JP4979817B2 - 炭素触媒及びその製造方法、これを用いた電極及び電池 - Google Patents
炭素触媒及びその製造方法、これを用いた電極及び電池 Download PDFInfo
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- JP4979817B2 JP4979817B2 JP2010541295A JP2010541295A JP4979817B2 JP 4979817 B2 JP4979817 B2 JP 4979817B2 JP 2010541295 A JP2010541295 A JP 2010541295A JP 2010541295 A JP2010541295 A JP 2010541295A JP 4979817 B2 JP4979817 B2 JP 4979817B2
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
- Fuel Cell (AREA)
Description
1.5gのビニルピリジンを20mLのジメチルホルムアミドに溶解させた後、70℃で5日間かけて高分子化を行い、ポリビニルピリジンを得た。このポリビニルピリジンに0.65gの塩化鉄六水和物を加え、室温で24時間攪拌することによりポリビニルピリジン鉄錯体を得た。
10gの8−キノリノール(オキシン)と、10gのホルムアルデヒドと、1gのシュウ酸二水和物を容積100mLのナスフラスコに入れ、100℃で一晩還流させた。次いで、1MのHClを5.5mL加え、同様に一晩還流させた。得られた固体を吸引ろ過し、蒸留水で3回洗浄し、一晩真空乾燥させて、高分子(Q高分子)を得た。
300mLのアセトンに3.275gのフェノ−ル樹脂(群栄化学工業株式会社)を加え、超音波を照射して溶解させた。さらに、1.0gのコバルトフタロシアニン錯体(東京化成工業株式会社)を加え、超音波を照射しながらロ−タリ−エバポレ−タ−を用いて40℃で溶媒を除去した。その後、残された組成物を温度80℃で24時間真空乾燥することにより、フェノ−ル樹脂を含有するコバルトフタロシアニン錯体を合成した。
実施例1で得られた5種類の炭素触媒、実施例2で得られた2種類の炭素触媒、実施例3で得られた4種類の炭素触媒のそれぞれについて、酸素還元活性を評価した。すなわち、まず、粉末状の炭素触媒を5mg量り取り、これに50μLのバインダー溶液(ナフィオン(登録商標)、デュポン株式会社)、150μLの水、150μLのエタノールを適量加え、この混合溶液を触媒スラリーとして調製した。
上述の実施例1と同様にして、ポリビニルピリジン鉄錯体とケッチェンブラックとを含有し、当該ケッチェンブラックを50重量%含有する原料を得た。そして、上述の実施例1と同様に、この原料を加熱して昇温し、窒素雰囲気下、500℃、600℃、700℃、800℃、900℃又は1000℃で1時間保持した。
上述の実施例3と同様にして、800℃又は1000℃で炭素化された2種類の炭素触媒(Pc/Co(C800)触媒、Pc/Co(C1000)触媒)を得た。また、同様に、コバルトフタロシアニン錯体に代えて、鉄フタロシアニン錯体を用いることにより、800℃で炭素化された炭素触媒(Pc/Fe(C800)触媒)を得た。そして、上述の実施例4と同様に、各炭素触媒の酸素還元活性を評価した。
上述の実施例5で得られた炭素触媒のうち8種類の炭素触媒、当該炭素触媒の製造に用いられたケッチェンブラック、及び実施例6で得られた3種類の炭素触媒の各々について、結晶子サイズLaの分布を評価した。
上述の実施例1で製造され熱処理が施されていないPVP/Fe/KB触媒、実施例2で製造されたQ/Co/KB触媒及びこれらの製造に用いられたケッチェンブラックのそれぞれについて、電子顕微鏡による観察を行った。
Claims (15)
- 導電性炭素材料と、
前記導電性炭素材料の表面を被覆する炭素構造と、
を有し、
酸素還元活性を有する
ことを特徴とする酸素還元用炭素触媒。 - 前記炭素構造を構成する炭素網面の7.2nm以下の結晶子サイズLa分布において、1〜5nmの割合が50%以上である
ことを特徴とする請求項1に記載された炭素触媒。 - 前記結晶子サイズLa分布において、1nm未満の割合が40%以下である
ことを特徴とする請求項2に記載された炭素触媒。 - 前記炭素構造は、熱可塑性樹脂と金属と前記導電性炭素材料とを含有する原料を加熱して炭素化することにより形成された炭素構造である
ことを特徴とする請求項1乃至3のいずれかに記載された炭素触媒。 - 請求項1乃至4のいずれかに記載された炭素触媒が担持されている
ことを特徴とする電極。 - 請求項5に記載された電極を有する
ことを特徴とする電池。 - 熱可塑性樹脂と金属と導電性炭素材料とを含有する原料を加熱することにより、溶融した前記熱可塑性樹脂で前記導電性炭素材料の表面を被覆するとともに、前記導電性炭素材料の表面で前記熱可塑性樹脂を炭素化して、酸素還元活性を有する炭素触媒を得る
ことを特徴とする酸素還元用炭素触媒の製造方法。 - 前記熱可塑性樹脂は、前記金属に配位可能な高分子配位子であり、
前記原料は、前記熱可塑性樹脂が前記金属に配位して形成された錯体を含有する
ことを特徴とする請求項7に記載された炭素触媒の製造方法。 - 前記熱可塑性樹脂は、その分子内に配位原子として1又は複数の窒素原子を含む
ことを特徴とする請求項8に記載された炭素触媒の製造方法。 - 前記熱可塑性樹脂は、ポリビニルピリジン、サレン重合物、ポリピロール、ポリビニルピロール、3−メチルポリピロール、ポリビニルカルバゾール、ポリアミド、ポリアニリン、ポリビスマレイミド、ポリアミドイミドからなる群より選択される1種又は2種以上を含有する
ことを特徴とする請求項9に記載された炭素触媒の製造方法。 - 前記導電性炭素材料は、カーボンブラックである
ことを特徴とする請求項7乃至10のいずれかに記載された炭素触媒の製造方法。 - 前記金属は遷移金属である
ことを特徴とする請求項7乃至11のいずれかに記載された炭素触媒の製造方法。 - 炭素化により得られた前記炭素触媒に前記金属を除去する処理を施す工程と、
前記処理が施された前記炭素触媒に熱処理を施すことにより前記炭素触媒の活性を向上させる工程と、
をさらに含む
ことを特徴とする請求項7乃至12のいずれかに記載された炭素触媒の製造方法。 - 前記熱処理は、前記炭素触媒を300〜1500℃の範囲内の温度で加熱することにより行う
ことを特徴とする請求項13に記載された炭素触媒の製造方法。 - 請求項7乃至14のいずれかに記載された方法により製造され、
酸素還元活性を有する
ことを特徴とする酸素還元用炭素触媒。
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