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CN101771153A - 电化学电池的复合膜 - Google Patents

电化学电池的复合膜 Download PDF

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CN101771153A
CN101771153A CN200810205082A CN200810205082A CN101771153A CN 101771153 A CN101771153 A CN 101771153A CN 200810205082 A CN200810205082 A CN 200810205082A CN 200810205082 A CN200810205082 A CN 200810205082A CN 101771153 A CN101771153 A CN 101771153A
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翟峻
顾志军
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Jiangsu Qingneng New Energy Technology Co., Ltd.
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QINGNENG FUEL CELL TECHNOLOGY Co Ltd SHANGHAI
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Abstract

本发明公开了一种电化学电池的复合膜(1)，也就是一种燃料电池或者电解系统，所述的复合膜包含一个具有原纤维(3)多微孔结构的垫子(2)，并且还包含一种填充垫子的多微孔结构中的孔洞的离聚物(5)，允许离子通过复合膜进行的交换，所述的原纤维(3)由膨体聚四氟乙烯(ePTFE)组成，并且被一层聚合物(10)覆盖，尤其是聚酰亚胺或者THV。

Description

电化学电池的复合膜
技术领域
本发明涉及一种电化学电池的复合膜，特别是燃料电池或者电解系统的复合膜，其包含一个具有原纤维多微孔结构的垫子；其由膨体聚四氟乙烯(ePTFE)和一种填充垫子的多微孔结构的孔洞的离聚物组成；其能允许离子通过该膜进行交换。
背景技术
上述复合膜由专利US 2002/0011684 A1报道过。当拉伸聚四氟乙烯(PTFE)时，根据拉伸的方向，得到的产品在不同方向上会有不同的抗张强度。这使得膜具有非均匀特性。PTFE极其疏水并且具有高度的机械不稳定性。这两点使得将离聚体加到ePTFE中比较困难。因而要把离聚物材料注入到多微孔结构中，就不得不加入表面活性剂，否则多微孔结构的湿润性很差，这种注入就会不完全。
专利US 4,954,388公开了一种多层复合膜，它含有一层连续的离子交联聚合物和一层由织物加固的ePTFE，所述的织物由含氟聚合物的原纤维组成。这种多层结构导致复合膜的厚度过大。
发明内容
本发明的目的之一是提供一种在各个方向上具有均匀性的、高的抗张强度的薄的复合膜，所述的膜在制备时不需要使用或使用较少的表面活性剂。
为达到此目的，本发明的复合膜的特征在于垫子的多微孔结构的原纤维被一层聚合物覆盖，这种聚合物优选聚酰亚胺或含氟聚合物，其中后者优选为四氟乙烯、六氟丙烯和偏二氟乙烯(THV)的三元共聚物。
所述的膜的厚度基本和单层垫子的厚度相当。所述的覆盖层起加固的作用，其使各个方向上都具有高的抗张强度。如果选用一种具有良好湿润性的聚合物，在将离聚物应用到垫子的过程中就可以减少或者不使用表面活性剂，由此提高加工速度，并且如果需要，在应用离聚物之前，离聚物溶液中的水分含量可以更高。此外，如果将所述的膜应用到电解电池中，它能够在电池中直接应用压力差。
附图说明
本发明前述的和进一步的目的、特征和优点在下述的优选实施例及其参照的相关附图中得到清晰的说明。
附图1是本发明的复合膜放大后的横截面，以及选取出的放大更多的部分。
附图2是复合膜的垫子中的由节点连接在一起的三个原纤维的透视图。
具体实施方式
一个复合膜1由原纤维3形成的垫子2和一种离聚物5组成。其中原纤维3通过节点4连接或者通过如专利US RE37,701E中报道的方式连接，以形成复合膜1的某种支架或者骨架，作为支撑结构。垫子2具有原纤维3的非织造布的缠结结构，具有不规则的空穴，这些空穴形成了具有平均孔径的多微孔，例如平均孔径为0.2μm时，垫子的孔隙率为85％～90％，厚度为3μm。原纤维3由膨体聚四氟乙烯(ePTFE)组成。为将垫子2制成复合膜1，用常规方法将离聚物5加入到微孔中，并且涂布在垫子2的两个表面上从而形成一个气密的膜。溶于溶剂中的离聚物要均匀地涂布，从而注入垫子2的微孔，使其闭塞。
在涂布离聚物5之前，将一种加固的和易润湿的材料10涂布到垫子2的原纤维3和节点4上，从而形成一个覆盖层，这种材料10实现了电化学电池无污染的目的，增加了ePTFE的抗张强度，改变了原纤维3的表面性质，使得它们更易润湿。根据所述的实施例，所述的材料10是THV或者是聚酰亚胺，THV是三种成分：四氟乙烯、六氟丙烯和偏二氟乙烯的三元共聚物。将其置于溶液或悬浮液中从而填满垫子2的微孔结构且不破坏它们。所述的溶剂可为酮类，较佳地，对THV采用丙酮溶解，对聚酰亚胺采用N-甲基吡咯烷酮。将所述的溶液涂布于原纤维3的方法中采用标准流程如空气中或无空气溅射、浸入或丝网印刷，优选超声波喷雾器溅射。然后溶剂蒸发，并且不破坏垫子2的结构，蒸发采用的温度依赖于所选用的材料10。在接下来的一个非必需的步骤中，特别若THV作为材料10，使用的温度可以稍高于它的熔点，优选比熔点高15℃，从而烧结原纤维3并固化原纤维3的覆盖层，尤其当垫子2包括节点4时。这增大了机械稳定性因为原纤维3会被材料10包裹得地更坚硬，并且相互粘着地更紧密。原纤维3和覆盖层中材料10的质量比可以为500∶5，优选10∶3。
由上述方法制得的复合膜1具有高度的机械稳定性和均一的抗张强度，尤其是收缩性和膨胀性没有传统的复合膜剧烈，因此使其更易操作，如在电化学电池中的封装技术操作。此外，其制造速度更快，因为它不需要表面活性剂，以及因为覆盖原纤维3的材料10的不同的疏水性致使离聚物溶液可能含有的更高的水分比率。复合膜1还可以没有空穴，也是因为材料10较低的疏水性和低级别的ePTFE，也就是说，由于可以将更低机械强度的材料用于垫子2上，从而节约了成本。
如果将复合膜1用于电解质电池中，压力差可以应用在复合膜1的两侧，从而形成一个更简易、更不复杂的系统配置。
实施例
垫子2UD160F来自上海优天高新材料有限公司(Uno-Tech Ltd.，Shanghai)，厚度3μm，孔隙率≥85％，孔径在0.1至1μm之间。垫子2装在一个架子上从而两个主要的表面不会接触到别的地方。然后将该架子置于超声波喷雾器下方，加热平板上方约3cm处，将该平板加热到100℃。
利用超声波喷雾器将一悬浮液溅射到垫子2的上表面。该悬浮液由3wt％的THV220G组成，它是一种氟橡胶，产自美国的Dyneon，Inc.of Oakdale，Minn.，比重1.95，熔点124℃，混合在丙酮中。
也可以使用Dyneon公司的THV400G或者THV500G，其中需要考虑其不同的熔点，分别为150℃～160℃和162℃～174℃。溅射本身是以一种交叉的方式进行，通过从左到右成排地溅射悬浮液，然后从上到下成列地溅射，由此将悬浮液涂布到垫子2的微孔中而不停留在垫子2的表面上，并且不会通过垫子2滴到加热平板上。几乎在进行溅射步骤的同时，加热平板将丙酮烘干。
下一步是在150℃下烧结15分钟。含有用强化材料10加固后的原纤维3的垫子2由10wt％的ePTFE组成，用总量为2.7wt％的THV加固，垫子2的总孔隙率大约为87.3％(为计算更简单，THV和ePTFE不同的比重忽略不计)。
在最后一步中，再次使用超声波喷雾器，将离聚物5溅射到仍置于架子上的强化垫子2的覆盖层上。该离聚物包含10wt％的
Figure G2008102050828D0000041
的水溶液(购自杜邦公司)和一种醇，优选乙醇；将两种成分混合，得到的溶液或悬浮液包含总量为5wt％的
Figure G2008102050828D0000042
将离聚物的溶液通过交叉的方式溅射到垫子2上。最后的生产步骤包含一个120分钟的干燥过程，干燥温度100℃，以及一个60分钟的烧结过程，烧结温度150℃。
在一个氢-空气燃料电池的单电池中，采用干燥气体，空气压力为环境常压，氢气压力为0.4Bar，该便宜的复合膜，例如在0.6V，58℃时可以达到650mA/cm2。

