CN1390366A - 用于自湿润式燃料电池的膜片式电极单元及其制造方法和燃料电池组 - Google Patents
用于自湿润式燃料电池的膜片式电极单元及其制造方法和燃料电池组 Download PDFInfo
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- H01M8/10—Fuel cells with solid electrolytes
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- H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
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Abstract
本发明涉及一种用于自湿润式燃料电池的膜片式电极单元及其制造方法。此外,本发明还涉及一种自湿润式燃料电池组。所述膜片式电极单元包括一个膜片电解质,其中至少夹有一催化剂层,这样在膜片内通过反应气体H2和O2的化合反应可生成水。
Description
本发明涉及一种用于自湿润式燃料电池的膜片式电极单元及其制造方法。此外,本发明还涉及一种自湿润式燃料电池组。
燃料电池组中的每个燃料电池单元分别具有一个膜片式电极单元,该电极单元具有一个设置在中央的电解质,该电解质例如在PEM燃料电池中是一种离子交换膜片,它的主要成分中有一种硫化合物。这种化合物将水结合在膜片中,以保证有足够的质子传导能力。但在较高的工作温度和/或较高的工作压力下,反应(生成的)水却没有被足够地结合到膜片中,膜片由此因脱水而变得干燥,这尤其发生在流出反应气体的区域内。由于膜片中的质子传导能力减弱,这将会导致功率损耗。
迄今为止,为防止膜片干燥,对反应气体加湿。但对反应气体的增湿会带来这样的困难,即,必须附加采用一个加湿器。
因此人们一直致力于用不加湿的反应气体来工作,迄今为止已找到了两种解决分案:
一种是由德国专利文献DE 19844983.6(尚未公开)提供的建议,其中,通过在燃料电池单元内在电极和分布气体之间设置液体阻挡层,将反应生成的水保持在膜片式电极单元内。
另一种是由M.Watanabe在J.Elektrochem.Soc.,Vol.145 No 4,第1137页(1998)上提供的建议,其中,在膜片中保证扩散的反应气体H2和O2发生反应。按照他所建议的方法,使一种铂盐溶液在膜片的一侧扩散到膜片中,而在膜片的另一侧则使一种还原剂,例如NaBH4扩散到膜片中。这样在膜片中形成很小的铂颗粒,它们在H2和O2化合成水的反应中起到催化剂的作用。但这种方法的缺点首先是制造需要较多时间,这是因为这种制造方法会涉及一种对扩散加以适当控制的反应,该反应可使铂颗粒在整个膜片厚度上有一个分布断面。除此之外,在极端情况下,不能排除有因铂颗粒发生短路的情形。
本发明的目的在于,在将铂颗粒加入膜片中的基础上,创造一种用于自湿润式燃料电池的膜片式电极单元。它适合于大批量生产并且克服了已公知的带有加湿器的膜片式电极单元的缺点。
此外,本发明的目的还在于,提供一种制造自湿润膜片式电极单元的方法,它无需控制扩散地生成铂颗粒。最后,本发明的目的在于创造一种自湿润燃料电池组。
本发明的内容是一种用于燃料电池的膜片式电极单元,它通过获得反应气体在膜片中化合反应所生成的水来加湿。在此,膜片至少包括一个催化剂层,以供化合反应在其上进行。
此外,本发明的内容是一种制造带有催化剂层的膜片式电极单元的方法,其中,所述膜片由至少两个分膜片构成,在第一个工作步骤中,在至少一个分膜片上涂覆一催化剂层,在随后的第二个工作步骤中将另一个分膜片与第一个分膜片层叠在一起。
最后,本发明的内容是一种燃料电池组,它能自湿润,其中的每个燃料电池中包括一个膜片式电极单元。它在膜片中具有一个催化剂层。
按照一个有利的改进设计,膜片式电极单元在催化剂层之外还包括吸湿颗粒,它们例如由ZrO2,SiO2和/或TiO2等材料制成,用于存储化合反应生成的水。
按照本发明方法的另一有利设计,催化剂层在第一个分膜片上作为墨汁和/或弥散剂涂刷上。
按照本发明方法的另一有利设计,将催化剂层喷涂上。
作为催化剂层可以采用纯铂或一种铂碳化合物或其它任意一种可使H2和O2有控制地在膜片内化合的催化剂。催化剂层定位在至少两层结构的膜片内部,这样可以避免铂颗粒的分布断面和公知的Watanabe式膜片中一样。
作为燃料电池可以是PEM(聚合物-电解质-膜片)燃料电池,或者其它任意一种其电解质需要液态水来传导的燃料电池。
所装入电解质的数量和类型(在碳材上镀铂或纯铂等)视电池单元的水需求量而定,并视不同的运行系统有所变化。在水的需求量较大时,膜片厚度可以减小和/或装入具有更高铂含量的催化剂和/或更多的吸湿颗粒。可以自由选择催化剂装入膜片内的位置,尤其是可在存在最大干燥问题的位置处装入催化剂。
在此,与按照Watanabe所述装入的催化剂不同,此处的“催化剂层”是一种局部化的(lokalisierte)层。它不仅可以是一种连续贯通层,也可以是一种纹理化层,亦即一种“网孔状”层,它例如可以通过印刷方法涂覆上。在极端的情况下,催化剂层仅仅是处在膜片中的一个或多个平面上的任意尺寸和浓度的“催化剂孤岛”。
下面借助实施例对本发明的膜片式电极单元及其制造方法进行详细说明:
为制造一种自润湿膜片,在第一个分膜片(例如为Nafion膜片1135(87μm))的一侧涂刷、喷涂或压印一种墨汁和/或弥散液,它们由铂的质量百分比为1%的碳-催化剂(40%Pt)和质量百分比为15%的Nafion溶液(5%溶液)组成。当墨汁在80℃下干燥后,将第二个分膜片(例如为Nafion膜片112(50μm))压紧在第一个分膜片的涂层侧。之后例如通过将一个铂制阳极热压在已层叠制好的膜片一侧,将一个铂制阴极热压在另一侧上,制造出膜片式电极单元。
第一个涂层分膜片也还可以借助液态墨汁和/或弥散液和/或纯铂粉与第二个或更多个分膜片(例如通过湿粘接)湿层叠起来。该层叠和/或粘接有时候可受到热压支持。膜片在已制好的层叠状态下干燥。
在将两个分膜片结合成膜片式电极单元之前,在这两个分膜片上涂覆催化剂层。
通过使催化剂层在膜片式电解质中分层所制造出的膜片式电极单元,使得掺合铂颗粒这一方案适用于工业上大批量生产。所述膜片式电极单元包括一个膜片式电解质,其中至少有一层催化剂,这样在膜片内通过使反应气体H2和O2化合反应可生成水。
Claims (4)
1.一种用于燃料电池的膜片式电极单元,它通过获取反应气体在膜片中化合反应所生成的水来加湿,其中,该膜片包括至少一个局部化的层,所述化合反应可在其上进行。
2.如权利要求1所述的膜片式电极单元,它添加有吸湿颗粒。
3.一种制造带有催化剂层的膜片式电极单元的方法,其中,所述膜片由至少两个分膜片构成,在第一个工作步骤中,在至少一个分膜片上涂覆一催化剂层,在随后的第二个工作步骤中将另一个分膜片与第一个分膜片层叠在一起。
