CN101230113A - 用于质子传导性电解质的接枝有磺酰基的杂环材料 - Google Patents
用于质子传导性电解质的接枝有磺酰基的杂环材料 Download PDFInfo
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Abstract
本发明涉及一种质子传导性聚合物，其包括聚合物骨架和与该聚合物骨架连接的杂环化合物。该杂环化合物包括与该杂环化合物连接的磺酰基官能团。
Description
技术领域
本发明涉及包含杂环的化合物和组合物。
背景技术
质子电解质膜(PEMs)可以用于多种装置中，包括燃料电池、净化和重整电池以及其它电化学应用。
已经研究了多种用作PEMs的材料。其例子包括全氟磺酸类聚合物，以及多种咪唑聚合物，包括聚苯并咪唑-H3PO4、聚乙烯基吖嗪HPO4(Polyvinazine HPO4)，以及其它基于咪唑的材料。咪唑是环上具有两个氮原子的芳香杂环。咪唑通过分子间质子传递或结构扩散来传导质子。但是，对于燃料电池的应用，基于咪唑环的材料的电化学稳定性似乎不足。
PEM燃料电池中包含的金属，例如铂或其它催化剂，能够与咪唑环中包含的氮形成强键，致使催化剂中毒或者活性变弱。另外，氧还原潜在区中咪唑的氧化以及咪唑产物的氧化可能被吸收到贵金属催化剂或电极的表面上，因而降低了电极表面积的功效。
因此，在本领域中需要一种用于燃料电池中的质子传导性聚合物，其具有高的质子传导性，但在不同湿度值和高于100℃的温度下其效力不发生变化。另外，在本领域中需要一种质子传导性聚合物，其在燃料电池环境中具有化学稳定性和与贵金属催化剂的相容性。
发明概要
质子传导性聚合物包括聚合物骨架和与该聚合物骨架连接的杂环化合物。该杂环化合物包括与该杂环化合物相连的磺酰基官能团。
附图简述
图1是2-乙基磺酰基-咪唑和咪唑的电流图；
图2是2-乙基磺酰基-咪唑和苯磺酸以及不同比例的咪唑和苯磺酸相对于温度的传导率图；
图3是具有接枝磺酰基咪唑的直链混合无机-有机聚合物相对于温度的传导率图。
具体实施方式
本文所述的聚合物包括直链聚合物、共聚物、聚合物前体以及混合的无机-有机聚合物和复合物，并且可用于质子交换膜(PEMs)中。
作为在整个说明书中使用的术语“聚合物”，其可以指聚合物、共聚物、以及混合的无机和有机聚合物。另外，术语“PEM”是指可以在多种电化学应用中用作质子传导材料的质子交换膜或聚合物电解质膜。
质子传导性聚合物包括聚合物骨架和与该聚合物骨架连接的杂环化合物。所述杂环化合物包括与该杂环化合物相连的磺酰基官能团。所述杂环化合物可以包括与其连接的直链有机化合物。该直链有机化合物可以具有1到20个碳原子。另外，杂环化合物可以包括具有1到20个碳原子的与磺酰基官能团连接的直链有机化合物。
可以在质子传导性聚合物中使用多种杂环化合物，其包括1，2，4-三唑、1，2，3-三唑、1H-苯并三唑、嘧啶、吡嗪、嘌呤、咪唑、吡唑、吡啶和它们的衍生物。虽然本发明可以使用多种杂环化合物，但优选的杂环包括咪唑。与杂环化合物连接的磺酰基具有很强的吸电子效应，并可以增加电化学稳定性，减小燃料电池中杂环和贵金属催化剂之间的相互作用。
可以使用多种聚合物骨架成分，其包括聚烯烃、聚环氧、全氟烯烃、聚硅氧烷、聚对苯撑、聚苯醚、聚对亚苯基砜、聚醚醚酮、Udel聚砜和聚苯并咪唑。聚合骨架还可以包括与其连接的酸基团，例如H3PO4、H2SO4、CF3SO2NHSO2CF3、CF3SO3H、CH3SO3H和CF3PO3H2。应当认识到，上述所列之外的其它酸基团也可以被合并到聚合物骨架中。聚合物骨架还可以包括磺化或膦酸化的聚合物或共聚物。所述磺化或膦酸化的聚合物或共聚物的例子包括聚苯乙烯磺酸、磺化的聚醚醚酮、全氟磺酸和磺化的聚苯硫醚。
另一方面，聚合物骨架可以是混合的无机-有机聚合物。示例性的混合无机-有机聚合物可以具有硅官能团。混合无机-有机聚合物中可以存在多种硅官能团，包括硅烷和硅氧烷官能团。另外，所述混合无机-有机聚合物可以包括与其连接的酸基团。所述酸基团可以与关于聚合物骨架所述的那些相似，或者可以包括其它已知的与所述混合无机-有机聚合物相容的酸性基团。
