CN1894817A - 进行电化学反应的方法 - Google Patents

进行电化学反应的方法 Download PDF

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CN1894817A
CN1894817A CNA200480037791XA CN200480037791A CN1894817A CN 1894817 A CN1894817 A CN 1894817A CN A200480037791X A CNA200480037791X A CN A200480037791XA CN 200480037791 A CN200480037791 A CN 200480037791A CN 1894817 A CN1894817 A CN 1894817A
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D·J·海盖特
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Abstract

在电化学电池内进行电化学反应的方法，所述电化学电池包括通过亲水离子交换膜隔开的电极，其中在其浓度得到控制的电解质水溶液存在下进行反应。

Description

进行电化学反应的方法
发明领域
本发明涉及进行电化学反应的方法。
发明背景
存在其中电极通过离子交换膜，例如固体聚合物电解质隔开的电化学电池。
WO-A-03/23890教导了可基于亲水聚合物，即固有地能通过其分子结构吸收并输送水的聚合物，生产离子交换材料。该材料尤其与氢-氧燃料电池有关，这是因为可再分配产物水，从而避免局部溢流或者膜干燥。基本上存在三种方式，其中可使得亲水材料是离子导电的。
第一种方式是通过由离子活性的单体溶液共聚，形成离子活性位点；在WO-A-03/23890中记载了这一方法。在所得聚合物内形成强阴离子或阳离子部分，从而使得它分别充当阴离子交换(AE)或阳离子交换(CE)材料。
第二种方式是通过接枝离子活性单体，在该材料内引入离子活性位点。这种材料的实例是Nafion，当通过在软化水内水合，从而活化离子位点时，Nafion变成为离子导电的。
第三种方式是通过在酸性或碱性液体内水合亲水材料。亲水材料，如HEMA(甲基丙烯酸2-羟乙酯)和MMA-VP(甲基丙烯酸甲酯-乙烯基吡咯烷酮)不具有固有的电性能，和若在去离子蒸馏(DD)水内水合的话，则是良好的电阻器。然而，若这些材料在酸性或碱性溶液内水合，则它们变为良好的导体。这一方法的局限为当电解质溶液被洗出时，电导率下降，该材料最终变得没有电活性。在其中反应物水通常大量存在的电解池内，和在其中产生水的氢-氧燃料电池中，这种电解质溶液的洗出尤其成问题。
发明概述
本发明解决了第三种方法的局限性，且基于下述认识：若可维持膜内电解质的浓度，则用电解质水合的电学上钝性的膜是其它亲水体系的可行的替代方案。类似地，可通过在酸性或碱性溶液内水合膜，来增加弱离子亲水膜的电导率。可通过控制例如膜的水合程度，来维持电解质的浓度。
根据本发明，在包括通过亲水离子交换膜隔开的电极的电化学电池内进行电化学反应的方法包括：在电解质的浓度得到控制的电解质的水溶液存在下进行反应。
优选实施方案的说明
电池可以是燃料电池或电解池形式。在涉及氢气和氧气上的燃料电池的情况下，在电池反应中产生水。接着必须从膜中除去足量的水，为的是维持电解质的浓度。在例如这种情况下，即其中需要从体系中除去水的情况下，优选通过蒸发实现除水。可通过使用远离膜的Peltier冷却的“冷却点(cold spot)”，实现蒸发，其中在所述的冷却点处，来自温热电池的湿气冷凝并被除去。对于其中消耗水的电池，例如电解池来说，可通过限制引入到电池内的水量来控制水合程度。可例如通过监控使用过程中膜的pH来评估水合程度。
亲水材料可以是离子钝性的，即它不具有固有的电性能。在此情况下，通过电解质溶液赋予该材料离子活性。或者，亲水材料可以是离子活性的，它在其结构内包括阴离子或阳离子位点。此处含水电解质增加亲水材料的离子活性。本发明对弱活性材料具有特别的应用性。弱活性材料是那些当在DD水内水合时，显示出离子电导率小于工业标准材料，例如Nafion 117的60％，典型地为50％的材料。
可使用本领域已知的任何合适的方法，获得亲水材料。例如，可根据WO-A-03/23890(其内容在此通过此刻引入)中所述的技术，形成离子活性材料。该材料优选是可通过(共)聚合诸如甲基丙烯酸甲酯、N-乙烯基-2-吡咯烷酮或丙烯腈之类的单体而获得的亲水聚合物，且优选是交联的。
电解质溶液可以是酸性或碱性的。合适的电解质的实例包括甲苯磺酸(TSA)、乙烯基磺酸、丙烯酰胺基-(2-甲基)丙磺酸(AMPSA)、氢氧化钠或氢氧化钾。
电化学电池优选为膜电极组件(MEA)或MEA组形式。MEA和制造方法是本领域公知的。WO-A-03/23890记载了生产MEA的“一步”法，该方法涉及通过就地聚合形成膜。
下述实施例阐述可如何如本发明所述控制亲水离子交换膜的电导率。
实施例1
通过在Co 60源内，用2兆拉德剂量辐照含有35％丙烯腈、35％N-乙烯基-2-吡咯烷酮、5％甲基丙烯酸烯丙酯和25％去离子蒸馏水的混合物，形成交联亲水聚合物。将所得固体聚合物分成两个样品。第一个样品在水中水合，并使用AC桥法测量其电导率。第二个样品在10wt％TSA在水中的溶液内水合，之后在与第一样品所使用的相同试验电池内测量其电导率。
表明第二样品的电导率大于第一样品，其比值为5.7∶0.07，即81.4。还发现第二样品的电导率比Nafion 117膜大36％。
然后在过量DD水中浸渍第二样品14天的时间段，之后测量其电导率。发现“残留”电导率仅仅是其起始电导率的15％，从而证明发生TSA的显著损失。随后的测量证明随着在DD水中洗涤时间的增加电导率继续下降。通过添加另外的TSA到膜中，恢复电导率，结果恢复起始pH。
实施例2
通过在Co 60源内，用2兆拉德剂量辐照含有24％甲基丙烯酸甲酯、72％N-乙烯基-2-吡咯烷酮和4％甲基丙烯酸烯丙酯的混合物，形成交联亲水聚合物。将所得固体聚合物分成两个样品。第一个样品在水中水合，并使用AC桥法测量其电导率。第二个样品在10wt％TSA在水中的溶液内水合，之后在与第一样品所使用的相同试验电池内测量其电导率。
表明第二样品的电导率大于第一样品，其比值为47.6∶0.05，即952。还发现第二样品的电导率比Nafion 117膜大13％。
然后在过量DD水中浸渍第二样品14天的时间段，之后测量其电导率。发现“残留”电导率仅仅是其起始电导率的12％，从而证明发生TSA的显著损失。随后的测量证明随着在DD水中洗涤时间的增加电导率继续下降。通过添加另外的TSA到膜中，恢复电导率，结果恢复起始pH。

