０〜２０ｎｍの範囲に限定したのは、１０ｎｍ未満では炭素粒子のシェル状構造が十分に発達せず、酸素還元活性の発現に寄与する炭素粒子表面の欠陥が未だ少ないからであり、２０ｎｍを越えると炭素粒子のシェル状構造が発達し過ぎて、酸素還元活性の発現に寄与する炭素粒子表面の欠陥が再び少なくなってしまうからである。またシェル状構造の炭素粒子の（００２）面反射に対応するＸ線回折線図における先鋭成分面積ＳSと略平坦成分面積ＳBとの合計面積ＳTに対する先鋭成分面積ＳVの割合ｆSは０．１以上、好ましくは０．２５以上である（図１）。この割合ｆSは炭素化材の炭素粒子のシェル状構造の発達程度を示す。ここで、割合ｆSを０．１以上としたのは、０．１未満ではシェル状構造の炭素粒子の平均粒径を１０〜２０ｎｍの範囲内に揃えることができず、酸素還元活性を炭素化材自体にもたせることができないからである。
Next, the best mode for carrying out the present invention will be described with reference to the drawings.
The fuel cell electrode catalyst is made of a carbonized material obtained by carbonization in the presence of a transition metal. This carbonized material is formed by aggregating a large number of shell-like carbon particles having an average particle diameter of 10 to 20 nm in a non-aggregated state. Here, the average particle diameter of the carbon particles having a shell-like structure is limited to the range of 10 to 20 nm because the shell-like structure of the carbon particles is not sufficiently developed if the particle diameter is less than 10 nm, and the carbon particles contribute to the expression of oxygen reduction activity. This is because there are still few surface defects. If the thickness exceeds 20 nm, the shell-like structure of the carbon particles develops too much, and the defects on the surface of the carbon particles contributing to the expression of the oxygen reduction activity are reduced again. The ratio f S of the pointed component area S V to the total area S T of the pointed component area S S substantially flat component area S B in the X-ray diffraction diagram corresponding to the (002) plane reflection of the carbon particles of shell-like structure Is 0.1 or more, preferably 0.25 or more (FIG. 1). This ratio f S indicates the degree of development of the shell-like structure of the carbon particles of the carbonized material. Here, the ratio f S is set to 0.1 or more. If the ratio is less than 0.1, the average particle diameter of the carbon particles having a shell-like structure cannot be set within the range of 10 to 20 nm, and the oxygen reduction activity is reduced to carbon. This is because the chemical material itself cannot be applied.
一方、シェル状構造の炭素粒子の炭素網面のエッジ面には、シェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２、好ましくは０．０２〜０．１の窒素を含むか、或いはシェル状構造の炭素粒子表面の炭素に対して原子比で０．０１〜０．２、好ましくは０．０２〜０．１の窒素を含み、かつシェル状構造の炭素粒子表面の炭素に対して原子比で０．００１〜０．７、好ましくは０．００５〜０．１のホウ素を含む。具体的には、Ｘ線光電子分光法（以下、ＸＰＳ法という）により測定した窒素内殻電子Ｎ１ｓに関するスペクトルを、結合エネルギ４０２．９±０．３ｅＶを有する酸化状態の窒素と、結合エネルギ４０１．２±０．３ｅＶを有する４級窒素と、結合エネルギ４００．５±０．３ｅＶを有するピリドン及びピロール型窒素と、結合エネルギ３９８．５±０．３ｅＶを有するピリジン型窒素の４種類に分ける。このときシェル状構造の炭素化材の炭素網面のエッジ面には、シェル状構造の炭素粒子表面の炭素に対して上記エッジ面に存在する窒素を原子比で０．０１〜０．２含むようにピリドン及びピロールとピリジンが存在する。ここで、シェル状構造の炭素粒子表面の炭素に対する炭素網面のエッジ面における窒素の含有量を原子比で０．０１〜０．２の範囲内に限定したのは、０．０１未満では窒素の効果が不十分であり、０．２を越えると電気伝導性が低下してしまうである。またシェル状構造の炭素粒子表面の炭素に対する炭素網面のエッジ面におけるホウ素の含有量を原子比で０．００１〜０．７の範囲内に限定したのは、０．００１未満ではホウ素の効果が不十分であり、０．７を越えると電気伝導性が低下してしまうからである。 On the other hand, the edge surface of the carbon network surface of the shell-like structure carbon particles has an atomic ratio of 0.01 to 0.2, preferably 0.02 to 0.1, with respect to the carbon on the surface of the shell-like structure carbon particles. Or a shell-like carbon containing 0.01 to 0.2, preferably 0.02 to 0.1 nitrogen in atomic ratio to the carbon on the surface of the shell-like carbon particles. It contains boron in an atomic ratio of 0.001 to 0.7, preferably 0.005 to 0.1 with respect to carbon on the particle surface. Specifically, a spectrum relating to nitrogen inner-shell electrons N1s measured by X-ray photoelectron spectroscopy (hereinafter referred to as XPS method) is obtained by comparing nitrogen in an oxidized state having a binding energy of 402.9 ± 0.3 eV with a binding energy of 401. It is divided into four types: quaternary nitrogen having 2 ± 0.3 eV, pyridone and pyrrole nitrogen having a binding energy of 400.5 ± 0.3 eV, and pyridine nitrogen having a binding energy of 398.5 ± 0.3 eV. At this time, the edge surface of the carbon network surface of the carbonized material having a shell-like structure contains 0.01 to 0.2 nitrogen in an atomic ratio with respect to the carbon on the surface of the shell-like structure carbon particles. Thus, pyridone and pyrrole and pyridine are present. Here, the nitrogen content in the edge surface of the carbon network surface with respect to the carbon on the surface of the shell-like structure carbon particles is limited to an atomic ratio in the range of 0.01 to 0.2. This effect is insufficient, and if it exceeds 0.2, the electrical conductivity is lowered. Further, the boron content in the edge surface of the carbon network surface with respect to the carbon on the surface of the shell-like carbon particles is limited to the range of 0.001 to 0.7 in terms of atomic ratio. This is because the electrical conductivity decreases if the ratio exceeds 0.7.
このように構成された燃料電池用電極触媒の製造方法を説明する。
［Ａ］ 炭素化材の調製方法
先ず遷移金属をイオン交換樹脂に導入して遷移金属含有イオン交換樹脂を調製する。イオン交換樹脂としては、キレート樹脂、カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリル酸等が挙げられる。また遷移金属としては、コバルト、鉄、ニッケル、マンガン、亜鉛、銅等が挙げられるけれども、炭素化材自体に付与されるカソード電極の触媒活性、即ち酸素還元活性を向上できるコバルト又は鉄を用いることが好ましい。これは、カソード電極の触媒活性を向上させるナノサイズのシェル状構造を形成するのにコバルト又は鉄が優れていることが分かっているからである。コバルトをイオン交換樹脂に導入する場合、硫酸コバルト七水和物水溶液にイオン交換樹脂を投入して撹拌してコバルト含有イオン交換樹脂を調製するけれども、この塩に限定されるものではない。鉄、ニッケル、マンガン、亜鉛、銅等についてもこれに準ずる。次いで上記遷移金属含有イオン交換樹脂を、窒素流通下、６００〜２０００℃、好ましくは６５０〜１５００℃に、５〜１８０分間、好ましくは２０〜１２０分間保持する熱処理を行う。これにより上記遷移金属含有イオン交換樹脂が炭素化されて炭素化材となる。ここで、上記熱処理温度を６００〜２０００℃の範囲内に限定したのは、６００℃未満では炭素化が不十分であり、２０００℃を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。また、上記熱処理時間を５〜１８０分の範囲内に限定したのは、５分未満では均一な熱処理が行えず、１８０分を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。
A method for producing the fuel cell electrode catalyst configured as described above will be described.