关于杂环化合物和磺酰基相对于聚合物骨架的关系，质子传导性聚合物的结构可以不同。一方面，质子传导性聚合物可以具有下述结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R1是氢或者具有1到20个碳原子的有机基团。从上述的结构可以看出，聚合物骨架可以通过具有1到20个碳原子的直链有机基团与磺酰基相连。杂环基团(在此例中是咪唑)与磺酰基相连，并且在空间位置上位于磺酰基的外侧。
质子传导性聚合物还可以具有下述结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R4是具有1到20个碳原子的直链有机基团。不同于前面所述的结构式，聚合物骨架这次与杂环化合物(显示的是咪唑基)相连。所述杂环化合物与磺酰基连接，在空间位置上，磺酰基在所述杂环化合物的外侧。
上述两种结构式的聚合物骨架可以是任意的前述聚合物骨架，包括任意的前述与酸相连的聚合物和共聚物、或者混合的无机-有机聚合物成分。
质子传导性聚合物可以用作燃料电池中的电解质膜。该电解质膜可以位于燃料电池的阳极和阴极之间，其中所述质子传递膜由前述各种质子传导性聚合物复合物形成。
质子传导性聚合物可以由多种机理形成，其包括前述和下述实施例中描述的不同结构。
实施例1
2-乙基磺酰基-咪唑的电化学稳定性
参照图1，其显示了2-乙基磺酰基-咪唑和咪唑在氮气吹扫的CH3CN溶液中的循环伏安图。循环伏安的测量是如下进行的：在具有六氟磷酸四丁铵(TBAPF6)0.1mol·dm-3的CH3CN溶液和5×10-3mol·dm-3咪唑或2-乙基磺酰基-咪唑的三电极电池中，使用铂工作电极、铂辅助电极以及具有0.1mol·dm-3 AgNO3-CH3CN包含0.1mol·dm-3TBAPF6的银Ag/Ag+参比电极。从图中可以看出，在咪唑的伏安图中接近1.0伏特处出现了大的氧化峰。发现咪唑的氧化产物被吸附到铂电极的表面，因而阻隔了电极的表面区域。相反，在较宽的电位范围(相对于参比电极0到1.8伏)之内观测不到2-乙基磺酰基-咪唑的氧化还原峰。在50次循环试验内没有发生改变。50次循环后，向含2-乙基磺酰基-咪唑的溶液中加入咪唑，出现了大的氧化峰。当用氧气吹扫CH3CN溶液时观测到了类似的结果，意味着2-乙基磺酰基-咪唑在燃料电池环境下具有提高的电化学稳定性。
实施例2
2-乙基磺酰基-咪唑和苯磺酸的混合物
用以下方法制备2-乙基磺酰基-咪唑。将2-巯基咪唑与卤代烷在碱性水溶液中反应，从而制备2-烷基硫代咪唑。然后使用常用的氧化剂将2-烷基硫代咪唑氧化，制得2-烷基咪唑。
将2-乙基磺酰基-咪唑和苯磺酸溶于甲醇并搅拌10分钟。然后在真空下除去溶剂，将所得混合物密封于玻璃管中，使用由两片铂制成的标准电极测量其传导率。还测量了咪唑与苯磺酸不同比率的混合物。测量结果显示在图2中，其显示了不同材料的传导率随温度变化的曲线。从图中可以看出，相对于各种咪唑混合物，乙基磺酰基-咪唑和苯磺酸的混合物在在整个变化的温度范围内显示出更加线性的传导性能。
实施例3
具有接枝磺酰基咪唑的混合无机-有机聚合物
混合无机-有机聚合物的形成可以由以下反应表示。
聚合物
从上面的反应可以看出，将2-巯基咪唑、EthOK和基于甲基乙基硅氧烷的材料的混合物在室温下搅拌24小时，然后通过用乙酸乙酯洗脱的硅胶柱色谱过滤从而分离前体II。然后用过氧化物3-氯过氧苯甲酸和20％水在乙醇中将前体II氧化，并用醚将产物沉淀。将所获产物在75℃下加热48小时，得到在室温下是固体在高于75℃软化的聚合物。图3中绘出了该聚合物随温度变化的质子传导率。该传导率是使用如上所述的类似的测量装置测量的。从图中可以看出，该传导率与温度具有线性关系，与关于前图所述的相似。
本发明已经以举例说明的方式进行了描述。应当理解，所用术语是为了表达描述词语的本质，而不是限定性的。根据上述教导，许多本发明的改进和变化都是可能的。因此，在所附的权利要求范围之内，本发明可以以不同于具体描述的方式实施。
Claims (20)
1.质子传导性聚合物，其包含：
聚合物骨架；和
与所述聚合物骨架连接的杂环化合物，该杂环化合物具有与该杂环化合物相连的磺酰基官能团。
2.如权利要求1所述的质子传导性聚合物，其中所述杂环化合物包括与其连接的直链有机化合物，该直链有机化合物具有1到20个碳原子。
3.如权利要求1所述的质子传导性聚合物，其中所述杂环化合物包括与磺酰基官能团连接的直链有机化合物，所述直链有机化合物具有1到20个碳原子。
