CN103904344B - 一种质子交换膜及其制备方法 - Google Patents
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Abstract
本发明涉及燃料电池领域，具体而言，涉及一种质子交换膜及其制备方法。该方法，包括以下步骤：(A)将质子交换膜树脂溶解在有机溶剂中得到质量浓度为1-20％的混合溶液；(B)将纳米金属氧化物、表面活性剂依次加入所述混合溶液中，搅拌均匀得到质子交换膜溶液；其中所述纳米金属氧化物与所述质子交换膜树脂的质量比为0.1:1-0.1:100，所述表面活性剂的加入量为所述纳米金属氧化物与所述质子交换膜树脂的质量之和的0.1-5％；(C)将质子交换膜溶液流延成膜或者将质子交换膜溶液浇铸到多孔薄膜内形成均匀的质子交换复合膜。本发明提供的质子交换膜及其制备方法，提高了制备的质子交换膜的均匀性以及自湿能力。
Description
技术领域
本发明涉及燃料电池领域，具体而言，涉及一种质子交换膜及其制备方法。
背景技术
质子交换膜燃料电池由于其具有高能量密度、高能量转化效率、易操作以及对环境友好等优点受到了广泛关注。作为其重要的组成部分质子交换膜，必须在有一定水分存在的条件下，才能保证燃料电池工作，因此需要质子交换膜必须具有一定的保湿能力。
现在普遍采用的保湿方式按与电堆的集成紧密程度可分为外增湿和内增湿两类：外增湿是将增湿子系统与电池分开，在反应气体进入电池之前增湿；内增湿是将增湿子系统与电池集成为一体，在反应气体进入电池之后进行增湿。
自增湿的燃料电池在结构上省去了复杂的增湿系统，结构简单、体积小、重量轻，这类燃料电池较适用于移动电子设备电源、便携式应急电源和低速运输工具等方面，更易实现产业化，因此燃料电池多采用自增湿方式。
为了增强具有自增湿能力的质子交换膜的自湿能力，目前主要的研究工作集中在了对质子交换膜进行改性，如纳米级的SiO2、TiO2或他们的混合物掺杂在质子交换膜溶液中重铸成膜，但是，由于纳米金属氧化物的颗粒直径小，比表面积大，表面能较高，颗粒之间容易在溶液中团聚成高达微米级的团聚体，且所形成的的团聚体也不能被有效的分散开，纳米金属氧化物的分散不均匀性一方面会影响溶液的稳定性和流变性能，另一方面也使得制备出的质子交换膜的电导率分散不均匀，电导率变化大，影响了生成的化学合成水在质子交换膜表面的分布，从而对电池的一致性及电化学性能都有较严重的影响。
发明内容
本发明的目的在于提供一种质子交换膜及其制备方法，以解决上述的问题。
本发明实施例提供了一种质子交换膜的制备方法，包括以下步骤：
(A)将质子交换膜树脂溶解在有机溶剂中得到质量浓度为1-20％的混合溶液；
(B)将纳米金属氧化物、表面活性剂依次加入所述混合溶液中，搅拌均匀得到质子交换膜溶液；其中所述纳米金属氧化物与所述质子交换膜树脂的质量比为0.1:1-0.1:100，所述表面活性剂的加入量为所述纳米金属氧化物与所述质子交换膜树脂的质量之和的0.1-5％；
(C)将质子交换膜溶液流延成膜或者将质子交换膜溶液浇铸到多孔薄膜内形成均匀的质子交换复合膜。
本发明实施例采用的质子交换膜的制备方法，加入了具有保水能力的金属氧化物，并通过添加表面活性剂有效的防止了纳米颗粒团聚，制备出的质子交换膜更加均匀，且由于使纳米金属颗粒分散性更好进而增强了质子交换膜的保水能力，自湿能力提高，由其组装出的电池电化学能力也比较好。
纳米金属氧化物与质子交换膜树脂以及表面活性剂的加入量，这三种物质的比例有严格的控制才能使表面活性剂起到有效防止纳米颗粒团聚的作用，制备出的质子交换膜均匀性更好且自湿效果好。
优选地，所述质子交换膜树脂为全氟磺酸树脂、磺化聚芳醚砜、磺化聚醚醚酮、氟化磺化聚苯乙烯、氟化磺化聚芳醚砜以及氟化磺化聚芳醚酮的一种或几种，这几种质子交换膜树脂均有耐热性能好、化学稳定性和机械强度高等特点，比较常用且成本低。
优选地，所述纳米金属氧化物为SiO2、TiO2、ZrO2、磺化处理过的SiO2、磺化处理过的TiO2以及磺化处理过的ZrO2中的一种或几种，这些纳米金属氧化物的保水能力好，改性后的质子交换膜的自湿性能提升。
优选地，所述纳米金属氧化物的粒径均在30-50nm，为了保证质子交换膜具有一定的保水能力，纳米颗粒度有严格的控制以使得保水能力最强。
优选地，所述多孔薄膜为聚四氟乙烯膜、聚偏氟乙烯膜、聚丙烯膜、聚砜膜或聚酰亚胺膜中的任意一种，这几种多孔薄膜具有耐酸碱耐高温的特点。