4.一种燃料电池组,它能自湿润,其中的每个燃料电池包括一个膜片式电极单元,该电极单元在膜片中具有一个催化剂层。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19917812.7 | 1999-04-20 | ||
DE19917812A DE19917812C2 (de) | 1999-04-20 | 1999-04-20 | Membranelektrodeneinheit für eine selbstbefeuchtende Brennstoffzelle, Verfahren zu ihrer Herstellung und Brennstoffzellenbatterie mit einer solchen Membranelektrodeneinheit |
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CN1390366A true CN1390366A (zh) | 2003-01-08 |
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CN00808005A Pending CN1390366A (zh) | 1999-04-20 | 2000-04-20 | 用于自湿润式燃料电池的膜片式电极单元及其制造方法和燃料电池组 |
Country Status (7)
Country | Link |
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US (1) | US20020058172A1 (zh) |
EP (1) | EP1175706A2 (zh) |
JP (1) | JP2002542590A (zh) |
CN (1) | CN1390366A (zh) |
CA (1) | CA2371129A1 (zh) |
DE (1) | DE19917812C2 (zh) |
WO (1) | WO2000063989A2 (zh) |
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CN110114512A (zh) * | 2016-12-22 | 2019-08-09 | 庄信万丰燃料电池有限公司 | 具有层合结构的催化剂涂覆的膜 |
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DE10145875B4 (de) * | 2001-09-18 | 2010-09-16 | Daimler Ag | Membran-Elektroden-Einheit für eine selbstbefeuchtende Brennstoffzelle |
US6824909B2 (en) * | 2002-07-09 | 2004-11-30 | General Motors Corporation | Low-humidification and durable fuel cell membrane |
US7112386B2 (en) * | 2002-09-04 | 2006-09-26 | Utc Fuel Cells, Llc | Membrane electrode assemblies with hydrogen peroxide decomposition catalyst |
DE10250355A1 (de) * | 2002-10-29 | 2004-05-13 | Volkswagen Ag | Verfahren zum Betreiben eines Brennstoffzellensystems bei Umgebungstemperaturen unter 0°C und Brennstoffzellensystem |
JP5021885B2 (ja) * | 2003-11-13 | 2012-09-12 | 東芝燃料電池システム株式会社 | 燃料電池 |
JP2006040703A (ja) * | 2004-07-27 | 2006-02-09 | Aisin Seiki Co Ltd | 固体高分子型燃料電池の触媒担持方法、膜電極接合体 |
US8101317B2 (en) * | 2004-09-20 | 2012-01-24 | 3M Innovative Properties Company | Durable fuel cell having polymer electrolyte membrane comprising manganese oxide |
US7572534B2 (en) * | 2004-09-20 | 2009-08-11 | 3M Innovative Properties Company | Fuel cell membrane electrode assembly |
EP1831940A4 (en) | 2004-12-28 | 2009-06-17 | Utc Fuel Cells Llc | MEMBRANE ELECTRODE ASSEMBLIES WITH A HYDROGEN PEROXIDE DECOMPOSITION CATALYST |
US8652705B2 (en) * | 2005-09-26 | 2014-02-18 | W.L. Gore & Associates, Inc. | Solid polymer electrolyte and process for making same |
US7622217B2 (en) * | 2005-10-12 | 2009-11-24 | 3M Innovative Properties Company | Fuel cell nanocatalyst |
US8628871B2 (en) | 2005-10-28 | 2014-01-14 | 3M Innovative Properties Company | High durability fuel cell components with cerium salt additives |
US8367267B2 (en) * | 2005-10-28 | 2013-02-05 | 3M Innovative Properties Company | High durability fuel cell components with cerium oxide additives |
DE102006012907A1 (de) * | 2006-03-10 | 2007-09-13 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Elektroden-Membran-Einheit und Brennstoffzelle |