4.如权利要求1所述的质子传导性聚合物，其中所述杂环化合物包括1，2，4-三唑、1，2，3-三唑、1H-苯并三唑、嘧啶、吡嗪、嘌呤、咪唑、吡唑、吡啶和它们的衍生物。
5.如权利要求1所述的质子传导性聚合物，其中所述聚合物骨架包括聚烯烃、聚环氧、全氟烯烃聚合物、聚硅氧烷、聚对苯撑、聚苯醚、聚对亚苯基砜、聚醚醚酮、Udel聚砜和聚苯并咪唑。
6.如权利要求5所述的质子传导性聚合物，其中所述聚合骨架包括与其相连的酸基团。
7.如权利要求6所述的质子传导性聚合物，其中所述酸基团包括H3PO4、H2SO4、CF3SO2NHSO2CF3、CF3SO3H、CH3SO3H和CF3PO3H2。
8.如权利要求1所述的质子传导性聚合物，其中所述聚合物骨架包括磺化或膦酸化的聚合物或共聚物。
9.如权利要求8所述的质子传导性聚合物，其中所述磺化或膦酸化的聚合物或共聚物包括聚苯乙烯磺酸、磺化的聚醚醚酮、全氟磺酸和磺化的聚苯硫醚。
10.如权利要求1所述的质子传导性聚合物，其中所述聚合物骨架包括混合的无机-有机聚合物。
11.如权利要求10所述的质子传导性聚合物，其中所述混合的无机-有机聚合物包括具有硅官能团的化合物。
12.如权利要求11所述的质子传导性聚合物，其中所述硅官能团包括硅烷和硅氧烷官能团。
13.如权利要求10所述的质子传导性聚合物，其中所述混合的无机-有机聚合物包括与其相连的酸基团。
14.如权利要求1所述的质子传导性聚合物，其具有结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R1是氢或者具有1到20个碳原子的有机基团。
15.如权利要求1所述的质子传导性聚合物，其具有结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R4是具有1到20个碳原子的直链有机基团。
16.电解质膜，其包含：
包括杂环化合物的聚合物，所述杂环化合物具有与该杂环化合物相连的磺酰基官能团。
17.如权利要求16所述的电解质膜，其中所述聚合物包括聚合物骨架和与该聚合物骨架连接的杂环化合物，所述杂环化合物具有与该杂环化合物相连的磺酰基官能团。
18.如权利要求16所述的电解质膜，其中所述聚合物具有结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R1是氢或者具有1到20个碳原子的有机基团。
19.如权利要求16所述的电解质膜，其中所述聚合物具有结构式：
其中R3表示聚合物骨架，R2是具有1到20个碳原子的直链有机基团，R4是具有1到20个碳原子的直链有机基团。
20.燃料电池，其包括：
阳极；
与阳极分离的阴极；
位于阳极和阴极之间的质子传递膜，所述质子传递膜由包括杂环化合物的聚合物形成，所述杂环化合物具有与该杂环化合物相连的磺酰基官能团。
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| CN107033350A (zh) * | 2017-03-31 | 2017-08-11 | 上海大学 | 质子交换膜用膦酸和1,2,3‑三唑功能化聚醚砜及其制备方法 |
| CN115850538A (zh) * | 2021-09-27 | 2023-03-28 | 山东东岳未来氢能材料股份有限公司 | 一类带有联吡啶侧基的全氟离子聚合物及合成方法与应用 |
| CN115873150A (zh) * | 2021-09-27 | 2023-03-31 | 山东东岳未来氢能材料股份有限公司 | 一类带有吡啶侧基的全氟离子聚合物及其合成方法与应用 |
| CN115873154A (zh) * | 2021-09-27 | 2023-03-31 | 山东东岳未来氢能材料股份有限公司 | 带有三联吡啶侧基的全氟离子聚合物及合成方法与应用 |
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| US8519074B2 (en) * | 2010-01-15 | 2013-08-27 | The University of Massachusettes | Comb polymers for supramolecular nanoconfinement |
| JP2014009190A (ja) * | 2012-06-29 | 2014-01-20 | Shikoku Chem Corp | イミダゾールシラン化合物、合成方法及びその利用 |