[A] Preparation Method of Carbonized Material First, a transition metal is introduced into an ion exchange resin to prepare a transition metal-containing ion exchange resin. Examples of the ion exchange resin include chelate resin, carboxymethyl cellulose, polyvinyl alcohol, polyacrylic acid and the like. Examples of the transition metal include cobalt, iron, nickel, manganese, zinc, copper, etc., but use of cobalt or iron that can improve the catalytic activity of the cathode electrode applied to the carbonized material itself, that is, oxygen reduction activity. Is preferred. This is because it has been found that cobalt or iron is excellent in forming a nano-sized shell-like structure that improves the catalytic activity of the cathode electrode. When cobalt is introduced into the ion exchange resin, the ion exchange resin is added to the cobalt sulfate heptahydrate aqueous solution and stirred to prepare the cobalt-containing ion exchange resin, but the salt is not limited to this salt. The same applies to iron, nickel, manganese, zinc, copper, and the like. Next, the transition metal-containing ion exchange resin is subjected to a heat treatment for holding at 600 to 2000 ° C., preferably 650 to 1500 ° C. for 5 to 180 minutes, preferably 20 to 120 minutes under a nitrogen flow. Thereby, the said transition metal containing ion exchange resin is carbonized and becomes a carbonized material. The reason why the heat treatment temperature is limited to the range of 600 to 2000 ° C. is that carbonization is insufficient when the temperature is less than 600 ° C., and when the temperature exceeds 2000 ° C., the shell-like structure of the carbon particles is enlarged and the crystal is grown. This is because the defects on the surface of the carbon particles are eliminated. Further, the heat treatment time is limited to the range of 5 to 180 minutes. If the heat treatment time is less than 5 minutes, uniform heat treatment cannot be performed. If the heat treatment time exceeds 180 minutes, the shell-like structure of the carbon particles is enlarged and the crystal is grown. This is because defects on the surface of the carbon particles are eliminated.
［Ｂ］ 窒素の導入方法
炭素化材に窒素を導入するには、液相ドープ法又は気相ドープ法が用いられる。
（１）液相ドープ法による窒素の導入
炭素化材と窒素源であるメラミンを混合した後に、この窒素源が混合された炭素化材を、窒素、アルゴン、ヘリウム等の不活性ガス雰囲気下、５５０〜１５００℃、好ましくは６００〜１０００℃に、５〜１８０分間、好ましくは２０〜６０分間保持する熱処理を行うことにより、炭素粒子表面に窒素を導入する。ここで、上記熱処理温度を５５０〜１５００℃の範囲内に限定したのは、５５０℃未満では炭素とメラミンとの反応が不十分となり、１５００℃を越えると窒素原子が離脱するとともに炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。また、上記熱処理時間を５〜１８０分の範囲内に限定したのは、５分未満では窒素ドープが十分に行われず、１８０分を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。
（２）気相ドープ法による窒素の導入
気相ドープ法を用いる場合、ＣＶＤ法又はアンモオキシデーション法を用いることが好ましい。
(a) ＣＶＤ法による窒素の導入
０〜８０℃にあるアセトニトリルに窒素ガスを通過させ、このアセトニトリルを含む窒素ガスを反応管内で５５０〜１５００℃、好ましくは６００〜８００℃に加熱された炭素化材に５〜１８０分間、好ましくは１０〜６０分間接触させる熱処理を行うことにより、炭素粒子表面に窒素を導入する。ここで、上記熱処理温度を５５０〜１５００℃の範囲内に限定したのは、５５０℃未満ではアセトニトリルの熱分解が不十分であり、１５００℃を越えると窒素原子が離脱するとともに炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。また、上記熱処理時間を５〜１８０分の範囲内に限定したのは、５分未満では窒素ドープが十分に行われず、１８０分を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。
(b) アンモオキシデーション法による窒素の導入
反応管に収容した炭素化材を酸素雰囲気中で５５０〜８００℃、好ましくは５５０〜６５０℃に保持し、この状態で空気とともに窒素源であるアンモニアガスを反応管内に流し、炭素化材をアンモニアガスと５〜１８０分間、好ましくは１０〜１２０分間接触させることにより、炭素粒子表面に窒素を導入する。ここで、上記炭素化材の酸化温度を５５０〜８００℃の範囲内に限定したのは、５５０℃未満では炭素表面の活性化が不十分であり、８００℃を越えると炭素の酸化が著しく加速されて炭素化材が消失してしまうからである。また、上記アンモニアとの接触時間を５〜１８０分の範囲内に限定したのは、５分未満では反応が不十分であり、１８０分を越えると炭素化材が著しく酸化消耗してしまうからである。
[B] Introduction Method of Nitrogen To introduce nitrogen into the carbonized material, a liquid phase doping method or a vapor phase doping method is used.
(1) Introduction of nitrogen by liquid phase doping method After mixing the carbonized material and melamine, which is a nitrogen source, the carbonized material mixed with this nitrogen source is subjected to an inert gas atmosphere such as nitrogen, argon, helium, etc. Nitrogen is introduced into the surface of the carbon particles by performing a heat treatment at 550 to 1500 ° C., preferably 600 to 1000 ° C., for 5 to 180 minutes, preferably 20 to 60 minutes. Here, the heat treatment temperature is limited to the range of 550 to 1500 ° C. The reaction between carbon and melamine is insufficient when the temperature is lower than 550 ° C., and when the temperature exceeds 1500 ° C., the nitrogen atoms are detached and the shell of carbon particles. This is because defects on the surface of the carbon particles are eliminated along with the enlargement of the structure and the crystal growth. Moreover, the heat treatment time was limited to the range of 5 to 180 minutes because the nitrogen doping was not sufficiently performed in less than 5 minutes, and with the increase in the shell-like structure of the carbon particles and the crystal growth in excess of 180 minutes. This is because the defects on the surface of the carbon particles are eliminated.
(2) Introduction of nitrogen by vapor phase doping method When the vapor phase doping method is used, it is preferable to use a CVD method or an ammoxidation method.
(a) Introduction of nitrogen by CVD method Nitrogen gas is passed through acetonitrile at 0 to 80 ° C., and the nitrogen gas containing this acetonitrile is heated to 550 to 1500 ° C., preferably 600 to 800 ° C. in a reaction tube. Nitrogen is introduced into the surface of the carbon particles by performing a heat treatment for contacting the material for 5 to 180 minutes, preferably 10 to 60 minutes. Here, the heat treatment temperature is limited to the range of 550 to 1500 ° C. The reason is that if the temperature is less than 550 ° C., the thermal decomposition of acetonitrile is insufficient. This is because defects on the surface of the carbon particles are eliminated with the enlargement of the structure and the crystal growth. Moreover, the heat treatment time was limited to the range of 5 to 180 minutes because the nitrogen doping was not sufficiently performed in less than 5 minutes, and with the increase in the shell-like structure of the carbon particles and the crystal growth in excess of 180 minutes. This is because the defects on the surface of the carbon particles are eliminated.
