JP6698148B2 - プロトン供与体とプロトン受容体を有する多面体オリゴマー型シルセスキオキサンを含むフッ素系ナノ複合膜及びその製造方法 - Google Patents
プロトン供与体とプロトン受容体を有する多面体オリゴマー型シルセスキオキサンを含むフッ素系ナノ複合膜及びその製造方法 Download PDFInfo
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- JP6698148B2 JP6698148B2 JP2018501968A JP2018501968A JP6698148B2 JP 6698148 B2 JP6698148 B2 JP 6698148B2 JP 2018501968 A JP2018501968 A JP 2018501968A JP 2018501968 A JP2018501968 A JP 2018501968A JP 6698148 B2 JP6698148 B2 JP 6698148B2
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- polyhedral oligomeric
- oligomeric silsesquioxane
- nanocomposite membrane
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Description
プロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンをフッ素系プロトン伝導性ポリマー溶液に混合するステップ;及び
前記混合溶液をキャストグし、溶媒を除去するステップを含むプロトン伝導性ナノ複合膜の製造方法に関する。
図2は、実施例1と比較例1で得られたナノ複合膜の引張強度を測定したものである。
図3は、実施例1と比較例1で製造されたナノ複合膜を利用して製造されたセルの性能を比較したものである。
本発明は、燃料電池用プロトン伝導性高分子ナノ複合膜に関する。
本発明のプロトン伝導性ナノ複合膜はプロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンがフッ素系プロトン伝導性ポリマー基材に導入されて形成される。
[化学式1]
上記RはR1R2である。
R1は(CH2)n(ここで、nは1〜6の整数)またはフェニレンである。
R2は酢酸、硝酸、リン酸、スルホン酸、過塩素酸、塩酸、炭酸、これらの塩またはこれらを含む化合物である。
[化学式2]
上記式中、Rは16個まで官能化されることができる。
また、前記Aは−A1A2であり、ここで、A1は(CH2)n(ここで、nは1〜6の整数)またはフェニレンであり、A2はNH2、NO3−、NH3、PH3、NH2−、Cl−、O2−、S2−、F−、これらの塩またはこれらを含む化合物である。前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンは、下記化学式4で表示されることができる。
[化学式4]
前記式中、Aは、Rが16個まで官能化されることができる。
実施例1
1.スルホン酸基を有する多面体オリゴマーシルセスキオキサン(POSS−SO3H(POSS−SA))の合成
FT−IR: 3070(OH of SO3H)、2330(SO3H−H2O)、1718、1590、1470、1446、1395,1298、1132(SO3 asymm)、1081(SO3 symm)、1023(SiOSi asymm)、991、806(SiOSisymm)
氷水に5gのOPSと30mlの発煙硝酸(fuming nitric acid)をビーカーに入れて30min程度混合した。常温で20hour程度反応させた。前記溶液を氷水に解いて粉末を生じるた後にフィルタリングした。継いて、フィルタリングして得た固体残留物を水で洗浄した後、エタノール100mlで2回ほど洗浄した(ONP取得)。
前で取得したONP0.5gを0.06gの10wt%Pd/Cと混合し、粉碎した。ここで、THF20mlとトリエチルアミン(triethylamine)20mlを入れた。混合物に蟻酸(formic acid)を少量添加した後、5hour反応させる。反応によって、二層に分離されるが、上記透明層は捨て、次の黒い層を集めて、ここに50mlのTHFと50mlの水を混合した。混合した溶液をシーライト(celite)でcolumnクロマトグラフィーをしてオクタニトロフェニル(Octanitrophenyl)POSS(ONPS)を得た。継いて、50mlの酢酸エチル(ethyl acetate)をfilterateに加え、純粋な水100mlを注ぎ込んで揺する。
Dupont社で製造されたナフィオン溶液(Nafion solution)を真空乾燥して、溶媒を除去し、ジメチルアセトアミド(DMAc)に1:19の重量比で溶解させる(5wt%溶液の調製)。前記5wt%溶液 11.76g(ナフィオンは0.588g)を、4つのガラス瓶にそれぞれ入れておいた。
POSS−SAとPOSS−Nを使用せず、ナフィオンのみを使用してプロトン伝導性高分子膜を製造した。
比較例1と実施例1でそれぞれ得られた複合膜サンプルなどの厚さを測定した後、Bekktech社の4プローブ導電率セル(probe conductivity cell)を交流インピーダンスと接続した後、80℃/100%RHの条件でイオン導電率を測定した。測定されたイオン導電率を図1に示した。
実施例1と比較例1の膜を乾燥した後、常温で万能材料試験機(UTM)装置を利用して、ASTM d882の標準的な実験方法によって、ナノ複合膜の機械的強度を測定した。実施例1と比較例1で得られたナノ複合膜の引張強度を測定した後、図2に示した。
前記実施例1(POSS−SA 2wt%、POSS−N 0.3wt%を使用)及び比較例1で製造されたナノ複合膜の両面に商業用の触媒電極層をホットプレス法でコーティングして膜−電極アセンブリー(Membrane−electrode assembly、MEA)をそれぞれ製造した。
下記は、本願の出願当初に記載の発明である。
<請求項1>
プロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンがフッ素系プロトン伝導性高分子膜に導入されたプロトン伝導性ナノ複合膜。
<請求項2>
前記フッ素系プロトン伝導性ポリマー基材は、末端基にスルホン酸基、リン酸基またはカルボキシル基の中から選択された官能基を持つフッ素系ポリマーで形成されたことを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
<請求項3>
前記フッ素系プロトン伝導性ポリマーは、ナフィオン(Nafion)、ハイフロン(Hyflon)、フレミオン(Flemion)、ダウ(Dow)、アクイヴィオン(Aquivion)、ゴア(Gore)またはエーシーアイプレックス(Aciplex)であることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
<請求項4>
前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが、前記ナノ複合膜に1〜20重量%で含有されることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
<請求項5>
前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが重量比で1:0.05〜1で含有されることを特徴とする請求項4に記載のプロトン伝導性ナノ複合膜。
