JP2011503300A - ヘテロポリ酸を含むポリマー電解質 - Google Patents
ヘテロポリ酸を含むポリマー電解質 Download PDFInfo
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- JP2011503300A JP2011503300A JP2010533275A JP2010533275A JP2011503300A JP 2011503300 A JP2011503300 A JP 2011503300A JP 2010533275 A JP2010533275 A JP 2010533275A JP 2010533275 A JP2010533275 A JP 2010533275A JP 2011503300 A JP2011503300 A JP 2011503300A
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- polymer electrolyte
- polyoxometalate
- polymer
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- covalently
- Prior art date
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Images
Classifications
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- 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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Abstract
Description
本開示は、米国特許仮出願番号第60/986749号(2007年11月9日出願)の権利を主張する。
本開示の主題事項は、米国エネルギー省から認められた協力協定第DE−FC36−02AL67621号のもと、政府支援を得てなされた。政府は、本発明における特定の権利を有する。
本開示は、ポリオキソメタレート(POM)又はヘテロポリ酸(HPA)を含有又は含む燃料電池に有用である可能性がある、ポリマー電解質、ポリマー電解質膜(PEM)及び膜電極アセンブリ(MEA)に関するものである。
目的:本研究の目的は、より高温で乾燥した条件下において、FER(フッ素放出率)の低減及び伝導度の増加について、新しいMn系HPA(ドーソン(Dawson)型H7[P2W17O61](Mn−OH2)]−NH2)の使用を評価することである。使用できるPEMの量は、異なるPEMタイプそれぞれについて、1つのMEAに対する試験に限定された。
開始−
図1及び2は、開始段階を示す。図1は、開始条件下で行われた最後の偏光スキャンを表わす。図2は、スキャン数の関数としての、偏光スキャンと偏光スキャンとの間に実施されたPSS(定電位スキャン)を示す。開始稼働のおよその時間は6時間である。
開始段階の後、手順指示により、乾燥攻撃試験に進んだ。この結果を図3及び4に示す。図3は、一定露点で、電池温度に対する関数としての各MEAの性能を示す。エラーバーは、最後のGSS(定電流スキャン)にわたる電圧変動である。図4は、電池温度に対する関数としてのHFR(高周波数抵抗)を示す。各温度及び試料についてのインピーダンスのコールコールプロット全幅が、図8〜10で等方向的にプロットされている。
加速試験の結果は図5に示されており、この図は負荷下の電圧対時間、図6ではFER対時間を表わしている。図6において、x軸は採取時間を表わす。
ECSA試験の結果は、表1にまとめられている。1%Mnが、SEF(表面積強化因子−触媒表面積/幾何学的表面積)において唯一、実際に異なっているように見受けられる。これは、ロールの劣る部分から採取されたためである可能性が十分にある。図7の延長スペクトルを見ると、Mnに関連した観測可能な明らかな特徴はなく、すべてのスペクトルがほぼ等しいことがわかる。
5cm2のPEM切片をダイカットし、計量して、室温で脱イオン水20ccが入った密閉ボトルに入れた。pH試験紙を用いて試験し、試料間に測定可能なpHの差はなかった。
1.欠損型ヘテロポリ酸の調製
一空位又は二空位の欠損型シリコタングステン酸のカリウム塩は、Teze,A.;Herve,G.,α−,β−,and γ−Dodecatungstosilicic acids:isomers and related lacunary compounds.Inorganic Syntheses 1990,27,85−96に記述されているように合成された(この文献の開示は、参考として本明細書に組み込まれる)。ハイブリッド有機−無機モノマーの合成には、任意の欠損型ヘテロポリ酸を使用することが可能である。欠損型シリコタングステン酸のカリウム塩は、調製次第すぐに使用された。
任意の数の官能基を有するシラン又はホスホリル誘導体を、欠損型ヘテロポリ酸に結合させて、無機−有機ハイブリッドモノマーを形成することができる。本プロジェクトに使用される、この官能基を有する有機前駆体は、メタクリルシラン及びスチリルシランであった。メタクリルオキシプロピルトリメトキシシランは、Gelest,Inc.から(form)購入された。トリエトキシスチリル−シランは、Judeinstein,P.,Synthesis and Properties of Polyoxometalates Based Inorganic−Organic Polymers.Chem.Mater.1992,4,4−7に記述されているグリニャール(Gringard)反応によって調製された(この文献の開示は、参考として本明細書に組み込まれる)。これらのモノマーに組み込まれ得る他の官能基を有する有機化合物は数多く存在する。
一空位又は二空位の欠損型シリコタングステン酸のカリウム塩又は酸形態は、水溶液中、又は水とアセトニトリルの混合物中で、有機ホスホリル又は有機シリル官能基を有する化合物(フェニルホスホン酸、ホスホン酸、トリエトキシスチリルシラン、又はメタクリルオキシプロピル−トリメトキシシランなど)と混合される。この混合物は必要に応じて塩酸を加えることにより酸性にされる。この混合物を室温又は還流温度で一晩、攪拌して反応させる。テトラブチル−又はテトラメチル−アンモニウム(TBA又はTMA)塩は、テトラブチルアンモニウムブロミド又はテトラメチルアンモニウムクロリドをそれぞれ、化学量論的量加えることによって得ることができる。形成される白色の沈殿を水及びイソプロピルアルコールで洗う。望ましい生成物を得るため、この溶液を回転濃縮機(rotovap)にかけ、モノマーのカリウム塩又は酸形態を得ることができる。典型的な反応式を次に示す:
無機−有機ハイブリッドポリマー及びコポリマーの調製には、2つの一般的な方法が使用される。これには、溶液ラジカル重合、酸化還元エマルション重合、及び水溶液ラジカル重合のための独自の方法が挙げられる。
Claims (30)
- a)ポリマー電解質と、
b)ポリオキソメタレートと、
c)該ポリオキソメタレートに対する対イオンと、
を含み、
該ポリオキソメタレートは、Mn及びCeからなる群から選択される遷移金属を含む、ポリマー電解質組成物。 - 前記ポリオキソメタレートがMnを含む、請求項1に記載のポリマー電解質組成物。
- 前記ポリオキソメタレートがCeを含む、請求項1に記載のポリマー電解質組成物。
- 前記ポリオキソメタレートがヘテロポリ酸である、請求項1〜3のいずれか一項に記載のポリマー電解質組成物。
- 請求項1〜4のいずれか一項のポリマー電解質組成物を含む、燃料電池ポリマー電解質膜。
- 請求項1〜4のいずれか一項のポリマー電解質組成物を含む、燃料電池膜電極アセンブリ。
- 共有結合しているポリオキソメタレートとそれに伴うポリオキソメタレートに対する対イオンとを含む第1ペンダント基を含み、前記ポリオキソメタレート及び前記対イオンの少なくとも1つが、Mn及びCeからなる群から選択される遷移金属を含む、ポリマー電解質。
- 前記ポリオキソメタレートがMn及びCeからなる群から選択される遷移金属を含む、請求項7に記載のポリマー電解質。
- 前記ポリオキソメタレートがMnを含む、請求項7に記載のポリマー電解質。
- 前記ポリオキソメタレートがCeを含む、請求項7に記載のポリマー電解質。
- 前記ポリオキソメタレートに対する前記対イオンが、Mn陽イオン及びCe陽イオンからなる群から選択される、請求項7〜10のいずれか一項に記載のポリマー電解質。
- 前記ポリオキソメタレートに対する前記対イオンがMn陽イオンである、請求項7〜10のいずれか一項に記載のポリマー電解質。
- 前記ポリオキソメタレートに対する前記対イオンがCe陽イオンである、請求項7〜10のいずれか一項に記載のポリマー電解質。
- フッ素化されている、請求項7〜13のいずれか一項に記載のポリマー電解質。
- ポリオキソメタレート以外の第2の酸官能基を含む、請求項7〜14のいずれか一項に記載のポリマー電解質。
- 前記第2の酸官能基が、ホスホン酸、スルホン酸及びビススルホニルイミドからなる群から選択される、請求項15に記載のポリマー電解質。
- 前記ポリオキソメタレートが、Ti又はZr原子を介して前記ポリマーに共有結合している、請求項7〜16のいずれか一項に記載のポリマー電解質。
- 前記ポリオキソメタレートが、シラン基を介して前記ポリマーに共有結合している、請求項7〜16のいずれか一項に記載のポリマー電解質。
- 前記ポリオキソメタレートが、ホスホネート基を介して前記ポリマーに共有結合している、請求項7〜16のいずれか一項に記載のポリマー電解質。
- 共有結合したポリオキソメタレートを含む第1ペンダント基を含む、フッ素化ポリマー電解質。
- 共有結合したポリオキソメタレートを含む第1ペンダント基と、ポリオキソメタレート以外の第2の酸官能基とを含む、ポリマー電解質。
- 前記第2の酸官能基が、ホスホン酸、スルホン酸及びビススルホニルイミドからなる群から選択される、請求項21に記載のポリマー電解質。
- ポリマー電解質であって、ポリオキソメタレートがTi又はZr原子を介して前記ポリマーに共有結合している、共有結合したポリオキソメタレートを含む第1ペンダント基を含む、ポリマー電解質。
- ポリマー電解質であって、ポリオキソメタレートがホスホネート基を介して前記ポリマーに共有結合している、共有結合したポリオキソメタレートを含む第1ペンダント基を含む、ポリマー電解質。
- 請求項7〜24のいずれか一項に記載のポリマー電解質を含む、燃料電池ポリマー電解質膜。
- 請求項7〜24のいずれか一項に記載のポリマー電解質を含む、燃料電池膜電極アセンブリ。
- a)Mn及びCeからなる群から選択される遷移金属を含む、共有結合したポリオキソメタレートを含むモノマーと、
b)少なくとも一種類のコモノマーと、
を共重合する工程を含む、ポリマー電解質の製造方法。 - a)欠損型ヘテロポリ酸の結合部位として作用し得る3つ以上の官能基を含むポリマーを提供する工程と、
b)ポリオキソメタレートを該ポリマーに共有結合させる工程と、を含む、ポリマー電解質の製造方法。 - a)3つ以上のシラン基を含むポリマーを提供する工程と、
b)ポリオキソメタレートを該ポリマーのシラン基に共有結合させる工程と、を含む、請求項28に記載の方法。 - a)ホスホン酸基を含むポリマーを提供する工程と、
b)ポリオキソメタレートを該ポリマーのホスホン酸基に共有結合させる工程と、を含む、ポリマー電解質の製造方法。
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Also Published As
Publication number | Publication date |
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WO2009108222A3 (en) | 2010-03-04 |
EP2218130A2 (en) | 2010-08-18 |
WO2009108222A2 (en) | 2009-09-03 |
US8206874B2 (en) | 2012-06-26 |
EP2218130B1 (en) | 2017-04-19 |
EP3012895A3 (en) | 2016-06-01 |
JP5432167B2 (ja) | 2014-03-05 |
CN101919100B (zh) | 2014-10-01 |
CN101919100A (zh) | 2010-12-15 |
EP3012895A2 (en) | 2016-04-27 |
US20090208809A1 (en) | 2009-08-20 |
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