(b) Introduction of nitrogen by ammoxidation method The carbonized material accommodated in the reaction tube is held at 550 to 800 ° C, preferably 550 to 650 ° C in an oxygen atmosphere, and in this state, ammonia gas which is a nitrogen source together with air Is introduced into the reaction tube, and the carbonized material is brought into contact with ammonia gas for 5 to 180 minutes, preferably for 10 to 120 minutes, thereby introducing nitrogen to the surface of the carbon particles. Here, the reason why the oxidation temperature of the carbonized material is limited to the range of 550 to 800 ° C. is that activation of the carbon surface is insufficient when the temperature is lower than 550 ° C., and the oxidation of carbon is remarkably accelerated when the temperature exceeds 800 ° C. This is because the carbonized material disappears. Moreover, the reason for limiting the contact time with the ammonia within the range of 5 to 180 minutes is that the reaction is insufficient if it is less than 5 minutes, and the carbonized material is significantly oxidized and consumed if it exceeds 180 minutes. is there.
［Ｃ］ 窒素及びホウ素の導入方法
炭素化材に窒素及びホウ素を導入するには、液相ドープ法、気相ドープ法又は気相−液相ドープ法が用いられる。
（１）液相ドープ法による窒素及びホウ素の導入
炭素化材と、窒素源であるメラミンと、ホウ素源であるＢＦ3メタノール錯体とを混合した後に、この窒素源及びホウ素源が混合された炭素化材を、窒素、アルゴン、ヘリウム等の不活性ガス雰囲気下、５５０〜１２００℃、好ましくは６００〜１０００℃に、５〜１８０分間、好ましくは２０〜１２０分間保持する熱処理を行うことにより、炭素粒子表面に窒素及びホウ素を導入する。ここで、上記熱処理温度を５５０〜１２００℃の範囲内に限定したのは、５５０℃未満では反応が不十分であり、１２００℃を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。また、上記熱処理時間を５〜１８０分の範囲内に限定したのは、５分未満では反応が不十分であり、１８０分を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。
（２）気相ドープ法による窒素及びホウ素の導入
上記ＣＶＤ法又はアンモオキシデーション法を用いて炭素化材の炭素粒子表面に窒素を導入した後に、この炭素化材を反応管から取出すことなく、ＢＣｌ3ガスを５５０〜１５００℃、好ましくは５５０〜１０００℃に加熱された炭素化材に５〜１８０分間、好ましくは２０〜１２０分間接触させることにより、炭素粒子表面にホウ素を導入する。ここで、上記ＢＣｌ3ガスとの接触温度を５５０〜１５００℃の範囲内に限定したのは、５５０℃未満では反応が不十分であり、１５００℃を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。また、上記ＢＣｌ3ガスとの接触時間を５〜１８０分の範囲内に限定したのは、５分未満では反応が不十分であり、１８０分を越えると炭素粒子のシェル状構造の巨大化と結晶成長に伴って炭素粒子表面の欠陥が解消してしまうからである。
（３）気相−液相ドープ法による窒素及びホウ素の導入
上記ＣＶＤ法又はアンモオキシデーション法を用いて炭素化材の炭素粒子表面に窒素を導入した後に、この炭素化材をホウ素源であるＢＦ3−メタノールと混合し、更にこのホウ素源を混合した炭素化材を、窒素、アルゴン、ヘリウム等の不活性ガス雰囲気下、５５０〜１５００℃、好ましくは６００〜１０００℃に、５〜１８０分間、好ましくは２０〜１２０分間保持する熱処理を行うことにより、炭素粒子表面にホウ素を導入する。
一方、遷移金属含有イオン交換樹脂を熱処理して炭素化材を調製する前に、遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製し、このポリマー混合物を熱処理して炭素化材を調製することが好ましい。炭素前駆体としては、フェノール樹脂、フラン樹脂、ピッチ（木材、石炭、石油等の有機物を乾留或いは高温熱分解して得られる残渣）等が挙げられるけれども、これらに限定されるものではない。またポリマー混合物の熱処理温度及び熱処理時間は上記遷移金属含有イオン交換樹脂の熱処理温度及び熱処理時間と同一である。
[C] Introduction Method of Nitrogen and Boron In order to introduce nitrogen and boron into the carbonized material, a liquid phase doping method, a gas phase doping method or a gas phase-liquid phase doping method is used.
(1) Introduction of nitrogen and boron by liquid phase doping method After mixing a carbonized material, melamine as a nitrogen source, and BF 3 methanol complex as a boron source, carbon in which the nitrogen source and boron source are mixed By performing a heat treatment in which the chemical is held at 550 to 1200 ° C., preferably 600 to 1000 ° C. for 5 to 180 minutes, preferably 20 to 120 minutes, in an inert gas atmosphere such as nitrogen, argon, helium, etc. Nitrogen and boron are introduced into the particle surface. Here, the heat treatment temperature is limited to the range of 550 to 1200 ° C. The reaction is insufficient when the temperature is less than 550 ° C., and when the temperature exceeds 1200 ° C., the shell-like structure of the carbon particles is enlarged and crystal growth occurs. This is because the defects on the surface of the carbon particles are eliminated. Further, the heat treatment time is limited to the range of 5 to 180 minutes because the reaction is insufficient when the heat treatment time is less than 5 minutes, and when the heat treatment time exceeds 180 minutes, the shell-like structure of the carbon particles is enlarged and the crystal is grown. This is because defects on the surface of the carbon particles are eliminated.
(2) Introduction of nitrogen and boron by vapor phase doping method After introducing nitrogen into the carbon particle surface of the carbonized material using the CVD method or ammoxidation method, without removing the carbonized material from the reaction tube, Boron is introduced into the surface of the carbon particles by bringing BCl 3 gas into contact with a carbonized material heated to 550 to 1500 ° C., preferably 550 to 1000 ° C. for 5 to 180 minutes, preferably 20 to 120 minutes. Here, the reason why the contact temperature with the BCl 3 gas is limited to the range of 550 to 1500 ° C. is that the reaction is insufficient when the temperature is lower than 550 ° C., and the shell-like structure of the carbon particles is enlarged when the temperature exceeds 1500 ° C. This is because defects on the surface of the carbon particles are eliminated as the crystal grows. Further, the contact time with the BCl 3 gas is limited to the range of 5 to 180 minutes because the reaction is insufficient if it is less than 5 minutes, and if it exceeds 180 minutes, the shell-like structure of the carbon particles is enlarged. This is because the defects on the surface of the carbon particles are eliminated with the crystal growth.
(3) Introduction of nitrogen and boron by vapor phase-liquid phase doping method After introducing nitrogen into the carbon particle surface of the carbonized material using the above-mentioned CVD method or ammoxidation method, this carbonized material is a boron source. The carbonized material mixed with BF 3 -methanol and further mixed with the boron source is 550 to 1500 ° C., preferably 600 to 1000 ° C., in an inert gas atmosphere such as nitrogen, argon, helium, etc. for 5 to 180 minutes. Preferably, boron is introduced to the surface of the carbon particles by performing a heat treatment for 20 to 120 minutes.