<請求項6>
前記多面体オリゴマーシルセスキオキサン粒子のサイズが1〜3nmであることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
<請求項7>
前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンは、下記化学式1で表示されることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
[化学式1]
<化4>
前記化学式1において、Rはプロトン供与体であり、
前記Rは、酢酸、硝酸、リン酸、スルホン酸、過塩素酸、塩酸、炭酸、これらの塩またはこれらを含む化合物である。
<請求項8>
前記Rは−R1−R2であり、
前記R1は(CH2)n(ここで、nは1〜6の整数)またはフェニレンであり、
ここで、R2は酢酸、硝酸、リン酸、スルホン酸、過塩素酸、塩酸、炭酸、これらの塩またはこれらを含む化合物である請求項7に記載のプロトン伝導性ナノ複合膜。
<請求項9>
前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンが下記化学式2で表示されることを特徴とする請求項7に記載のプロトン伝導性ナノ複合膜。
[化学式2]
<化5>
上記式中、Rのうち少なくとも一つはSO3Hであり、前記Rは16個まで官能化されることができる。
<請求項10>
前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが下記化学式3で表示されることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
[化学式3]
<化6>
前記化学式1において、前記Aは非共有電子対を有する窒素、酸素、リン-硫黄、フッ素、塩素原子を含む化合物である。
<請求項11>
前記Aは−A1A2であり、
前記A1は、(CH2)n(ここで、nは1〜6の整数)またはフェニレンであり、A2はNH2、NO3−、NH3、PH3、NH2−、Cl−、O2−、S2−、F−、これらの塩またはこれらを含む化合物である請求項10に記載のプロトン伝導性ナノ複合膜。
<請求項12>
前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが下記化学式4で表示されることを特徴とする請求項10に記載のプロトン伝導性ナノ複合膜。
[化学式4]
<化7>
上記式中、Aのうち少なくとも一つはNH2であり、前記Aは16個まで官能化されることができる。
<請求項13>
プロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンをフッ素系プロトン伝導性ポリマー溶液に混合するステップ;及び
前記混合溶液をキャストし、溶媒を除去するステップを含むプロトン伝導性ナノ複合膜製造方法。
<請求項14>
前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンを前記ナノ複合膜に1〜20重量%で添加させるが、前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンを重量比で1:0.05〜1で添加することを特徴とする請求項13に記載のプロトン伝導性ナノ複合膜の製造方法。
Claims (11)
- プロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンがフッ素系プロトン伝導性高分子膜に導入されたプロトン伝導性ナノ複合膜。
- 前記フッ素系プロトン伝導性高分子膜は、末端基にスルホン酸基、リン酸基またはカルボキシル基の中から選択された官能基を持つフッ素系ポリマーで形成されたことを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
- 前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが、前記ナノ複合膜に1〜20重量%で含有されることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
- 前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンが重量比で1:0.05〜1で含有されることを特徴とする請求項3に記載のプロトン伝導性ナノ複合膜。
- 前記多面体オリゴマーシルセスキオキサン粒子のサイズが1〜3nmであることを特徴とする請求項1に記載のプロトン伝導性ナノ複合膜。
- 前記Rは−R1−R2であり、
前記R1は(CH2)n(ここで、nは1〜6の整数)またはフェニレンであり、
ここで、R2は−SO3Hである請求項6に記載のプロトン伝導性ナノ複合膜。 - プロトン供与体を有する多面体オリゴマーシルセスキオキサンとプロトン受容体を有する多面体オリゴマーシルセスキオキサンをフッ素系プロトン伝導性ポリマー溶液に混合するステップ;及び
前記混合溶液をキャストし、溶媒を除去するステップを含むプロトン伝導性ナノ複合膜の製造方法。 - 前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンを前記ナノ複合膜に1〜20重量%で添加させるが、前記プロトン供与体を有する多面体オリゴマーシルセスキオキサンと前記プロトン受容体を有する多面体オリゴマーシルセスキオキサンを重量比で1:0.05〜1で添加することを特徴とする請求項10に記載のプロトン伝導性ナノ複合膜の製造方法。
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JP6202431B2 (ja) * | 2012-09-04 | 2017-09-27 | 学校法人神奈川大学 | かご型シルセスキオキサン誘導体 |
KR20140142036A (ko) | 2013-06-03 | 2014-12-11 | 서강대학교산학협력단 | 아민기-함유 실세스퀴옥산을 이용한 폴리벤즈이미다졸 나노복합막, 이의 제조 방법, 및 이를 포함하는 연료전지 |
KR101773246B1 (ko) | 2015-03-09 | 2017-09-01 | 서강대학교산학협력단 | 프로톤 주게와 프로톤 받게를 갖는 다면체 올리고머형 실세스퀴옥산을 포함하는 불소계 나노 복합막 및 이의 제조방법 |
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2016
- 2016-03-15 US US15/742,010 patent/US10374244B2/en active Active
- 2016-03-15 WO PCT/KR2016/002572 patent/WO2017159889A1/ko active Application Filing
- 2016-03-15 JP JP2018501968A patent/JP6698148B2/ja active Active
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US10374244B2 (en) | 2019-08-06 |
JP2018525778A (ja) | 2018-09-06 |
US20180198147A1 (en) | 2018-07-12 |
WO2017159889A1 (ko) | 2017-09-21 |
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