JP2004193136A - ナノ複合電解質膜及びこれを採用した燃料電池 - Google Patents
ナノ複合電解質膜及びこれを採用した燃料電池 Download PDFInfo
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Abstract
【解決手段】 陽イオン交換基を有するポリマーと、前記ポリマー中に分散しているシリケートナノ粒子と、を含み、前記シリケートナノ粒子は層状構造を有し、前記ナノ粒子の層間に前記ポリマーが挿入されている燃料電池用ナノ複合電解質膜。本発明のナノ複合電解質膜は、メタノールなどの極性有機燃料の浸入を抑制する、非常に向上した性能を有するだけでなく、適切なイオン伝導度を有しているか、前記ナノ粒子の層が剥離している。本発明のナノ複合電解質膜を採用した燃料電池において、メタノール水溶液を燃料として使用する場合に、メタノールのクロスオーバーがさらに抑制され、それにより前記燃料電池の作動効率及び寿命が向上する。
【選択図】 図1
Description
カソード反応:1.5 O2+6H++6e−→3H2O
全反応:CH3OH+1.5 O2→2H2O+CO2
前記反応式に示されるように、アノードではメタノールと水とが反応して二酸化炭素、6つの水素イオン及び6つの電子が生成し、生成した水素イオンは高分子電解質膜を媒体としてカソードに移動する。カソードでは水素イオン、外部回路を通じて伝えられた電子及び酸素が反応して水が生成する。DMFCの全反応では、メタノールと酸素とが反応して水及び二酸化炭素を生成し、この過程でメタノールの燃焼熱に該当するエネルギーの相当量が電気エネルギーに転換される。
ナノ複合電解質膜の製造
220〜270m2/gの表面積を有するモンモリロナイトナノ粒子(Montmorillonite K10、Aldrich社製)10g、セチルピリジウムクロライド0.1g、イオン交換水30mlを混合した後、24時間攪拌した。次に、モンモリロナイトナノ粒子をろ過によって分離した。分離されたモンモリロナイトナノ粒子をイオン交換水で3回洗浄した後、凍結乾燥して膨潤モンモリロナイトナノ粒子を得た。
ナノ複合電解質膜を採用した燃料電池
実施例1で得たナノ複合電解質膜、白金−ルテニウム触媒を有するアノード、白金触媒を有するカソードを接合して燃料電池を構成した。
ナノ複合電解質膜の代りにデュポン社のナフィオン115を使用したことを除いては、実施例2と同じ方法で燃料電池を製造し、実施例2と同じ条件下で電流密度による電池電圧の変化を測定し、その結果を図1に示す。
実施例1で得たナノ複合電解質膜のイオン伝導度を、4点探針法を利用して25℃、50℃及び75℃の温度で測定し、その結果を表1に示す。比較のため、商業的に入手したポリマー電解質膜であるナフィオン117(Nafion 117、デュポン社製)のイオン伝導度を表1に共に示す。
ナノ複合電解質膜にメタノールが浸入すればナノ複合電解質膜の体積が増加して膨潤現象が発生する。ナノ複合電解質膜のメタノールの浸入抑制性能はナノ複合電解質膜をメタノール水溶液に浸漬した後、膨潤の程度を測定することによって評価できる。
図1に示されるように、同じ電流密度で実施例2の電圧が比較例1の電圧より非常に高い。電圧がさらに高いということは作動効率がさらに高いということを意味する。これは本発明のナノ複合電解質膜がメタノールのクロスオーバーを非常に抑制するだけでなく、優れたイオン伝導度を有することを示す。
Claims (13)
- 陽イオン交換基を有するポリマーと、
前記ポリマー中に分散しているシリケートナノ粒子と、を含み、
前記シリケートナノ粒子は層状構造を有し、前記ナノ粒子の層間に前記ポリマーが挿入されているか前記ナノ粒子の層が剥離している、ことを特徴とする燃料電池用ナノ複合電解質膜。 - 前記シリケートはスメクタイト、バーミキュライト、ハロイサイト、セリサイト、マイカ及びこれらの混合物のうちから選択されたことを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記スメクタイトはモンモリロナイト、サポナイト、バイデライト、ノントロナイト、ヘクトライト、ステベンサイト及びこれらの混合物のうちから選択されたことを特徴とする請求項2に記載のナノ複合電解質膜。
- 前記シリケートナノ粒子の平均粒子径は1〜100nmであることを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記ナノ複合電解質膜のうち前記シリケートナノ粒子の含量は1〜30質量%であることを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記ポリマーの陽イオン交換基はスルホン酸基、カルボキシル基、リン酸基、イミド基、スルホンイミド基、スルホンアミド基及びヒドロキシ基のうちから選択されたことを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記ポリマーは、陽イオン交換基を有するポリマーであって、トリフルオロエチレン、テトラフルオロエチレン、スチレン−ジビニルベンゼン、α,β,β−トリフルオロスチレン、スチレン、イミド、スルホン、ホスファゼン、エーテルエーテルケトン、エチレンオキシド、ポリフェニレンスルフィドまたは芳香族基のホモポリマー及びコポリマー及びこれらの誘導体及びこれらの混合物のうちから選択されたことを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記ポリマーは、側鎖の末端に陽イオン交換基としてスルホン酸基を有し、その主鎖及び側鎖の炭素原子に結合しているフッ素原子の数と水素原子の数との総和のうちフッ素原子の数が90%以上である、スルホネート高フッ化ポリマーを含むことを特徴とする請求項1に記載のナノ複合電解質膜。
- 前記ナノ複合電解質膜の厚さは30〜200μmであることを特徴とする請求項1に記載のナノ複合電解質膜。
- 酸化剤の還元反応がおきるカソード、燃料の酸化反応がおきるアノード、及び前記カソードとアノード間に位置する電解質膜を含む燃料電池において、