On the other hand, before preparing the carbonized material by heat-treating the transition metal-containing ion exchange resin, a transition metal-containing ion exchange resin is introduced into the carbon precursor to prepare a polymer mixture, and the polymer mixture is heat-treated to prepare carbon. It is preferable to prepare a chemical. Examples of the carbon precursor include, but are not limited to, phenol resins, furan resins, pitches (residues obtained by dry distillation or high-temperature pyrolysis of organic substances such as wood, coal, and petroleum). The heat treatment temperature and heat treatment time of the polymer mixture are the same as those of the transition metal-containing ion exchange resin.
［Ｄ］ 固体燃料電池の製造方法
固体高分子形燃料電池は電池モジュール内に組込まれたセルがシート状の固体高分子電解質膜を挟むようにして対向配置されるアノード（燃料極）及びカソード（酸化剤極）とから構成されている。この固体高分子電解質膜としては、パーフルオロスルホン酸樹脂膜（例えば、デュポン社製ナフィオン膜）を代表とするフッ素系イオン交換樹脂膜が用いられている。また上記熱処理された燃料電池用電極触媒は平均粒径０．０５〜０．１μｍの粉状に粉砕され、この粉状の燃料電池用電極触媒を上記固体高分子電解質膜の一方又は双方の面に塗布することにより層状の電極反応層が形成される。即ち、アノード及びカソード（以下、電極と略称）は、上記燃料電池用電極触媒を含む電極反応層と電極基材を備えて構成される。両電極を電極反応層側で固体高分子電解質膜の両主面にホットプレスにより密着することにより、ＭＥＡ(Membrane Electrode Assembly)として一体化される。
上記電極基材は、触媒層を支持するとともに反応ガス（燃料ガスと酸化剤ガス）の供給・排出を行い、集電体としての機能も有する多孔質のシート（例えば、カーボンペーパー）が用いられる。そして、上記電極のそれぞれに反応ガスが供給されると、両電極に備えられた白金系の貴金属を担持した触媒層と固体高分子電解質膜との境界に気相（反応ガス）、液相（固体高分子電解質膜）、固相（両電極が持つ触媒）の三相界面が形成され、電気化学反応を生じさせることで直流電力を発生する。
上記電気化学反応において、
カソード側：Ｏ2＋４Ｈ+＋４ｅ-→２Ｈ2Ｏ
アノード側：Ｈ2→２Ｈ+＋２ｅ-
の反応が起こり、アノード側で生成されたＨ+イオンは固体高分子電解質膜中をカソード側に向かって移動し、ｅ-（電子）は外部の負荷を通ってカソード側に移動する。一方、カソード側では酸化剤ガス中に含まれる酸素と、アノード側から移動してきたＨ+イオン及びｅ-とが反応して水が生成される。この結果、固体高分子形燃料電池は、水素と酸素とから直流電力を発生し、水を生成することになる。
[D] Production Method of Solid Fuel Cell A solid polymer fuel cell is an anode (fuel electrode) and cathode (oxidant) in which cells built in a battery module are opposed to each other with a sheet-like solid polymer electrolyte membrane sandwiched between them. Poles). As this solid polymer electrolyte membrane, a fluorine ion exchange resin membrane represented by a perfluorosulfonic acid resin membrane (for example, Nafion membrane manufactured by DuPont) is used. The heat-treated fuel cell electrode catalyst is pulverized into a powder having an average particle size of 0.05 to 0.1 μm, and the powdered fuel cell electrode catalyst is applied to one or both surfaces of the solid polymer electrolyte membrane. A layered electrode reaction layer is formed by applying to the substrate. That is, the anode and the cathode (hereinafter abbreviated as “electrode”) are configured to include an electrode reaction layer including the fuel cell electrode catalyst and an electrode substrate. Both electrodes are brought into close contact with both main surfaces of the solid polymer electrolyte membrane on the electrode reaction layer side by hot pressing, thereby being integrated as an MEA (Membrane Electrode Assembly).
The electrode base material uses a porous sheet (for example, carbon paper) that supports the catalyst layer and supplies / discharges the reaction gas (fuel gas and oxidant gas) and also has a function as a current collector. . When a reactive gas is supplied to each of the electrodes, a gas phase (reactive gas), a liquid phase (at the boundary between the catalyst layer supporting the platinum-based noble metal provided on both electrodes and the solid polymer electrolyte membrane) are provided. A solid polymer electrolyte membrane) and a solid phase (catalyst possessed by both electrodes) are formed, and a DC power is generated by causing an electrochemical reaction.
In the above electrochemical reaction,
Cathode side: O 2 + 4H + + 4e − → 2H 2 O
Anode side: H 2 → 2H + + 2e −
The H + ions generated on the anode side move toward the cathode side through the solid polymer electrolyte membrane, and e − (electrons) move to the cathode side through an external load. On the other hand, on the cathode side, oxygen contained in the oxidant gas reacts with H + ions and e − that have moved from the anode side to generate water. As a result, the polymer electrolyte fuel cell generates DC power from hydrogen and oxygen to generate water.
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
先ずキレックス（バイオラッド社製のキレート樹脂）を５ｇを計り取る。次に予め調製しておいた硫酸コバルト七水和物水溶液（イオン濃度：０．９ｇ／リットル、ｐＨ調整剤として硫酸アンモニウムを５０ｇ／リットル添加）１００ｃｃに上記キレックスを投入し、マグネチックスターラーにより１〜２時間撹拌することにより、コバルトをイオン交換した樹脂を調製した。上記コバルト水溶液は、撹拌を開始してから２時間後に略完全に脱色し、所定量のコバルトがキレックスに定量的に導入された。また、上記キレックスのイオン交換量は１８ｍｇ／ｇであり、コバルト水溶液の濃度は、キレックスの飽和交換量の２５％を意図して設定した。即ち、キレックスの飽和交換量に対するコバルト交換率を２５％に設定した。ここで、飽和交換量とは、バイオラッド社のカタログに記載されたキレックスのイオン交換量、即ちキレックスが０．６１ミリ当量／ｇのコバルト含有イオンを吸着したときのイオン交換量をいう。イオン交換終了後、コバルト含有イオン交換樹脂に対して吸引ろ過とイオン交換水による洗浄とを繰返した後、コバルト含有イオン交換樹脂中の水分を凍結乾燥により除去した。更にこの水分の除去されたコバルト含有イオン交換樹脂を窒素流通下１０００℃に６０分間保持して炭素化材を調製した。この炭素化材を実施例１とした。
＜実施例２＞
キレックスの飽和交換量に対するコバルト交換率を５０％に設定したこと以外は、実施例１と同様にして炭素化材を調製した。この炭素化材を実施例２とした。
＜実施例３＞
キレックスの飽和交換量に対するコバルト交換率を７５％に設定したこと以外は、実施例１と同様にして炭素化材を調製した。この炭素化材を実施例３とした。
＜実施例４＞
キレックスの飽和交換量に対するコバルト交換率を１００％に設定したこと以外は、実施例１と同様にして炭素化材を調製した。この炭素化材を実施例４とした。
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
First, 5 g of Kilex (a chelating resin manufactured by Bio-Rad) is weighed. Next, the above-mentioned chelex was introduced into 100 cc of a cobalt sulfate heptahydrate aqueous solution (ion concentration: 0.9 g / liter, ammonium sulfate added as a pH adjuster added at 50 g / liter) prepared in advance. By stirring for 2 hours, a resin in which cobalt was ion-exchanged was prepared. The cobalt aqueous solution was almost completely decolored 2 hours after the start of stirring, and a predetermined amount of cobalt was quantitatively introduced into Kilex. The ion exchange amount of the above-mentioned Chelex was 18 mg / g, and the concentration of the cobalt aqueous solution was set with the intention of 25% of the saturation exchange amount of Chelex. That is, the cobalt exchange rate with respect to the saturation exchange amount of Kirex was set to 25%. Here, the saturation exchange amount refers to the ion exchange amount of Kilex described in the BioRad catalog, that is, the ion exchange amount when the Kilex adsorbs cobalt-containing ions with 0.61 meq / g. After completion of the ion exchange, the cobalt-containing ion exchange resin was repeatedly subjected to suction filtration and washing with ion-exchanged water, and then water in the cobalt-containing ion exchange resin was removed by freeze drying. Further, this carbon-containing material was prepared by holding the cobalt-containing ion exchange resin from which moisture was removed at 1000 ° C. for 60 minutes under a nitrogen flow. This carbonized material was designated as Example 1.