| CN103467991A (zh) * | 2013-09-23 | 2013-12-25 | 上海大学 | 双草酸硼酸盐离子液体掺杂磺化聚苯硫醚质子交换膜材料及其制备方法 |
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| US5827602A (en) * | 1995-06-30 | 1998-10-27 | Covalent Associates Incorporated | Hydrophobic ionic liquids |
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| US6310110B1 (en) * | 1999-07-30 | 2001-10-30 | Michael A. Markowitz | Molecularly-imprinted material made by template-directed synthesis |
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| US20040122256A1 (en) * | 2001-02-01 | 2004-06-24 | Masanori Ikeda | Perfluorvinyl ether monomer having sulfonamide group |
| DE10163518A1 (de) * | 2001-12-21 | 2003-07-10 | Fraunhofer Ges Forschung | Protonenleitfähige Membranen/Schichten und Verfahren zu deren Herstellung |
| US6987163B2 (en) * | 2002-08-07 | 2006-01-17 | Research Foundation Of The State University Of New York | Modified polybenzimidazole (PBI) membranes for enhanced polymer electrochemical cells |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107033350A (zh) * | 2017-03-31 | 2017-08-11 | 上海大学 | 质子交换膜用膦酸和1,2,3‑三唑功能化聚醚砜及其制备方法 |
| CN107033350B (zh) * | 2017-03-31 | 2019-07-23 | 上海大学 | 质子交换膜用膦酸和1,2,3-三唑功能化聚醚砜及其制备方法 |
| CN115850538A (zh) * | 2021-09-27 | 2023-03-28 | 山东东岳未来氢能材料股份有限公司 | 一类带有联吡啶侧基的全氟离子聚合物及合成方法与应用 |
| CN115873150A (zh) * | 2021-09-27 | 2023-03-31 | 山东东岳未来氢能材料股份有限公司 | 一类带有吡啶侧基的全氟离子聚合物及其合成方法与应用 |
| CN115873154A (zh) * | 2021-09-27 | 2023-03-31 | 山东东岳未来氢能材料股份有限公司 | 带有三联吡啶侧基的全氟离子聚合物及合成方法与应用 |
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| US7964651B2 (en) | 2011-06-21 |
| JP2011507979A (ja) | 2011-03-10 |
| JP5650403B2 (ja) | 2015-01-07 |
| WO2008091475A1 (en) | 2008-07-31 |
| CN101230113B (zh) | 2013-05-22 |
| DE102007060692A1 (de) | 2008-09-11 |
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