JP4920889B2 - 膜電極接合体、高分子膜、固体高分子形燃料電池、膜電極接合体の製造方法および固体高分子形燃料電池の製造方法 - Google Patents
膜電極接合体、高分子膜、固体高分子形燃料電池、膜電極接合体の製造方法および固体高分子形燃料電池の製造方法 Download PDFInfo
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- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- H—ELECTRICITY
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- H01M8/0289—Means for holding the electrolyte
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- H—ELECTRICITY
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- 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
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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- 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
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
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- H—ELECTRICITY
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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Description
本発明は、膜電極接合体(membrane-electrode assembly, Membran-Elektroden-Einheit)、膜電極接合体用の高分子膜、および250℃までの動作温度範囲の固体高分子形燃料電池(polymer electrolyte fuel cells, Polymerelektrolyt-Brennstoffzelle)、ならびにこれらの製造方法に関する。
本発明の目的は、固体高分子形燃料電池用の膜電極接合体(MEA)、MEAのための高分子膜および、上記に記載の欠点を克服でき、50℃を越える動作温度範囲において高い出力を有する固体高分子形燃料電池を利用可能にすること、ならびに、これらを製造するための容易に実行できる方法を提案することである。
この目的は、独立クレーム1、14、18、21および27の規定により達成される。本発明の有利な態様は従属クレームに規定されている。
本発明の膜電極接合体は、少なくとも2つのガス拡散平面電極と、その間に挟まれた、少なくとも1種の塩基性ポリマーを有する平面高分子膜とからなる;該高分子膜はまた、ガス拡散電極に負荷されてガス拡散電極が高分子膜のためのドーパント溜めを形成するための、ドーパントからなる。高分子膜は、ガス拡散電極に、圧力と温度の作用の後にドーパントを介してプロトン伝導性の様式で固定して結合され、ドーピング状態において25℃以上の動作温度で、少なくとも0.1S/mの伝導率を有する。MEAは、250℃までの動作温度を有する固体高分子形燃料電池に好適である。
本発明の他の好ましい態様においては、ドーパントは強多塩基無機酸であり、リン酸が特に好ましい。
Xは、アミノ基または酸素原子またはイオウ原子を示してよく、Zは、酸素またはイオウ原子を表してよい。
さらに塩基性ポリマーは、米国特許第5,599,639号に記載されているようにスルホン酸化またはホスホン酸化することができるが、ホスホン酸化が好ましい。これは、MEAからのドーパントの放出を防止するのに適切である。1種または2種以上の平面構造形態の塩基性材料はまた、1種または2種以上の塩基性ポリマーに加えて、セラミクスなどの他の物質を含むこともできる。
含むが、リン酸(V)が好ましい。これらの遊離の酸をドーパントとして用いることは、100℃を越える燃料電池の動作温度において好ましい。