<Example 2>
A carbonized material was prepared in the same manner as in Example 1 except that the cobalt exchange rate with respect to the saturation exchange amount of Kirex was set to 50%. This carbonized material was designated as Example 2.
<Example 3>
A carbonized material was prepared in the same manner as in Example 1 except that the cobalt exchange rate with respect to the saturation exchange amount of Kirex was set to 75%. This carbonized material was designated as Example 3.
<Example 4>
A carbonized material was prepared in the same manner as in Example 1 except that the cobalt exchange rate with respect to the saturation exchange amount of Kirex was set to 100%. This carbonized material was designated as Example 4.
＜実施例５＞
実施例１と同様にしてコバルト交換率２５％のコバルト含有イオン交換樹脂を調製し、このコバルト含有イオン交換樹脂と、ノボラック型フェノールホルムアルデヒド樹脂（群栄化学社製のフェノール樹脂）とを、ラボプラストミルμ（東洋精機社製の小型セグメントミキサー）を用いて混練することにより、ポリマー混合物を調製した。コバルト交換率２５％のコバルト含有イオン交換樹脂のフェノール樹脂に対する混合割合を、フェノール樹脂に対するコバルト重量比が３％になるように、重量比で１２：８とした。このポリマー混合物を窒素流通下１０００℃に６０分間保持して炭素化材を調製した。この炭素化材を実施例５とした。
＜実施例６＞
コバルト交換率５０％のコバルト含有イオン交換樹脂を用い、コバルト交換率５０％のコバルト含有イオン交換樹脂のフェノール樹脂に対する混合割合を、フェノール樹脂に対するコバルト重量比が３％になるように、重量比で６：８としたこと以外は、実施例５と同様にして炭素化材を調製した。この炭素化材を実施例６とした。
＜実施例７＞
コバルト交換率７５％のコバルト含有イオン交換樹脂を用い、コバルト交換率７５％のコバルト含有イオン交換樹脂のフェノール樹脂に対する混合割合を、フェノール樹脂に対するコバルト重量比が３％になるように、重量比で４：８としたこと以外は、実施例５と同様にして炭素化材を調製した。この炭素化材を実施例７とした。
＜実施例８＞
コバルト交換率１００％のコバルト含有イオン交換樹脂を用い、コバルト交換率１００％のコバルト含有イオン交換樹脂のフェノール樹脂に対する混合割合を、フェノール樹脂に対するコバルト重量比が３％になるように、重量比で３：８としたこと以外は、実施例５と同様にして炭素化材を調製した。この炭素化材を実施例８とした。
<Example 5>
A cobalt-containing ion exchange resin having a cobalt exchange rate of 25% was prepared in the same manner as in Example 1, and this cobalt-containing ion exchange resin and a novolac type phenol formaldehyde resin (phenol resin manufactured by Gunei Chemical Co., Ltd.) A polymer mixture was prepared by kneading using a mill μ (a small segment mixer manufactured by Toyo Seiki Co., Ltd.). The mixing ratio of the cobalt-containing ion exchange resin with a cobalt exchange rate of 25% to the phenol resin was set to 12: 8 in a weight ratio so that the weight ratio of cobalt to the phenol resin was 3%. This polymer mixture was held at 1000 ° C. for 60 minutes under a nitrogen stream to prepare a carbonized material. This carbonized material was designated as Example 5.
<Example 6>
Using a cobalt-containing ion exchange resin having a cobalt exchange rate of 50%, the mixing ratio of the cobalt-containing ion exchange resin having a cobalt exchange rate of 50% with respect to the phenol resin is such that the weight ratio of cobalt to the phenol resin is 3%. A carbonized material was prepared in the same manner as in Example 5 except that the ratio was 6: 8. This carbonized material was designated as Example 6.
<Example 7>
Using a cobalt-containing ion exchange resin with a cobalt exchange rate of 75%, the mixing ratio of the cobalt-containing ion exchange resin with a cobalt exchange rate of 75% to the phenol resin is such that the weight ratio of cobalt to the phenol resin is 3%. A carbonized material was prepared in the same manner as in Example 5 except that the ratio was 4: 8. This carbonized material was designated as Example 7.
<Example 8>
Using a cobalt-containing ion exchange resin having a cobalt exchange rate of 100%, the mixing ratio of the cobalt-containing ion exchange resin having a cobalt exchange rate of 100% with respect to the phenol resin is such that the weight ratio of cobalt to the phenol resin is 3%. A carbonized material was prepared in the same manner as in Example 5 except that the ratio was 3: 8. This carbonized material was designated as Example 8.
＜比較例１＞
キレックスの飽和交換量に対するコバルト交換率を０％に設定したこと以外は、実施例１と同様にして炭素化材を調製した。この炭素化材を比較例１とした。
＜比較例２＞
コバルト交換率０％のコバルト含有イオン交換樹脂を用い、コバルト交換率０％のコバルト含有イオン交換樹脂のフェノール樹脂に対する混合割合を、フェノール樹脂に対するコバルト重量比が３％になるように、重量比で６：８としたこと以外は、実施例５と同様にして炭素化材を調製した。この炭素化材を比較例２とした。
<Comparative Example 1>
A carbonized material was prepared in the same manner as in Example 1 except that the cobalt exchange rate with respect to the saturation exchange amount of Kirex was set to 0%. This carbonized material was referred to as Comparative Example 1.
<Comparative example 2>
Using a cobalt-containing ion exchange resin having a cobalt exchange rate of 0%, the mixing ratio of the cobalt-containing ion exchange resin having a cobalt exchange rate of 0% with respect to the phenol resin is such that the weight ratio of cobalt to the phenol resin is 3%. A carbonized material was prepared in the same manner as in Example 5 except that the ratio was 6: 8. This carbonized material was designated as Comparative Example 2.