优选地，所述有机溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜以及1-甲基-2-吡咯烷酮中的一种或几种，这几种有机溶剂溶解效果好，混合后均匀。
优选地，所述表面活性剂为萘酚聚氧乙烯醚、苯乙烯-马来酸酐树脂、聚乙烯吡咯烷酮和十二烷基苯磺酸钠中的一种或几种，这几种表面活性剂常用且分散效果好。
优选地，所述步骤(B)与步骤(C)之间还包括如下步骤：将所述多孔薄膜用无水乙醇和双氧水的混合溶液进行清洗后用去离子水冲洗干净，再用无水乙醇和硫酸的混合溶液清洗后用去离子水冲洗干净后烘干，多孔薄膜在使用前需要先进行除杂，排出杂离子的干扰避免影响质子交换膜的性能。
优选地，所述多孔薄膜的孔径为0.1-0.8μm；厚度为5-40μm；孔隙率为70％-90％。
优选地，所述步骤(B)中，所述纳米金属氧化物与所述质子交换膜树脂的质量比为为0.1:1-50，所述表面活性剂的加入量为所述纳米金属氧化物与所述质子交换膜树脂的质量之和的0.1-3％。
本发明还提供了一种用上述质子交换膜的制备方法制备出的质子交换膜。
本发明实施例提供的一种质子交换膜及其制备方法，其在制备质子交换膜时添加了表面活性剂，有效防止了纳米颗粒发生团聚，纳米金属氧化物在外力的作用下分散开，然后可以迅速吸附表面活性剂，防止了纳米小颗粒重新聚集进而提升了纳米金属氧化物的保水能力，提高了制备的质子交换膜的均匀性以及自湿能力。
附图说明
图1示出了本发明对比例1与实施例3制备出的质子交换膜组装的电池的电化学性能测试图。
具体实施方式
下面通过具体的实施例子结合附图对本发明做进一步的详细描述。
实施例1
质子交换膜的制备方法如下：
(A)以N，N-二甲基甲酰胺为溶剂，将全氟磺酸树脂溶解，制备成5％的全氟磺酸树脂溶液。
(B)将磺化SiO2和聚乙烯基吡咯烷酮加入到全氟磺酸树脂溶液中搅拌均匀得到质子交换膜溶液，其中全氟磺酸树脂、磺化SiO2和聚乙烯基吡咯烷酮的质量比为1:0.1:0.0011；
(C)将得到的质子交换膜溶液流延成膜得到质子交换膜。
实施例2
(A)以二甲基亚砜与N,N-二甲基甲酰胺的混合溶液为溶剂，将磺化聚芳醚砜溶解，制备成1％的磺化聚芳醚砜溶液。
(B)将颗粒度为50nm的磺化TiO2和苯乙烯-马来酸酐树脂加入到磺化聚芳醚砜溶液中超声2小时混合均匀后得到质子交换膜溶液，其中磺化聚芳醚砜、磺化TiO2和苯乙烯-马来酸酐树脂的质量比为100:0.1:5.005；
(C)将聚偏氟乙烯膜用无水乙醇和双氧水的混合溶液进行清洗后用去离子水冲洗干净，再用无水乙醇和硫酸的混合溶液清洗后用去离子水冲洗干净后烘干，其中聚偏氟乙烯膜的孔径为0.8μm，厚度为5μm；孔隙率为70％。
(D)将得到的质子交换膜溶液浇铸到聚偏氟乙烯膜内得到质子交换膜。
实施例3
(A)以1-甲基-2-吡咯烷酮溶液为溶剂，将氟化磺化聚苯乙烯溶解，制备成20％的氟化磺化聚苯乙烯溶液。
(B)将颗粒度为30nm的磺化ZrO2与SiO2的混合物和十二烷基苯磺酸钠加入到氟化磺化聚苯乙烯溶液中超声2小时混合均匀后得到质子交换膜溶液，其中氟化磺化聚苯乙烯、磺化ZrO2与SiO2的混合物和十二烷基苯磺酸钠的质量比为50:0.1:1.503；
(C)将聚酰亚胺膜用无水乙醇和双氧水的混合溶液进行清洗后用去离子水冲洗干净，再用无水乙醇和硫酸的混合溶液清洗后用去离子水冲洗干净后烘干，其中聚酰亚胺膜的孔径为0.1μm，厚度为40μm；孔隙率为90％。
(D)将得到的质子交换膜溶液浇铸到聚酰亚胺膜内得到质子交换膜。
对比例1
质子交换膜的制备方法如下：
(A)以N，N-二甲基甲酰胺为溶剂，将全氟磺酸树脂溶解，制备成5％的全氟磺酸树脂溶液。
(B)将磺化SiO2加入到全氟磺酸树脂溶液中搅拌均匀得到质子交换膜溶液，其中全氟磺酸树脂、磺化SiO2的质量比为1:0.1；
(C)将聚四氟乙烯膜用无水乙醇和双氧水的混合溶液进行清洗后用去离子水冲洗干净，再用无水乙醇和硫酸的混合溶液清洗后用去离子水冲洗干净后烘干，其中聚酰亚胺膜的孔径为0.1μm，厚度为40μm；孔隙率为90％。
(D)将得到的质子交换膜溶液浇铸到聚四氟乙烯膜内得到质子交换膜。
实验例1
将实施例1-3与对比例1做出的质子交换膜的性能进行对比，具体结果如下：
表1质子交换膜的性能测试
从表1可以看出，本发明加入分散剂制备的质子交换膜表面光滑，质子交换膜溶液存放4小时后基本无变化，而对比例1未加入分散剂的质子交换膜表面有小颗粒，且溶液存在沉降现象。同时，可以看到加入分散剂的质子交换膜保水能力更强，这主要是由于分散剂的加入使纳米金属氧化物在质子交换膜内分布更加均匀，使金属氧化物的保水功效得以全部表现。
