JP4297850B2 - 高分子ナノ複合膜及びこれを採用した燃料電池 - Google Patents
高分子ナノ複合膜及びこれを採用した燃料電池 Download PDFInfo
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Description
まず、層構造を有する無機物の一つであるモンモリロナイトを利用して水素イオン伝導性無機物を次の通り調製した。
前記反応混合物に3−MPTMS 24.50ミリモル(4.63g)を添加する前に、反応混合物にドデシルアミン24.5ミリモルをさらに加えたことを除いては、実施例1と同じ過程によって水素イオン伝導性無機物を製造した。
前記反応混合物に3−MPTMS 24.50ミリモル(4.63g)を添加する前に、反応混合物にセシルトリメチルアンモニウムブロマイド24.5ミリモルをさらに加えたことを除いては、実施例1と同じ過程によって水素イオン伝導性無機物を製造した。
前記反応混合物に3−MPTMS 24.50ミリモル(4.63g)を添加する前に、反応混合物にドデシルトリメチルアンモニウムブロマイド24.5ミリモルをさらに加えたことを除いては、実施例1と同じ過程によって水素イオン伝導性無機物を製造した。
前記反応混合物に3−MPTMS 24.50ミリモル(4.63g)を添加する前に、反応混合物にテトラブチルアンモニウムヒドロキシド24.5ミリモルをさらに加えたことを除いては、実施例1と同じ過程によって水素イオン伝導性無機物を製造した。
実施例3で得られた水素イオン伝導無機物0.03gと、伝導性高分子のテトラフルオロエチレンとパーフルオロ−3,6−ジオキサ−4−メチル−7−オクテンスルホニルフルオライドとの共重合体5wt%溶液20gとをよく混合した。これを90℃に加熱した後、900rpmの速度で強く撹拌を行った。次に、反応混合物を3日間撹拌した後、高分子膜製造プレートに移した。これを130℃に調節されたオーブンで4時間熱処理して高分子ナノ複合膜を製造した。
実施例3で得られた水素イオン伝導性無機物0.03gと、テトラフルオロエチレンとパーフルオロ−3,6−ジオキサ−4−メチル−7−オクテンスルホニルフルオライドとの共重合体5wt%溶液20gとをよく混合し、この混合物をオートクレーブ容器に入れた後、90℃、80psiで24時間反応を行った。
実施例3で得られた水素イオン伝導性無機物0.03gと、テトラフルオロエチレンとパーフルオロ−3,6−ジオキサ−4−メチル−7−オクテンスルホニルフルオライドとの共重合体5wt%溶液20gとをよく混合し、これをホモゲナイザで10,000rpmの速度で30分撹拌した後、90℃900rpmで12時間反応を行った。
実施例3で得られた水素イオン伝導性無機物0.03gと、テトラフルオロエチレンとパーフルオロ−3,6−ジオキサ−4−メチル−7−オクテンスルホニルフルオライドとの共重合体3wt%溶液20gとをよく混合した後、これを90℃に加熱して900rpmの速度で強く撹拌した。前記反応混合物を3日間反応させた後、この高分子と無機物との溶液を高分子膜製造プレートに移した。高分子膜製造プレートを130℃に調節されたオーブンで4時間熱処理して高分子ナノ複合膜を製造した。
実施例3で得られた水素イオン伝導性無機物0.03gとパーフルオロ化スルホン酸10wt%溶液20gとをよく混合した後、これを90℃に加熱し、10,000rpmの速度で強く撹拌した。前記反応混合物を3日間反応させた後、これを高分子膜製造プレートに移した。この高分子製造プレートを130℃に調節されたオーブンで4時間熱処理して高分子ナノ複合膜を形成した。
実施例8で得られた高分子ナノ複合膜を利用してMEAを製作した後、これを利用して2モルのメタノール溶液と空気とを燃料に使用する直接メタノール燃料電池を製造した。
現在商業化されているナフィオン115膜(デュポン社)を利用してMEAを製造し、2モルのメタノール溶液と空気とを燃料に使用して直接メタノール燃料電池を製造した。
Claims (13)
- ナノサイズの層間距離の層構造を有する無機物の層間に、前記無機物とエーテル(−O−)結合で連結されており、末端に遊離スルホン酸基を有するシリケートであるスルホン酸基が導入されてなる、層構造を有する水素イオン伝導性無機物。
- 前記スルホン酸基が、
末端に遊離チオール基を有するアルコキシシランを加水分解及び脱水縮合反応させ、前記無機物とエーテル結合で連結した後、酸化剤との反応でチオール基を酸化させることにより得られてなることを特徴とする請求項1に記載の層構造を有する水素イオン伝導性無機物。 - 前記アルコキシシランが3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルメチルジメトキシシランよりなる群から選択された一つ以上であることを特徴とする請求項2に記載の層構造を有する水素イオン伝導性無機物。
- ナノサイズの層間距離を有する無機物がモンモリロナイト、ハイドレートナトリウムカルシウムアルミニウムマグネシウムシリケートヒドロキシド、パイロフィライト、タルク、バーミキュライト、ソーコナイト、サポナイト、ノントロナイト、アメサイト、ベイレークロア、チャモサイト、クリノクロア、クーカイト、コランドフィライト、ダフネ石、デレス石、ゴニヤライト、ニマイト、オディナイト、斜方シャモス石、ペンニン、ペナント石、リピドライト、須藤石、チュリンゲン石、カオリナイト、ディッカイト及びナクライトよりなる群から選択された一つ以上であることを特徴とする請求項1に記載の層構造を有する水素イオン伝導性無機物。