Claims (14)

1.在电化学电池内进行电化学反应的方法，所述电化学电池包括通过亲水离子交换膜隔开的电极，其中在其浓度得到控制的电解质水溶液存在下进行反应。
2.权利要求1的方法，其中控制膜的水合程度。
3.权利要求2的方法，其中通过从膜中除去水来控制水合程度。
4.权利要求3的方法，其中通过从膜中蒸发水来控制水合程度。
5.权利要求2-4任何一项的方法，其中水是反应物，并控制输入到电池内的水。
6.前述任何一项权利要求的方法，其中电解质是甲苯磺酸、乙烯基磺酸、丙烯酰胺基-(2-甲基)丙磺酸、氢氧化钠或氢氧化钾。
7.前述任何一项权利要求的方法，其中亲水材料是离子钝性材料。
8.权利要求1-6任何一项的方法，其中亲水材料是离子活性材料。
9.前述任何一项权利要求的方法，其中亲水材料是聚合物材料。
10.权利要求9的方法，其中通过聚合包含甲基丙烯酸甲酯、N-乙烯基-2-吡咯烷酮或丙烯腈的单体，可获得亲水材料。
11.权利要求9或10的方法，其中亲水材料被交联。
12.前述任何一项权利要求的方法，其中电池是燃料电池或电解池。
13.前述任何一项权利要求的方法，其中电池为膜-电极组件(MEA)或MEA组形式。
14.前述任何一项权利要求的方法，其中通过添加进一步的电解质来控制浓度。
CNA200480037791XA 2003-12-19 2004-12-20 进行电化学反应的方法 Pending CN1894817A (zh)

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