JP2007265844A - 燃料電池用触媒層及びこれを用いた膜電極接合体並びに燃料電池 - Google Patents
燃料電池用触媒層及びこれを用いた膜電極接合体並びに燃料電池 Download PDFInfo
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- JP2007265844A JP2007265844A JP2006090482A JP2006090482A JP2007265844A JP 2007265844 A JP2007265844 A JP 2007265844A JP 2006090482 A JP2006090482 A JP 2006090482A JP 2006090482 A JP2006090482 A JP 2006090482A JP 2007265844 A JP2007265844 A JP 2007265844A
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- sulfonic acid
- amorphous carbon
- water
- fuel cell
- catalyst layer
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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
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- Catalysts (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
【解決手段】水に沈殿するスルホン酸基導入無定形炭素15と、水に分散又は溶解するスルホン酸基を導入した無定形炭素16を用いて電極を形成後、水に分散乃至溶解するスルホン酸基を導入した無定形炭素16を除去することで、低白金触媒量でも高い燃料電池特性を持った膜電極接合体、それを用いた燃料電池を提供できる。
【選択図】図1
Description
(A)13C核磁気共鳴スペクトルにおいて縮合芳香族炭素6員環及びスルホン酸基が結合した縮合芳香族炭素6員環の化学シフトが検出される。
(B)粉末X線回折において半値幅(2θ)が5〜30°である炭素(002)面の回折ピークが少なくとも検出される。
(C)プロトン伝導性を示す。
(D)スルホン酸密度が0.5〜14mmol/gである。
(E)スルホン酸基が結合した炭素原子が全炭素原子の3%〜20%である。
(F)硫黄含有量は、0.3〜15atm%である。
0atm%であることが好ましく、白金触媒付きカーボンの凝集を防ぎやすい。
率を増加させる。真空排気は排気速度10L/min以上、到達圧力13.3kPa以下の排気装置を用いることが好ましい。好ましい加熱温度は140〜300℃、より好ましい温度は200〜280℃である。この温度における真空排気の時間は、通常2〜20時間である。
[触媒ワニスの調製]
表1に示す重量%濃度で、 水に沈殿するスルホン酸基が導入された無定形炭素と、水に分散乃至溶解するスルホン酸基が導入された無定形炭素と、プロトン伝導性高分子電解質と、白金触媒付きカーボンとを溶媒に混合し触媒ワニスを調製した。プロトン伝導性物質(化合物1+ナフィオン)と白金触媒付きカーボンの量はほぼ1:2になるように調整した。ここで固形分とはスルホン酸基が導入された無定形炭素とプロトン伝導性高分子電解質と白金触媒付きカーボンをいう。これらをボールミルで混錬し調製した。全固形分%は10%、15%を用意した。粘度は山一電機株式会社製ビスコメイトVM−1A−MHで測定した。
水に分散乃至溶解するスルホン酸基導入無定形炭素 : 化合物2(下記)
プロトン伝導性高分子電解質 :ナフィオン
全固形分%=(化合物1+化合物2又はベンゼンスルホン酸重量+プロトン伝導性高分子電解質重量+白金触媒付きカーボン重量)/(化合物1+化合物2又はベンゼンスルホン酸重量+プロトン伝導性高分子電解質重量+白金触媒付きカーボン重量+溶媒重量)×100
[化合物1]
ナフタレンを濃硫酸(96%)に加え、250℃で15時間加熱した後、過剰の濃硫酸を250℃での減圧蒸留によって除去し、黒色粉末を得た。この黒色粉末を300mlの蒸留水で洗浄し、洗浄後の蒸留水中の硫酸が元素分析の検出限界以下になるまでこの操作を繰り返し、スルホン酸基が導入された無定形炭素を得た。スルホン酸密度は4.5mmol/gであった。この化合物をふるいにかけ、体積平均径1.2μmと水に沈殿するものを取り出した。50mgのスルホン酸基が導入された無定形炭素を10mlの水に分散し、これを日機装社製ナノトラック粒度分析計UPA−EXにより分散性を計測した。その体積平均径の値を求めた。
ナフタレンを濃硫酸(96%)に加え、250℃で15時間加熱した後、過剰の濃硫酸を250℃での減圧蒸留によって除去し、黒色粉末を得た。この黒色粉末を300mlの蒸留水で洗浄し、洗浄後の蒸留水中の硫酸が元素分析の検出限界以下になるまでこの操作を繰り返し、スルホン酸基が導入された無定形炭素を得た。スルホン酸密度は4.5mmol/gであった。この化合物をふるいにかけ、体積平均径15nmと水への分散性が良好なものを取り出した。50mgのスルホン酸基が導入された無定形炭素を10mlの水に分散し、これを日機装社製ナノトラック粒度分析計UPA−EXにより分散性を計測した。その体積平均径の値を求めた。
上記触媒ワニスa〜fをカーボン繊維(E−TEC社製LT−1200)に白金触媒担持量が0.2mg/cm2になるよう塗布し乾燥を行い、触媒層を含有する電極を作った。この電極をプレス機でナフィオン112及びスルホン化エンジニアリングプラスチックの電解質膜に熱圧着することで、アノード及びカソード電極が形成された膜電極接合体を得た。