高分子膜の架橋は、好ましくは、高分子膜注型溶液に添加される架橋剤によって実施される。架橋剤は、共有結合を形成するために用いられる、ポリマー(単数または複数)と反応可能な少なくとも2個の官能基を有する全ての化合物を含んでよい。本発明の好ましい態様によれば、用いる架橋剤は、WO 00/44816 A1に記載のように、エポキシ基および/またはイソシアネート基を有する。分子中に少なくとも2個のエポキシ基を有する化合物が好ましい。1,4−ブタンジオールジグリシジルエーテル(III)を架橋剤として用いるのが特に好ましい。
好ましい態様においては、工業機械延伸による高分子膜生成のステップの間に、同時に架橋され可塑化された高分子膜を用いる。
A.塩基性ポリマーと高分子膜の重量の60%〜120%のドーパント含有量まで、前記ガス拡散平面電極にドーパントを含浸させること、
B.含浸させたガス拡散電極の間に、高分子膜を挟むこと、
C.ステップBで挟んだものを、2つのプレス板の間に配置すること、
D.100℃〜250℃の温度および1bar〜5barの圧力で、5秒〜60分間、前記配置したものを加熱プレスすること、
を含む、前記方法に関する。
ガス拡散電極(単数または複数)に含浸させるドーパントの量は、好ましくは、ガス拡散電極(単数または複数)と高分子膜との間のドーパント交換の質量輸送平衡に達した後に、高分子膜で少なくとも0.1S/m(25℃)の伝導率が達成されるように選択される。
A.塩基性ポリマー重量の60%〜120%のドーパント含有量まで、ガス拡散電極にドーパントを含浸させること、
B.ドーピングされたガス拡散電極の間に、高分子膜を挟むこと、
C.ステップBで挟んだものを、固体高分子形燃料電池の2つのプレスした双極板の間に配置すること、
D.固体高分子形燃料電池の高分子膜−電極層に50℃〜250℃の温度で接触圧力をかけ、燃料電池を反応ガスに少なくとも1分〜10時間の間、好ましくは1分〜60分間暴露すること、
によって製造される。
ポリ電解質燃料電池の起動操作の第1相において、含浸されたケース分散電極と高分子膜との間で、ドーパントが再分配され、高分子膜の伝導率が少なくとも25℃の温度において0.1S/mより高い値に上昇する。同時に、ガス拡散電極の高分子膜へのプロトン伝導性結合が生じる。
本発明を以下の例および図1と図2に基づいて説明するが、これは本発明の範囲を限定するものではない。
例1
ポリマー注型溶液の製造
0.86dL/gの固有粘度を有するPBI216gを、200℃の加圧反応装置内で3時間攪拌することにより、DMAc684gに溶解する。得られた溶液を冷却し、間隙径が20μmのGoettingen、Sartorius AGからのSartopure(登録商標)PP2(P9)フィルターカプセルを通してろ過し、ガス抜きする。溶液は24%の固体含有量を有する。
例2
高分子膜の製造
例3
引張り応力の測定
例4
架橋の程度の決定
例5
膜電極接合体の製造
例6
例5による膜電極接合体の電力パラメータの決定
例7
架橋剤とドーパントを含有するポリマー注型溶液の製造
例8
高分子膜の製造
例9
引張り応力の測定
例10
架橋の程度の決定
例11
膜電極接合体の製造
例12
例11による膜電極接合体の電力パラメータの決定
Claims (17)
- 250℃までの動作温度を有する固体高分子形燃料電池用の膜電極接合体であって、
2つのガス拡散平面電極と、該2つのガス拡散平面電極の間に挟まれた少なくとも1種の塩基性ポリマーを有する高分子膜と、ドーパントとから少なくともなり、
ここで、前記ガス拡散電極は、前記高分子膜のためのドーパント溜めを形成するように、前記高分子膜中の塩基性ポリマー重量に対して60%〜120%の含有量のドーパントが負荷されており、それによって前記高分子膜は、固体高分子形燃料電池の動作条件下で、ドーパントの前記ガス拡散電極からの前記高分子膜への再分配により、固定されるようにまたプロトン伝導性の様式でガス拡散電極に結合され、ドーピング状態において25℃以上の温度で少なくとも0.1S/mの伝導率を有する、
前記膜電極接合体。 - 塩基性ポリマーが、ポリベンズイミダゾール、ポリピリジン、ポリピリミジン、ポリイミダゾール、ポリベンズチアゾール、ポリベンズオキサゾール、ポリオキサジゾール、ポリキノキサリン、ポリチアジアゾール、ポリ(テトラアザピレン)からなる群、および/またはこの群の2種もしくは3種以上の代表物のコポリマーもしくは混合物、から選択されることを特徴とする、請求項1に記載の膜電極接合体。
- 少なくとも1種の塩基性ポリマーが、ポリベンズイミダゾールであることを特徴とする、請求項1または2に記載の膜電極接合体。
- 高分子膜が、工業機械延伸により製造される乾燥非ドーピング高分子膜であることを特徴とする、請求項1〜3のいずれかに記載の膜電極接合体。
