CN1147018C - 制备吸酸聚苯并咪唑纤维的织物的方法、聚苯并咪唑织物及包含该织物的燃料电池 - Google Patents

制备吸酸聚苯并咪唑纤维的织物的方法、聚苯并咪唑织物及包含该织物的燃料电池 Download PDF

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CN1147018C
CN1147018C CNB988072440A CN98807244A CN1147018C CN 1147018 C CN1147018 C CN 1147018C CN B988072440 A CNB988072440 A CN B988072440A CN 98807244 A CN98807244 A CN 98807244A CN 1147018 C CN1147018 C CN 1147018C
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F��J��ŷŵ��ͼ
F·J·欧诺拉图
ɣɭ
M·J·桑森
D·W·金
S·M·弗兰奇
￨
F·马里卡
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Abstract

一种制备用作为燃料电池或蓄电池电解质的聚苯并咪唑(PBI)织物的方法，此方法是将已磺化或未磺化的PBI织物浸泡在酸性溶液中，藉以使PBI织物的纤维因酸性溶液而膨胀、及将织物烘干以移去残余的水或甲醇并将酸浓缩。

Description

制备吸酸聚苯并咪唑纤维的织物的 方法、聚苯并咪唑织物及包含该织物的燃料电池
技术领域
本发明涉及制备在燃料电池中用作聚合物电解质的织物。
背景技术
燃料电池可用各种各样的电解质，燃料及操作温度以各种方式作成各种构型。例如，像氢或甲醇之类的燃料可以直接提供给燃料电池的电极。或者，燃料如甲烷或甲醇可在电池本身外面转化成富含氢的气体混合物，然后提供给燃料电池。虽然在某些用途中，氧是借过氧化氢分解或自低温储藏系统而得，但在大多数的燃料电池中空气是氧气的来源。
虽然理论上电解质，燃料，氧化剂，温度等有无数种的组合，但实际系统包括用氢或肼作为燃料源及纯氧作为氧化剂的固聚合物电解质系统。掺杂着强酸的聚苯并咪唑(PBI)是一个用于电解质系统的适当固体聚合物的实例。
本领域已知用强酸使聚苯并咪唑(PBI)密实薄膜吸取以作成质子导介质。最近，美国专利第5,525,436号，(1996年6月11日颁予专利)描述了在PBI中掺杂强酸例如磷酸或硫酸以致形成一个单一相系统-亦即，酸溶于聚合物中的方法。
即使由于本领域有所进展，合适聚合物电解质物质的性能，高成本和加工性能，就燃料电池的聚合物介质而言，仍是燃料电池构造上的重要考虑。本领域仍需要用于制备燃料电池和燃料电池组件的新方法和材料。
发明内容
一方面，本发明提供一种制备用于燃料电池中作为电解液的聚合织物，较佳PBI织物的方法。在一实施方案中，该方法包含将未磺化或已磺化PBI纤维所组成的织物浸泡在酸性溶液中。织物的孔隙是由于吸入酸的纤维膨胀而关闭。为了使隔膜气密并阻止气体在燃料电池运作时流动穿过织物，关闭这些孔隙是必须的。
因此，本发明提供一种制造吸酸聚苯并咪唑织物的方法，包括以下几个步骤：提供包含PBI纤维而纤维间有孔隙的织物；及将织物浸泡在包含酸和溶剂的酸性溶液中，一段足够的时间，以使该纤维织物吸入该酸性溶液，藉以使纤维膨胀而关闭纤维间的孔隙，其中所述酸是自磷酸、硫酸、三氟乙酸、甲磺酸及其混合物所组成的组中所选出。
另一方面，本发明提供由聚合物纤维的纤维织物，较佳PBI磺化或未磺化纤维所组成的织物，该织物的特征为具有高酸含量及令人满意的电化学和/或机械性能。“高酸含量”是指织物含有介于约40至约95重量％的吸入酸。这些织物可以用标准的编织和针织方法制备。PBI织物的特征可为比先有技术生产出的织物具有更好的保留酸的能力。
还有另一方面，本发明提供一种包含根据本发明的磺化或未磺化吸酸PBI织物的燃料电池。
本发明的另外一些方面与优点将在下面本发明优选实施方案的详细说明中加以进一步说明。
具体实施方式
本发明提供一种对本领域制备用在燃料电池中作为电解质的聚合织物的方法及对织物本身的改良。一般而言，根据本发明，包含聚合纤维的织物是以酸溶液供其吸或浸泡在酸中直到织物含有约40至约95重量％的酸为止。
根据本发明，构成可用于本发明的织物的聚合纤维包括，但不限于，聚苯并咪唑(PBI)、聚(吡啶)、聚(嘧啶)、聚咪唑、聚苯并咪唑、聚苯并噻唑、聚苯并噁唑、聚噁二唑、聚喹喔啉、聚噻二唑、聚四吖芘及磺化，未磺化PBI和/或这些聚合纤维的混合物。
目前，较佳的织物含有PBI纤维，其可磺化或未磺化。本发明人等发现，由于PBI是一种碱性聚合物，它对酸有亲合力且将在极端状态下保留酸。特定言之，磺化织物，是一种交联织物，将比未交联织物保留额外量的酸且机械性能降低更少。由于吸入的速度和制造出的织物的形态，所以本发明的方法是很有利的。然而，即使有此优越性，本领域技术人员也可轻易的以包含其他聚合纤维的其他织物取代。
适当的织物可以容易地从各种商业来源获得，优选经过编织的织物。然而，如此处所述，能吸取酸的针织或不织织物也可以使用。
目前，本发明中所用织物的纤维宜为小直径，即，直径在10克/9000米到500克/9000米(约10至约500旦尼尔)的范围。更佳为，纤维的直径为约20克/9000米(20旦尼尔)。需要小尺寸的纤维，所得织物的厚度才会在1.27×10-5-1.27×10-4米(0.5至5密耳)的范围内。