出力特性1(水に分散乃至溶解するスルホン酸基が導入された無定形炭素除去前):各種膜電極接合体にセパレータを張り合わせ、これをそのまま燃料電池測定装置(東陽テクニカ社製GFT−SG1)で80℃RH100%の条件下、電流電圧測定を行い、1A/cm2時の出力mW/cm2を計測した。この時一方の極には酸素を、一方の極には水素を流し発電させた。
、一方の極には水素を流し発電させた。また、比較例1〜3も同様の操作を行い、電流が一定になったところを計測した。
すると性能が低くなってしまった(実施例4)。セパレータとの接触がより一層悪くなった為と考えられる。このことから水に分散又は溶解するスルホン酸基導入無定形炭素の固形分%が重要であることがわかる。
12・・・ガス供給若しくはプロトン伝導ができず、三相界面が形成されていない白金触媒付きカーボン
13・・・プロトン伝導性高分子電解質
14・・・白金触媒
15・・・水に沈殿するスルホン酸基が導入された無定形炭素
16・・・水に分散又は溶解する、スルホン酸基が導入された無定形炭素
Claims (8)
- 水に沈殿するスルホン酸基が導入された無定形炭素と、水に分散乃至溶解するスルホン酸基が導入された無定形炭素を含有して形成された燃料電池用触媒層であって、その後、水に分散乃至溶解するスルホン酸基が導入された無定形炭素が除去された燃料電池用触媒層。
- 前記、水に沈殿若しくは分散乃至溶解するスルホン酸基が導入された無定形炭素が、13C核磁気共鳴スペクトルにおいて縮合芳香族炭素6員環及びスルホン酸基が結合した縮合芳香族炭素6員環の化学シフトが検出され、粉末X線回折において半値幅(2θ)が5〜30°である炭素(002)面の回折ピークが少なくとも検出されることを特徴とする請求項1に記載の燃料電池用触媒層。
- 前記水に分散乃至溶解するスルホン酸基が導入された無定形炭素が粒度分布測定時に、水中に体積平均径が500nm未満で測定されることを特徴とする請求項1乃至2いずれか一項に記載の燃料電池用触媒層。
- 前記水に沈殿するスルホン酸基が導入された無定形炭素が粒度分布測定時に、体積平均径が500nm以上で検出されることを特徴とする請求項1乃至3いずれか一項に記載の燃料電池用触媒層。
- スルホン酸基が導入された無定形炭素を除去する前に、水に分散乃至溶解するスルホン酸基が導入された無定形炭素が重量比で0.1%から20%含まれて形成されたことを特徴とする請求項1乃至4いずれか一項に記載の燃料電池用触媒層。
- 白金担持量が単極で0.2mg/cm2以下で80℃1A時0.7W/cm2以上の出力を満たすところの請求項1乃至5いずれか一項に記載の燃料電池用触媒層。
- 請求項1乃至6いずれか一項に記載の触媒層を用いたことを特徴とする膜電極接合体。
- 請求項1乃至7いずれか一項に記載の触媒層を用いたことを特徴とする燃料電池。
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Cited By (5)
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JP2008077956A (ja) * | 2006-09-21 | 2008-04-03 | Toppan Printing Co Ltd | 燃料電池用触媒電極形成用ワニス、それを用いた触媒電極、それを用いた膜電極接合体、それを用いた燃料電池 |
JP2008218260A (ja) * | 2007-03-06 | 2008-09-18 | Toppan Printing Co Ltd | 燃料電池用電極触媒層、それを用いて成るmea(電解質膜電極接合体)および固体高分子型燃料電池 |
JP2008234900A (ja) * | 2007-03-19 | 2008-10-02 | Toppan Printing Co Ltd | 触媒電極の製造方法 |
JP2009231158A (ja) * | 2008-03-25 | 2009-10-08 | Toppan Printing Co Ltd | 燃料電池用電極触媒層、膜電極接合体、燃料電池及び燃料電池用電極触媒層の製造方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2008077956A (ja) * | 2006-09-21 | 2008-04-03 | Toppan Printing Co Ltd | 燃料電池用触媒電極形成用ワニス、それを用いた触媒電極、それを用いた膜電極接合体、それを用いた燃料電池 |
JP2008218260A (ja) * | 2007-03-06 | 2008-09-18 | Toppan Printing Co Ltd | 燃料電池用電極触媒層、それを用いて成るmea(電解質膜電極接合体)および固体高分子型燃料電池 |
JP2008234900A (ja) * | 2007-03-19 | 2008-10-02 | Toppan Printing Co Ltd | 触媒電極の製造方法 |
JP2009231158A (ja) * | 2008-03-25 | 2009-10-08 | Toppan Printing Co Ltd | 燃料電池用電極触媒層、膜電極接合体、燃料電池及び燃料電池用電極触媒層の製造方法 |
US9431661B2 (en) | 2010-12-20 | 2016-08-30 | Toyota Jidosha Kabushiki Kaisha | Cathode catalyst layer, membrane electrode assembly and polymer electrolyte fuel cell and manufacturing method thereof |
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