＜比較試験１及び評価＞
実施例１〜８と比較例１及び２の粉末状の炭素化材について粉末Ｘ線回折を測定し、その炭素化材の炭素粒子のシェル状構造の発達程度ｆSを求めた。具体的には、シェル状構造の炭素粒子の（００２）面反射に対応するＸ線回折線図における先鋭成分面積ＳSと略平坦成分面積ＳBとの合計面積ＳTに対する先鋭成分面積ＳVの割合ｆSを求めた。その結果を表１に示す。
<Comparative test 1 and evaluation>
Powder X-ray diffraction was measured for the powdered carbonized materials of Examples 1 to 8 and Comparative Examples 1 and 2, and the degree of development f S of the shell-like structure of the carbon particles of the carbonized material was determined. Specifically, the shell-like structure of carbon particles (002) plane pointed component area S V to the total area S T of the pointed component area S S substantially flat component area S B in the X-ray diffraction diagram corresponding to the reflection The ratio f S was obtained. The results are shown in Table 1.
表１から明らかなように、比較例１及び２ではｆSがともにゼロであり、炭素粒子のシェル状構造が十分に発達していなかったのに対し、実施例１〜８ではｆSが０．１９〜０．４５と大きく、炭素粒子のシェル状構造が十分に発達していたことが分かった。 As is clear from Table 1, in Comparative Examples 1 and 2, both f S was zero and the shell-like structure of the carbon particles was not sufficiently developed, whereas in Examples 1 to 8, f S was 0. .19-0.45, indicating that the shell-like structure of the carbon particles was sufficiently developed.
＜比較試験２及び評価＞
実施例３及び６と比較例１の粉末状の炭素化材の酸素還元活性を回転電極法で評価した。即ち、実施例３及び６と比較例１の炭素化材の酸素還元に関する電極活性を、図２に模式的に示す３極回転電極セル１を用いて測定した。具体的には中央部の作用電極（回転電極）２は周囲が高分子絶縁体、中央部にガラス状炭素からなる電極部を持つ。この電極部にそれぞれ以下のようにして調製した触媒インクを塗布し、作用電極とした。符号３は参照電極（Ａｇ／ＡｇＣｌ）であり、符号４は対極（Ｐｔ）である。
先ず、実施例３及び６の粉末状の炭素化材を、それぞれ５ｍｇ量り取り、これにバインダー（商品名：ナフィオン、デュポン社）溶液、水、エタノールを適量加え、各触媒インクを調製した。次いで、得られた触媒インクを微量ピペットにより吸い取り、回転電極装置のガラス状炭素部分（直径５ｍｍ）に塗布し、乾燥させることにより、作用電極を作製した。
電解質溶液としては、１Ｍ硫酸水溶液に酸素を常温で溶解したものを用いた。回転速度１５００ｒｐｍで電極を回転し、電位を掃引速度０．５ｍＶｓ-1で掃引して、そのときの電流を電位の関数として記録した。その結果を図３に示す。なお、図３において、縦軸は反応速度を表す電流であり、縦軸の電流密度の絶対値が大きくなるほど反応速度が大きくなることを示し、また横軸は反応を進ませる力としての電圧であり、横軸の電圧が小さくなるほど反応を引き起す力が大きくなり、更にこの反応は燃料電池のプラス極の反応であるため、より電圧の高いところで大きな電流が流れるものほど触媒としての性能が高いことを意味する。
図３から明らかなように、実施例３及び６の炭素化材は比較例１の炭素化材と比べて、極めて高い電位から酸素還元電流が流れ始め、同じ電位で比較すると、極めて大きな電流密度を示すことが分かった。
<Comparative test 2 and evaluation>
The oxygen reduction activity of the powdered carbonized materials of Examples 3 and 6 and Comparative Example 1 was evaluated by the rotating electrode method. That is, the electrode activity relating to oxygen reduction of the carbonized materials of Examples 3 and 6 and Comparative Example 1 was measured using the tripolar rotating electrode cell 1 schematically shown in FIG. Specifically, the central working electrode (rotating electrode) 2 has a polymer insulator on the periphery and an electrode portion made of glassy carbon in the central portion. The catalyst ink prepared as follows was applied to each electrode part to obtain a working electrode. Reference numeral 3 is a reference electrode (Ag / AgCl), and reference numeral 4 is a counter electrode (Pt).
First, 5 mg of each of the powdered carbonized materials of Examples 3 and 6 was weighed, and appropriate amounts of binder (trade name: Nafion, DuPont) solution, water, and ethanol were added to prepare each catalyst ink. Next, the obtained catalyst ink was sucked with a small amount of pipette, applied to the glassy carbon portion (diameter 5 mm) of the rotating electrode device, and dried to produce a working electrode.
As the electrolyte solution, a 1 M sulfuric acid aqueous solution in which oxygen was dissolved at room temperature was used. The electrode was rotated at a rotational speed of 1500 rpm, the potential was swept at a sweep speed of 0.5 mVs −1 , and the current at that time was recorded as a function of the potential. The result is shown in FIG. In FIG. 3, the vertical axis represents the current representing the reaction rate, the larger the absolute value of the current density on the vertical axis, the greater the reaction rate, and the horizontal axis represents the voltage as the force for advancing the reaction. Yes, the smaller the voltage on the horizontal axis, the greater the force that triggers the reaction, and since this reaction is a positive reaction of the fuel cell, the higher the voltage, the higher the performance as a catalyst. Means that.
As is clear from FIG. 3, the carbonized materials of Examples 3 and 6 start to flow an oxygen reduction current from an extremely high potential as compared with the carbonized material of Comparative Example 1, and when compared at the same potential, an extremely large current density is obtained. It was found that
＜比較試験３及び評価＞
実施例３及び６の粉末状の炭素化材を透過型電子顕微鏡にて撮影した。その結果を図４（ａ）及び（ｂ）に示す。
図４（ａ）及び（ｂ）から明らかなように、炭素化材の原料としてイオン交換樹脂を用いることにより、凝集の抑制されたシェル状構造の炭素粒子を形成できることが分かった。またイオン交換樹脂を熱処理した炭素化材（図４（ａ））より、イオン交換樹脂にフェノール樹脂を混合したポリマー混合物を熱処理した炭素化材（図４（ｂ））の方が、上記シェル状構造の炭素粒子の凝集の抑制効果を増強する傾向にあることが分かった。
<Comparative test 3 and evaluation>
The powdered carbonized materials of Examples 3 and 6 were photographed with a transmission electron microscope. The results are shown in FIGS. 4 (a) and (b).
As is clear from FIGS. 4A and 4B, it was found that by using an ion exchange resin as a raw material for the carbonized material, carbon particles having a shell-like structure in which aggregation is suppressed can be formed. Further, the carbonized material (FIG. 4 (b)) obtained by heat-treating a polymer mixture obtained by mixing a phenol resin with an ion-exchange resin is more shell-like than the carbonized material obtained by heat-treating the ion-exchange resin (FIG. 4 (a)). It was found that there was a tendency to enhance the effect of suppressing the aggregation of carbon particles with structure.