Claims (4)

1.一种电化学电池的复合膜(1)，其包含一个垫子(2)和一种离聚物；该垫子(2)具有原纤维(3)的多微孔结构，由膨体聚四氟乙烯(ePTFE)组成；该离聚物填充垫子多微孔结构中的空洞，允许离子通过所述的膜进行交换；其特征在于：所述的垫子(2)的多微孔结构中的原纤维(3)被一层聚合物(10)覆盖。
2.如权利要求1所述的复合膜，其特征在于：所述的聚合物(10)为聚酰亚胺。
3.如权利要求1所述的复合膜，其特征在于：所述的聚合物(10)为含氟聚合物。
4.如权利要求3所述的复合膜，其特征在于：所述的含氟聚合物为四氟乙烯、六氟丙烯和偏二氟乙烯(THV)的三元共聚物。
CN200810205082A 2008-12-30 2008-12-30 电化学电池的复合膜 Pending CN101771153A (zh)

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CN108539215A (zh) * 2017-03-03 2018-09-14 丰田自动车株式会社 燃料电池用催化剂油墨、燃料电池用催化剂层和膜电极接合体
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CN105794031A (zh) * 2013-11-29 2016-07-20 旭化成株式会社 高分子电解质膜
US10644339B2 (en) 2013-11-29 2020-05-05 Asahi Kasei Kabushiki Kaisha Polymer electrolyte membrane
US10688448B2 (en) 2013-11-29 2020-06-23 Daikin Industries, Ltd. Porous body, polymer electrolyte membrane, filter material for filter, and filter unit
US10944121B2 (en) 2013-11-29 2021-03-09 Asahi Kasei Kabushiki Kaisha Polymer electrolyte film
US11084895B2 (en) 2013-11-29 2021-08-10 Daikin Industries, Ltd. Modified polytetrafluoroethylene fine powder and uniaxially stretched porous body
CN108539215A (zh) * 2017-03-03 2018-09-14 丰田自动车株式会社 燃料电池用催化剂油墨、燃料电池用催化剂层和膜电极接合体
CN108539215B (zh) * 2017-03-03 2021-06-11 丰田自动车株式会社 燃料电池用催化剂油墨、燃料电池用催化剂层和膜电极接合体

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