- 高分子膜が、多官能性架橋剤との反応により架橋されていることを特徴とする、請求項4に記載の膜電極接合体。
- 架橋剤が、エポキシ基および/またはイソシアネート基を含むことを特徴とする、請求項5に記載の膜電極接合体。
- 高分子膜が、40重量%までの可塑剤による可塑化高分子膜であることを特徴とする、請求項1〜6のいずれかに記載の膜電極接合体。
- 可塑剤が、少なくとも二塩基酸と有機化合物との反応生成物であることを特徴とする、請求項7に記載の膜電極接合体。
- 前記有機化合物が、リン酸ジエステルであることを特徴とする、請求項8に記載の膜電極接合体。
- リン酸ジエステルが、ジ−(2−エチルヘキシル)リン酸エステルおよび/またはジフェニルリン酸エステルであることを特徴とする、請求項9に記載の膜電極接合体。
- ドーパントが、強多塩基無機酸であることを特徴とする、請求項1に記載の膜電極接合体。
- 酸が、リン酸であることを特徴とする、請求項11に記載の膜電極接合体。
- 双極板の間に配置された請求項1に記載の膜電極接合体を有する、250℃までの動作温度のための固体高分子形燃料電池。
- 2つのガス拡散平面電極と、その間に挟まれた、少なくとも1種の塩基性ポリマーおよびドーパントを有する高分子膜とからなる、250℃までの動作温度を有する固体高分子形燃料電池用の、膜電極接合体の製造方法であって、以下のステップ:
A.高分子膜中の塩基性ポリマー重量に対して60%〜120%のドーパント含有量まで、前記ガス拡散電極にドーパントを含浸させること、
B.含浸させたガス拡散電極の間に、前記高分子膜を挟むこと、
C.挟んだものを、2つのプレス板の間に配置すること、
D.50℃〜250℃の温度および1barより大きい圧力で、5秒〜60分間、前記配置したものを加熱プレスすること、
を有する、前記方法。 - ステップA〜Dを連続プロセスで行うことを特徴とする、請求項14に記載の膜電極接合体の製造方法。
- 2つのガス拡散平面電極と、少なくとも1種の塩基性ポリマーおよびドーパントを有し該電極間に挟まれた高分子膜とからなる、請求項1〜12のいずれかに記載の膜電極接合体を有する、250℃までの動作温度の固体高分子形燃料電池の製造方法であって、以下のステップ:
A.塩基性ポリマー重量に対して60%〜120%のドーパント含有量まで、前記ガス拡散電極にドーパントを含浸させること、
B.前記ドーピングされたガス拡散電極の間に、前記高分子膜を挟むこと、
C.ステップBで挟んだものを、固体高分子形燃料電池の2つの双極板の間に配置すること、
D.前記燃料電池内の挟まれた高分子膜−電極に、50℃〜250℃の温度で接触圧力をかけ、前記燃料電池を反応ガスに1分〜10時間の間暴露すること、
を含む、前記方法。 - 水素および空気を反応ガスとして用いることを特徴とする、請求項16に記載の固体高分子形燃料電池の製造方法。
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DK1593172T4 (da) | 2018-10-22 |
DK1722435T3 (da) | 2012-06-25 |
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DK1593172T3 (da) | 2007-11-12 |
JP2006513544A (ja) | 2006-04-20 |
EP1722435B1 (de) | 2012-05-16 |
EP1593172A2 (de) | 2005-11-09 |
CN1729590A (zh) | 2006-02-01 |
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WO2004066428A2 (de) | 2004-08-05 |
ATE367658T1 (de) | 2007-08-15 |
EP1722435A1 (de) | 2006-11-15 |
AU2003300536A8 (en) | 2004-08-13 |
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CN1729590B (zh) | 2010-05-05 |
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US7682722B2 (en) | 2010-03-23 |
US20070087244A1 (en) | 2007-04-19 |
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