- 前記ナノサイズの層間距離を有する無機物の層間距離が0.1ないし10nmであることを特徴とする請求項1に記載の層構造を有する水素イオン伝導性無機物。
- 界面活性剤がさらに添加されてなることを特徴とする請求項1に記載の層構造を有する水素イオン伝導性無機物。
- 前記界面活性剤がドデシルアミン、セチルトリメチルアンモニウムブロマイド、ドデシルトリメチルアンモニウムブロマイド、テトラブチルアンモニウムヒドロキシドよりなる群から選択された一つ以上であることを特徴とする請求項6に記載の層構造を有する水素イオン伝導性無機物。
- 前記水素イオン伝導性無機物の層間距離が0.1ないし50nmであることを特徴とする請求項1に記載の層構造を有する水素イオン伝導性無機物。
- 請求項1ないし8のうちいずれか1項に記載の層構造を有する水素イオン伝導性無機物と水素イオン伝導性高分子との反応生成物を含む高分子ナノ複合膜。
- 前記水素イオン伝導性高分子がパーフルオロ化スルホン酸高分子、スルホン化ポリイミド、スルホン化ポリエーテルケトン、スルホン化ポリスチレン、スルホン化ポリスルホンよりなる群から選択された一つ以上であることを特徴とする請求項9に記載の高分子ナノ複合膜。
- 前記水素イオン伝導性高分子が、層構造を有する水素イオン伝導性無機物100質量部を基準とし、500ないし10000質量部の範囲にあることを特徴とする請求項9に記載の高分子ナノ複合膜。
- 請求項1ないし8のうちいずれか1項に記載の層構造を有する水素イオン伝導性無機物と水素イオン伝導性高分子との反応生成物を含む高分子ナノ複合膜を、水素イオン伝導膜として採用した燃料電池。
- 直接メタノール燃料電池であることを特徴とする請求項12に記載の燃料電池。
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KR100696521B1 (ko) * | 2005-05-25 | 2007-03-19 | 삼성에스디아이 주식회사 | 수소 이온 전도성 무기물, 이를 포함한 고분자 나노 복합막및 이를 채용한 연료 전지 |
KR100670340B1 (ko) | 2005-05-25 | 2007-01-16 | 삼성에스디아이 주식회사 | 수소 이온 전도성 티타네이트, 이를 포함한 고분자 나노복합막 및 이를 채용한 연료 전지 |
US9045607B2 (en) | 2005-06-28 | 2015-06-02 | Samsung Sdi Co., Ltd. | Polymer membrane and membrane-electrode assembly for fuel cell and fuel cell system comprising same |
DE602006008536D1 (de) * | 2005-06-28 | 2009-10-01 | Samsung Sdi Co Ltd | Polymerelektrolytmembran und Membran-Elektroden-Einheit für ein Brennstoffzellensystem diese enthaltend |
EP1760110B1 (en) | 2005-09-03 | 2011-11-02 | Samsung SDI Co., Ltd. | Polybenzoxazine-based compound, electrolyte membrane including the same, and fuel cell employing the electrolyte membrane |
KR100708713B1 (ko) | 2005-09-24 | 2007-04-17 | 삼성에스디아이 주식회사 | 나노복합체, 나노복합 전해질막 및 이를 이용한 연료전지 |
KR100739643B1 (ko) * | 2005-10-28 | 2007-07-13 | 삼성에스디아이 주식회사 | 연료 전지용 고분자 전해질 막, 이를 포함하는 연료 전지용막-전극 어셈블리 및 이를 포함하는 연료 전지 시스템 |
KR100717798B1 (ko) * | 2005-10-28 | 2007-05-11 | 삼성에스디아이 주식회사 | 이온 전도성 실리케이트 화합물 및 그의 제조 방법 |
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US20050084728A1 (en) | 2005-04-21 |
CN1618846A (zh) | 2005-05-25 |
KR20050022744A (ko) | 2005-03-08 |
EP1511112A1 (en) | 2005-03-02 |
CN1320039C (zh) | 2007-06-06 |
US7368198B2 (en) | 2008-05-06 |
JP2005079099A (ja) | 2005-03-24 |
KR100528345B1 (ko) | 2005-11-15 |
EP1511112B1 (en) | 2016-12-14 |
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