实验例2
将实施例3组装的电池的电学性能与对比例1组装出的电池的电学性能进行对比，组装电池的方法如下：将制得的质子交换膜先后经过5％的H2O2和1mol/L稀硫酸处理，再按照一定比例把催化剂Pt/C和5％全氟磺酸树脂溶液混合然后用超声波制成墨水状，均匀的涂在已经处理过的质子交换膜的两面，烘干后制得三合一膜电极，最后将三合一电极组装成电池。
图1中横坐标为电流密度，纵坐标为电池的电压，具体测试结果如图1所示，从图1中可以看出，本发明实施例3采用制备的具有保湿功能的质子交换膜组装成燃料电池后，电化学性能要好于未加入分散剂制备的质子交换膜组装的燃料电池。其原因主要是本发明制备的质子交换膜中的纳米粒子分散更加均匀，质子交换膜的电导率也较为一致，膜的保水性能均匀，使得电池在自增湿条件下，具有良好的电化学性能。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (9)
1.一种质子交换膜的制备方法，其特征在于，包括以下步骤：
(A)将质子交换膜树脂溶解在有机溶剂中得到质量浓度为1-20％的混合溶液；
(B)将纳米金属氧化物、表面活性剂依次加入所述混合溶液中，搅拌均匀得到质子交换膜溶液；其中所述纳米金属氧化物与所述质子交换膜树脂的质量比为0.1:1-0.1:100，所述表面活性剂的加入量为所述纳米金属氧化物与所述质子交换膜树脂的质量之和的0.1-5％；
(C)将质子交换膜溶液流延成膜或者将质子交换膜溶液浇铸到多孔薄膜内形成均匀的质子交换复合膜；所述纳米金属氧化物为TiO2、ZrO2、磺化处理过的TiO2以及磺化处理过的ZrO2中的一种或几种，其中所述纳米金属氧化物的粒径为30-50nm。
2.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述质子交换膜树脂为全氟磺酸树脂、磺化聚芳醚砜、磺化聚醚醚酮、氟化磺化聚苯乙烯、氟化磺化聚芳醚砜以及氟化磺化聚芳醚酮的一种或几种。
3.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述多孔薄膜为聚四氟乙烯膜、聚偏氟乙烯膜、聚丙烯膜、聚砜膜或聚酰亚胺膜中的任意一种。
4.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述有机溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜以及1-甲基-2-吡咯烷酮中的一种或几种。
5.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述表面活性剂为萘酚聚氧乙烯醚、苯乙烯-马来酸酐树脂、聚乙烯吡咯烷酮和十二烷基苯磺酸钠中的一种或几种。
6.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述步骤(B)与步骤(C)之间还包括如下步骤：
将所述多孔薄膜用无水乙醇和双氧水的混合溶液进行清洗后用去离子水冲洗干净，再用无水乙醇和硫酸的混合溶液清洗后用去离子水冲洗干净后烘干。
7.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述多孔薄膜的孔径为0.1-0.8μm；厚度为5-40μm；孔隙率为70％-90％。
8.根据权利要求1所述的一种质子交换膜的制备方法，其特征在于，所述步骤(B)中，所述纳米金属氧化物与所述质子交换膜树脂的质量比为为0.1:1-50，所述表面活性剂的加入量为所述纳米金属氧化物与所述质子交换膜树脂的质量之和的0.1-3％。
9.一种权利要求1-8任一项所述质子交换膜的制备方法制备出的质子交换膜。
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| CN108242553A (zh) * | 2016-12-27 | 2018-07-03 | 天津风伟雨众能源科技有限公司 | 燃料电池用保水型质子交换膜的制备方法 |
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| CN112144076B (zh) * | 2020-09-18 | 2023-08-22 | 碳能科技（北京）有限公司 | 一体化膜电极及其制备方法和应用 |
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