＜比較例３＞
フルフリルアルコールにフェロセン錯体を鉄重量基準で１重量％となるように導入し、炭素化した。具体的には、先ずフルフリルアルコール３ｇに対して、所定量のフェロセンを混合した後、酸触媒を加え７０℃で２４時間重合を行った。次にこの重合物を窒素流通下７００℃に６０分間保持して炭素化材を調製した。この炭素化材を比較例３とした。
＜比較例４＞
フルフリルアルコールにフェロセン錯体を鉄重量基準で２重量％となるように導入したこと以外は、上記比較例３と同様にして炭素化材を調製した。この炭素化材を比較例４とした。
＜比較例５＞
フルフリルアルコールにフェロセン錯体を鉄重量基準で３重量％となるように導入したこと以外は、上記比較例３と同様にして炭素化材を調製した。この炭素化材を比較例５とした。
＜比較例６＞
フラン樹脂（日立化成社製のフラン樹脂）にコバルトアセチルアセトン錯体をコバルト重量基準で３重量％となるように導入し、炭素化した。具体的には、先ずフラン樹脂３ｇに対して、相当量のコバルトアセチルアセトナートを混合した。次にこの混合物を窒素流通下８００℃に６０分間保持して炭素化材を調製した。この炭素化材を比較例６とした。
＜比較例７＞
混合物を窒素流通下１０００℃に６０分間保持したこと以外は、上記比較例６と同様にして炭素化材を調製した。この炭素化材を比較例７とした。
＜比較例８＞
フラン樹脂（日立化成社製のフラン樹脂）に鉄アセチルアセトン錯体を鉄重量基準で３重量％となるように導入し、炭素化した。具体的には、先ずフラン樹脂３ｇに対して、相当量の鉄アセチルアセトナートを混合した。次にこの混合物を窒素流通下１０００℃に６０分間保持して炭素化材を調製した。この炭素化材を比較例８とした。
＜比較例９＞
フラン樹脂（日立化成社製のフラン樹脂）にニッケルアセチルアセトン錯体をニッケル重量基準で３重量％となるように導入し、炭素化した。具体的には、先ずフラン樹脂３ｇに対して、０．４４８ｇのニッケルアセチルアセトナートを混合した。次にこの混合物を窒素流通下１０００℃に６０分間保持して炭素化材を調製した。この炭素化材を比較例９とした。
<Comparative Example 3>
A ferrocene complex was introduced into furfuryl alcohol so as to be 1% by weight based on the weight of iron and carbonized. Specifically, first, a predetermined amount of ferrocene was mixed with 3 g of furfuryl alcohol, an acid catalyst was added, and polymerization was performed at 70 ° C. for 24 hours. Next, this polymer was held at 700 ° C. for 60 minutes under a nitrogen flow to prepare a carbonized material. This carbonized material was designated as Comparative Example 3.
<Comparative example 4>
A carbonized material was prepared in the same manner as in Comparative Example 3 except that a ferrocene complex was introduced into furfuryl alcohol so as to be 2% by weight based on the weight of iron. This carbonized material was referred to as Comparative Example 4.
<Comparative Example 5>
A carbonized material was prepared in the same manner as in Comparative Example 3 except that a ferrocene complex was introduced into furfuryl alcohol so as to be 3% by weight based on the weight of iron. This carbonized material was designated as Comparative Example 5.
<Comparative Example 6>
A cobalt acetylacetone complex was introduced into furan resin (furan resin manufactured by Hitachi Chemical Co., Ltd.) so as to be 3% by weight based on the weight of cobalt, and carbonized. Specifically, first, a considerable amount of cobalt acetylacetonate was mixed with 3 g of furan resin. Next, this mixture was kept at 800 ° C. for 60 minutes under a nitrogen flow to prepare a carbonized material. This carbonized material was designated as Comparative Example 6.
<Comparative Example 7>
A carbonized material was prepared in the same manner as in Comparative Example 6 except that the mixture was held at 1000 ° C. for 60 minutes under a nitrogen flow. This carbonized material was designated as Comparative Example 7.
<Comparative Example 8>
An iron acetylacetone complex was introduced into furan resin (furan resin manufactured by Hitachi Chemical Co., Ltd.) so as to be 3% by weight based on the weight of iron and carbonized. Specifically, first, a considerable amount of iron acetylacetonate was mixed with 3 g of furan resin. Next, this mixture was kept at 1000 ° C. for 60 minutes under a nitrogen flow to prepare a carbonized material. This carbonized material was designated as Comparative Example 8.
<Comparative Example 9>
A nickel acetylacetone complex was introduced into furan resin (furan resin manufactured by Hitachi Chemical Co., Ltd.) so as to be 3% by weight based on the weight of nickel, and carbonized. Specifically, 0.448 g of nickel acetylacetonate was first mixed with 3 g of furan resin. Next, this mixture was kept at 1000 ° C. for 60 minutes under a nitrogen flow to prepare a carbonized material. This carbonized material was designated as Comparative Example 9.
＜比較試験４及び評価＞
実施例１〜８及び比較例３〜９の炭素化材のシェル状構造の発達程度ｆSと、これらの炭素化材を用いた電極触媒の酸素還元電位Ｅ02とをそれぞれ測定した。上記ｆSは上記比較試験１と同様に測定して求めた。また酸素還元電位Ｅ02は、酸素還元ボルタモグラムにおける１０μＡ／ｃｍ2の還元電流を与える電位と定義した。実施例１〜８及び比較例３〜９の炭素化材のシェル状構造の発達程度ｆSと酸素還元電位Ｅ02との関係を図５に示す。
図５から明らかなように、比較例３〜９では、シェル状構造の発達、即ちｆSの増加とともに酸素還元活性が増加するけれども、ｆSが約０．３から更に増加すると酸素還元活性が次第に低下した。これに対し、実施例１〜８では、シェル状構造の発達、即ちｆSの増加とともに酸素還元活性が増加し続け、酸素還元活性が低下しなかった。これは、実施例で高分子錯体（イオン交換樹脂又はイオン交換樹脂及び炭素前駆体のポリマー混合物）を用いることにより金属の凝集が抑えられたため、ナノサイズのシェル状構造の発達が表面欠陥の解消に結びつかず、酸素還元活性をもつ微細なシェル状構造の炭素粒子が多数発生したことによるものと考えられる。
<Comparative test 4 and evaluation>
The development degree f S of the shell-like structures of the carbonized materials of Examples 1 to 8 and Comparative Examples 3 to 9 and the oxygen reduction potential E 02 of the electrode catalyst using these carbonized materials were measured. The f S was determined by measurement in the same manner as in the comparative test 1. The oxygen reduction potential E 02 was defined as a potential giving a reduction current of 10 μA / cm 2 in the oxygen reduction voltammogram. FIG. 5 shows the relationship between the development degree f S of the shell-like structures of the carbonized materials of Examples 1 to 8 and Comparative Examples 3 to 9 and the oxygen reduction potential E 02 .
As is clear from FIG. 5, in Comparative Examples 3 to 9, the oxygen reduction activity increases with the development of the shell-like structure, that is, the increase of f S , but the oxygen reduction activity increases when f S further increases from about 0.3. It gradually decreased. On the other hand, in Examples 1 to 8, the oxygen reduction activity continued to increase with the development of the shell-like structure, that is, the increase of f S , and the oxygen reduction activity did not decrease. This is because the use of a polymer complex (an ion exchange resin or a polymer mixture of an ion exchange resin and a carbon precursor) in the examples suppresses the aggregation of the metal, so that the development of the nano-sized shell-like structure eliminates surface defects. This is probably because a large number of fine shell-like carbon particles having oxygen reduction activity were generated.