目前较佳的织物是一种经涂覆的织物，其是如同时提出申请，同在审查中的美国专利案“制造用于燃料电池的聚苯并咪唑糊及凝胶的方法”中所述制备，并将该申请案并于此以供参考。该聚合物织物，较佳为可吸入酸的PBI，附有介于0.1微米至100微米(较佳10～30微米)的PBI糊或凝胶涂层，且含有介于70-99.9重量％，较佳约95～99重量％的酸。PBI糊或凝胶是由PBI聚合物片和酸溶液混合而制备，酸溶液可让聚合物膨胀而形成在室温下具糊状或凝胶状稠度的基体。这种方法已详细说明于上面所述并于本文供参考的专利申请案中。PBI糊或凝胶涂层是使用常规方法施涂。经涂膜织物的制备已详细说明于上述申请案中。
一旦选出合适的织物，即将织物浸入酸溶液中足够时间以使酸被吸入而不失去织物状的形态。目前，较佳的酸溶液包括溶于溶剂中的磷酸、硫酸、三氟乙酸、甲磺酸及其混合物。磷酸用于本发明未磺化纤维特佳。目前，最佳的酸溶液包括磷酸和水或甲醇。然而，此酸及其他选用的酸的其他适当溶剂如二甲基乙酰胺和N-甲基吡咯烷酮(NMP)，或这些溶剂与水及/或甲醇的混合物，已为本领域技术人员所知且可轻易决定。
酸溶液宜含有约5至约100重量％的酸和约0至约95重量％的溶剂。在目前的一较佳实施方案中，酸溶液含有约50重量％酸及50重量％水或甲醇。
在本发明方法的一实施方案中，织物是浸入酸浴中，在另一实施方案中，织物和酸是在合适的混合容器中混合。这种混合可以在室温下进行，但在酸凝固点和沸点间的任何温度都可以使用。
视情况而定，将混合物加热以能使织物吸酸比在室温下更快进行。宜将混合物加热至介于约30℃至约200℃之间。更佳的温度范围为在约50℃至约90℃之间。加热宜适当地进行约30秒至约8小时。所要加热时间持续约5分钟至2小时。就挑选的织物中纤维而言，例如，由未磺化PBI纤维构成的织物可吸入少于约65％至约70％的酸。相对而言，由磺化PBI纤维构成的织物是交联的，可以吸入大于约65％至约70％的酸而且还保持令人满意的机械性能。
所得经酸浸泡的织物在室温至约200℃，较佳在约80℃至约180℃下烘干，以除去残余溶剂如二甲基乙酰胺、N-甲基吡咯烷酮、水、和/或甲醇。此一干燥步骤将酸捕住而形成吸取酸的织物。织物中的孔隙是藉吸取酸的纤维膨胀而关闭，它使织物变成气密(亦即，气体传输的有效障壁)和阻止气体在燃料电池运作时流动通过织物。
根据本发明的方法，所得吸取酸的织物含有高酸含量，其量占吸酸织物重量的约40％至约95％。一般而言，为使织物在燃料电池中充分发挥作电解质的功能，需要约50重量％或更多的酸。更佳为织物含有约50％至约75％的酸，以吸酸织物的重量为准。所得织物吸入的酸数量取决于，且可藉纤维、织物、编织织物中编织的紧密度、温度、浸泡时间及溶液中的酸浓度控制。以本说明书内容而言，本领域技术人员可以容易地作出这些选择和修改本发明，而仍在本发明之内。本发明方法的一个优点在于酸吸取是在短时间范围内发生，而先有技术的方法则需用10至72小时。这个优点反应在电解质成本降低性能又更佳。
本发明的吸酸织物特别适合用在燃料电池中作为电解液。本发明的吸酸织物由于其为织物形式很容易处理和无需在电解质中使用溶剂。再者，已发现，本发明的吸酸聚合物织物保留酸而因此电解能力的时间比先有技术的电解质更长久。这在本发明的吸酸织物尤其如此。因此，本发明更进一步提供含有本发明吸酸织物的燃料电池。
以下实例将用PBI作为代表性聚合物说明本发明的较佳组合物和方法。这些实例仅是例证性而不限制本发明的范围。
实例1-未磺化PBI吸酸织物
将未磺化PBI浸在含有85重量％磷酸的酸性水溶液中。酸浸是在温度约21℃下进行约24小时。然后，在约120℃下将织物烘箱烘干约12小时以除去残余的水。所得吸酸织物含有约50重量％的酸。
实例2-磺化PBI吸酸织物
将磺化PBI织物浸在含有85重量％磷酸的酸性水溶液中。酸浸是在温度约60℃下进行浸约4小时。然后，在约120℃下将织物烘箱烘干约12小时以除去残余的水。所得吸酸织物含有约65重量％的酸。
实例3-吸酸和经涂膜的PBI
根据本发明的吸酸织物基本上是如上述实例1所述制备。然而，吸酸PBI织物在用于电极总成之前也予以涂膜。简言之，这种织物是如下制备。
用下面方法制备的PBI糊涂覆实例1的吸酸PBI织物的两边。把PBI聚合物(1克)加入到低速混合机中含有117克85重量％磷酸和15％水的溶液中。在升高温度下，即在100℃下将混合物搅拌以除去残余的水直至得到均一糊。所得糊或凝胶含有约99重量％的酸。所得每一边涂层的厚度为约2.54×10-5米(1密耳)。在电极总成中，与电极的接触是藉凝胶/糊涂层的存在促进而产生优越的燃料电池性能。
实例4-隔膜电极总成
将由未磺化PBI构成的织物浸泡在含85重量％磷酸的酸性水溶液中。此一酸泡是在温度约60℃下进行约4小时。然后，织物可在约150℃下烘干6小时以从酸处理中除去残余的水。或者，把织物制造成隔膜电极总成，然后在燃料电池中就地干燥。所得吸酸织物含有约65重量％的酸。
然后制造隔膜电极总成，其法是将吸酸织物放在两个电极之间，并在温度130℃及压力50公斤/平方厘米下热压结一段约30秒的时间。然后把隔膜电极放入燃料电池中。在典型的0.7伏特操作条件下，所得电流密度及功率密度分别为约450毫安/平方厘米及315毫瓦特/平方厘米。
本发明的许多修正和变异已包括在上述已验证的说明书中，且预期本领域技术将很明白。据信，本发明组合物及方法的这些修正及变化将涵盖于后附权利要求书的范围内。