DE102006012908A1 (de) * | 2006-03-10 | 2007-09-13 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Elektroden-Membran-Einheit und Brennstoffzelle |
EP2036157A1 (en) * | 2006-06-12 | 2009-03-18 | ReVolt Technology Ltd | Metal-air battery or fuel cell |
US20080096061A1 (en) * | 2006-06-12 | 2008-04-24 | Revolt Technology Ltd | Metal-Air Battery or Fuel Cell |
US8815468B2 (en) * | 2009-06-24 | 2014-08-26 | Ford Global Technologies, Llc | Layered electrodes and membrane electrode assemblies employing the same |
CN102738482B (zh) | 2011-04-01 | 2015-05-20 | 香港科技大学 | 自增湿膜和自增湿燃料电池及其制备方法 |
US9048471B2 (en) | 2011-04-01 | 2015-06-02 | The Hong Kong University Of Science And Technology | Graphene-based self-humidifying membrane and self-humidifying fuel cell |
DE102014118892A1 (de) | 2014-12-17 | 2016-06-23 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Kohlenstoffmembran, Verfahren zur Herstellung von Kohlenstoffmembranen und deren Verwendung |
DE102016102088A1 (de) | 2016-02-05 | 2017-08-10 | Volkswagen Ag | Membran, Membran-Elektroden-Einheit, Brennstoffzelle und Verfahren zur Herstellung einer Membran |
ES2968670T3 (es) | 2016-08-25 | 2024-05-13 | Proton Energy Sys Inc | Conjunto de electrodos de membrana y método de fabricación del mismo |
US11560632B2 (en) * | 2018-09-27 | 2023-01-24 | 3M Innovative Properties Company | Membrane, membrane electrode assembly, and water electrolyzer including the same |
DE102020102390A1 (de) | 2020-01-31 | 2021-08-05 | Audi Aktiengesellschaft | Brennstoffzelle und Brennstoffzellensystem |
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GB9822576D0 (en) * | 1998-10-16 | 1998-12-09 | Johnson Matthey Plc | Membrane |
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1999
- 1999-04-20 DE DE19917812A patent/DE19917812C2/de not_active Expired - Fee Related
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2000
- 2000-04-20 JP JP2000613019A patent/JP2002542590A/ja not_active Withdrawn
- 2000-04-20 EP EP00940142A patent/EP1175706A2/de not_active Withdrawn
- 2000-04-20 CN CN00808005A patent/CN1390366A/zh active Pending
- 2000-04-20 WO PCT/DE2000/001244 patent/WO2000063989A2/de not_active Application Discontinuation
- 2000-04-20 CA CA002371129A patent/CA2371129A1/en not_active Abandoned
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2001
- 2001-10-22 US US10/007,392 patent/US20020058172A1/en not_active Abandoned
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CN110114512A (zh) * | 2016-12-22 | 2019-08-09 | 庄信万丰燃料电池有限公司 | 具有层合结构的催化剂涂覆的膜 |
CN110114512B (zh) * | 2016-12-22 | 2021-08-10 | 庄信万丰燃料电池有限公司 | 具有层合结构的催化剂涂覆的膜 |
CN113529121A (zh) * | 2016-12-22 | 2021-10-22 | 庄信万丰燃料电池有限公司 | 具有层合结构的催化剂涂覆的膜 |
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WO2000063989A3 (de) | 2001-02-22 |
US20020058172A1 (en) | 2002-05-16 |
WO2000063989A2 (de) | 2000-10-26 |
EP1175706A2 (de) | 2002-01-30 |
CA2371129A1 (en) | 2000-10-26 |
DE19917812A1 (de) | 2000-10-26 |
DE19917812C2 (de) | 2002-11-21 |
JP2002542590A (ja) | 2002-12-10 |
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