前記電解質膜は請求項1〜9のいずれか1項に記載のナノ複合電解質膜であることを特徴とする燃料電池。 - 前記カソードは白金担持カーボン触媒を含む触媒層を含むことを特徴とする請求項10に記載の燃料電池。
- 前記アノードは白金担持カーボン触媒を含む触媒層を含むことを特徴とする請求項10に記載の燃料電池。
- 前記アノードは白金−ルテニウム担持カーボン触媒を含む触媒層を含むことを特徴とする請求項10に記載の燃料電池。
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WO2006051749A1 (ja) * | 2004-11-10 | 2006-05-18 | Toyo Boseki Kabushiki Kaisha | 芳香族炭化水素系プロトン交換膜およびこれを使用した直接メタノール型燃料電池 |
US8574785B2 (en) * | 2005-08-31 | 2013-11-05 | Samsung Sdi Co., Ltd. | Membrane-electrode assembly for fuel cell with binder layer having inorganic additive and fuel cell system using the same |
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KR100528345B1 (ko) | 2003-08-29 | 2005-11-15 | 삼성에스디아이 주식회사 | 고분자 나노 복합막 및 이를 채용한 연료 전지 |
KR100804195B1 (ko) * | 2003-09-04 | 2008-02-18 | 연세대학교 산학협력단 | 고온에서 수소이온 전도가 가능한 고분자 전해질막의제조방법 및 이를 이용한 고분자 전해질형 연료전지의고온 운전 |
US7713629B2 (en) * | 2004-03-26 | 2010-05-11 | Florida State University Research Foundation | Hydrophobic fluorinated polyelectrolyte complex films and associated methods |
US9346673B2 (en) | 2004-06-23 | 2016-05-24 | Samsung Sdi Co., Ltd. | Electrode for fuel cell, membrane-electrode assembly for fuel cell comprising the same, fuel cell system comprising the same, and method for preparing the electrode |
US20060047025A1 (en) * | 2004-06-29 | 2006-03-02 | Matthew Piazza | Viscous materials and method for producing |
KR100542228B1 (ko) * | 2004-06-30 | 2006-01-10 | 삼성에스디아이 주식회사 | 연료전지용 고분자 막/전극 접합체 및 이를 포함하는연료전지 |
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- 2003-07-11 US US10/616,998 patent/US7357999B2/en not_active Expired - Fee Related
- 2003-12-12 JP JP2003415762A patent/JP3768991B2/ja not_active Expired - Fee Related
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WO2006051749A1 (ja) * | 2004-11-10 | 2006-05-18 | Toyo Boseki Kabushiki Kaisha | 芳香族炭化水素系プロトン交換膜およびこれを使用した直接メタノール型燃料電池 |
US8216727B2 (en) | 2004-11-10 | 2012-07-10 | Toyo Boseki Kabushiki Kaisha | Aromatic hydrocarbon based proton exchange membrane and direct methanol fuel cell using same |
US8574785B2 (en) * | 2005-08-31 | 2013-11-05 | Samsung Sdi Co., Ltd. | Membrane-electrode assembly for fuel cell with binder layer having inorganic additive and fuel cell system using the same |
Also Published As
Publication number | Publication date |
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US7357999B2 (en) | 2008-04-15 |
KR20040051287A (ko) | 2004-06-18 |
KR100486728B1 (ko) | 2005-05-03 |
JP3768991B2 (ja) | 2006-04-19 |
CN1288784C (zh) | 2006-12-06 |
US20080008918A1 (en) | 2008-01-10 |
CN1507098A (zh) | 2004-06-23 |
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