Claims (13)

1.一种制造吸酸聚苯并咪唑织物的方法，包括以下几个步骤：提供包含PBI纤维而纤维间有孔隙的织物；及将织物浸泡在包含酸和溶剂的酸性溶液中，一段足够的时间，以使该纤维织物吸入该酸性溶液，藉以使纤维膨胀而关闭纤维间的孔隙，其中所述酸是自磷酸、硫酸、三氟乙酸、甲磺酸及其混合物所组成的组中所选出。
2.根据权利要求1的方法，其中该溶剂是自水、甲醇、二甲基乙酰胺、N-甲基吡咯烷酮，及其混合物所组成的组中所选出。
3.根据权利要求2的方法，进一步包含将织物烘干以除去残余水及其他溶剂而使酸浓缩至所需程度。
4.根据权利要求1的方法，其中在该织物吸取的酸性溶液为介于40至95重量％之间，以该吸酸织物的总重为准。
5.根据权利要求1的方法，其中在该织物吸取的酸性溶液为介于50至75重量％之间，以该吸酸织物的总重为准。
6.根据权利要求1的方法，其中该酸性溶液进一步包含介于5至100重量％的酸。
7.根据权利要求6的方法，其中该酸性溶液包含50％的酸和50％的溶剂。
8.根据权利要求1的方法，其中该织物是由未磺化聚苯并咪唑纤维所形成。
9.根据权利要求1的方法，其中该织物是由磺化聚苯并咪唑纤维所形成。
10.一种聚苯并咪唑织物，包含含量介于40至95重量％的酸。
11.根据权利要求10的织物，其中该织物是由未磺化聚苯并咪唑纤维所形成。
12.根据权利要求10的织物，其中该织物是由磺化聚苯并咪唑纤维所形成。
13.一种包含聚苯并咪唑织物的燃料电池，该聚苯并咪唑织物包含含量介于40至95重量％的酸。
CNB988072440A 1997-07-16 1998-05-19 制备吸酸聚苯并咪唑纤维的织物的方法、聚苯并咪唑织物及包含该织物的燃料电池 Expired - Fee Related CN1147018C (zh)

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