＜実施例９＞
実施例３の炭素化材に気相ドープ法（アンモオキシデーション法）により窒素を導入した後に、気相ドープ法によりホウ素を導入した。具体的には、先ず反応管に収容した炭素化材０．４ｇを窒素ガスにより流動化し、反応管内の温度を６００℃まで昇温し、反応管内の炭素化材を、７０％アンモニア：３０％空気の混合ガスと１２０分接触させることにより、炭素粒子表面に窒素を導入した。次に窒素を導入した炭素化材を反応管から取出すことなく、反応管内にＢＣｌ3ガス（濃度１％−Ｈｅバランスガス）を５０ミリリットル／分で流し、１７分間保持した。そして昇温速度３０℃／分で昇温し、１０００℃に１５分間保持することにより、炭素化材にホウ素を導入した。その後１０００℃の温度に保持した状態で反応管内のガスをＮ2ガスに切替えて２０分間保持することにより、炭素化材の炭素粒子の炭素網面のエッジ部にホウ素を組込んだ。更に自然冷却により室温まで冷却した。この窒素及びホウ素の導入された炭素化材を実施例９とした。
＜実施例１０＞
実施例６の炭素化材を用いたこと以外は、実施例９と同様にして窒素及びホウ素を導入した。この窒素及びホウ素の導入された炭素化材を実施例１０とした。
＜比較試験５及び評価＞
実施例３、６、９及び１０の粉末状の炭素化材の酸素還元活性を上記比較試験２と同様に回転電極法で評価した。その結果を図６に示す。
図６から明らかなように、実施例９及び１０の炭素化材は実施例３及び６の炭素化材と比べて、高い電位から酸素還元電流が流れ始め、同じ電位で比較すると、大きな電流密度を示すことが分かった。
<Example 9>
After introducing nitrogen into the carbonized material of Example 3 by a vapor phase doping method (ammoxidation method), boron was introduced by a vapor phase doping method. Specifically, first, 0.4 g of the carbonized material accommodated in the reaction tube was fluidized with nitrogen gas, the temperature in the reaction tube was raised to 600 ° C., and the carbonized material in the reaction tube was changed to 70% ammonia: 30%. Nitrogen was introduced into the surface of the carbon particles by contacting with a mixed gas of air for 120 minutes. Next, without removing the carbonized material introduced with nitrogen from the reaction tube, BCl 3 gas (concentration 1% -He balance gas) was allowed to flow into the reaction tube at 50 ml / min and held for 17 minutes. Then, the temperature was raised at a rate of temperature rise of 30 ° C./min and held at 1000 ° C. for 15 minutes to introduce boron into the carbonized material. Thereafter, the gas in the reaction tube was switched to N 2 gas while maintaining the temperature at 1000 ° C. and held for 20 minutes to incorporate boron into the edge of the carbon network surface of the carbon particles of the carbonized material. Furthermore, it cooled to room temperature by natural cooling. This carbonized material into which nitrogen and boron were introduced was taken as Example 9.
<Example 10>
Nitrogen and boron were introduced in the same manner as in Example 9 except that the carbonized material of Example 6 was used. This carbonized material into which nitrogen and boron were introduced was taken as Example 10.
<Comparative test 5 and evaluation>
The oxygen reduction activity of the powdered carbonized materials of Examples 3, 6, 9 and 10 was evaluated by the rotating electrode method in the same manner as in Comparative Test 2 above. The result is shown in FIG.
As is clear from FIG. 6, the carbonized materials of Examples 9 and 10 start to flow an oxygen reduction current from a higher potential than the carbonized materials of Examples 3 and 6, and when compared at the same potential, a large current density is obtained. It was found that
Claims (10)
前記炭素化材は、多数の平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子が非凝集状態で集合して形成されたことを特徴とする燃料電池用電極触媒。 In an electrode catalyst for a fuel cell comprising a carbonized material prepared by carbonization in the presence of a transition metal,
An electrode catalyst for a fuel cell, wherein the carbonized material is formed by aggregating a number of shell-shaped carbon particles having an average particle diameter of 10 to 20 nm in a non-aggregated state.
前記遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、
前記炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入する工程と
を含む燃料電池用電極触媒の製造方法。 Introducing a transition metal into the ion exchange resin to prepare the transition metal-containing ion exchange resin;
A step of heat-treating the transition metal-containing ion exchange resin at a temperature of 600 to 2000 ° C. to prepare a carbonized material that is an aggregate of carbon particles having a shell-like structure with an average particle size of 10 to 20 nm;
A step of introducing nitrogen or nitrogen and boron into an edge surface of a carbon network surface of the carbon particles by a liquid phase doping method.
前記遷移金属含有イオン交換樹脂を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、
前記炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入する工程と
を含む燃料電池用電極触媒の製造方法。 Introducing a transition metal into the ion exchange resin to prepare the transition metal-containing ion exchange resin;
A step of heat-treating the transition metal-containing ion exchange resin at a temperature of 600 to 2000 ° C. to prepare a carbonized material that is an aggregate of carbon particles having a shell-like structure with an average particle size of 10 to 20 nm;
A step of introducing nitrogen or nitrogen and boron into the edge surface of the carbon network surface of the carbon particles by a vapor phase doping method.
前記遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製する工程と、
前記ポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、
前記炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を液相ドープ法により導入する工程と
を含む燃料電池用電極触媒の製造方法。 Introducing a transition metal into the ion exchange resin to prepare the transition metal-containing ion exchange resin;
Introducing the transition metal-containing ion exchange resin into a carbon precursor to prepare a polymer mixture;
A step of heat-treating the polymer mixture at a temperature of 600 to 2000 ° C. to prepare a carbonized material that is an aggregate of shell-shaped carbon particles having an average particle diameter of 10 to 20 nm;
A step of introducing nitrogen or nitrogen and boron into an edge surface of a carbon network surface of the carbon particles by a liquid phase doping method.
前記遷移金属含有イオン交換樹脂を炭素前駆体中に導入してポリマー混合物を調製する工程と、
前記ポリマー混合物を６００〜２０００℃の温度で熱処理して平均粒径１０〜２０ｎｍのシェル状構造の炭素粒子の集合体である炭素化材を調製する工程と、
前記炭素粒子の炭素網面のエッジ面に窒素又は窒素及びホウ素を気相ドープ法により導入する工程と
を含む燃料電池用電極触媒の製造方法。 Introducing a transition metal into the ion exchange resin to prepare the transition metal-containing ion exchange resin;
Introducing the transition metal-containing ion exchange resin into a carbon precursor to prepare a polymer mixture;
A step of heat-treating the polymer mixture at a temperature of 600 to 2000 ° C. to prepare a carbonized material that is an aggregate of shell-shaped carbon particles having an average particle diameter of 10 to 20 nm;
A step of introducing nitrogen or nitrogen and boron into the edge surface of the carbon network surface of the carbon particles by a vapor phase doping method.
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