CN117423877A - 一种苯甲酸官能化氧化石墨烯改性质子交换膜制备方法 - Google Patents
一种苯甲酸官能化氧化石墨烯改性质子交换膜制备方法 Download PDFInfo
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Abstract
本发明属于膜材料制备领域,涉及一种官能化氧化石墨烯和聚合物膜的复合质子交换膜及其制备方法。本发明先制备得到苯甲酸官能化的氧化石墨烯,再将其掺入到聚合物中,得到苯甲酸官能化的氧化石墨烯复合质子交换膜。其中,苯甲酸官能化氧化石墨烯由氧化石墨烯和对氨基苯甲酸进行重氮盐反应后得到的。所制备的复合膜具有优良的质子传导性的同时,也具有很强的耐久性,具体表现为:在过氧化氢(H2O2)加速降解中,保持更优越的质子传导率。本发明方法操作过程简单,制备条件温和,同时也具有较低的生产成本,具有良好的工业化生产基础和广阔的应用前景。
Description
技术领域
本发明涉及一种基于官能化氧化石墨烯和聚合物膜的复合质子交换膜及其制备方法,具体涉及对氧化石墨烯进行苯甲酸官能化,而后作为添加剂加入到聚合膜中,提高质子交换膜的质子传导性和耐久性。
背景技术
高功率密度的质子交换膜燃料电池(PEMFC)以氢气为原料,提高了氢能的利用效率。聚合物电解质膜作为质子交换膜燃料电池的关键部件之一,其耐久性一直是影响其商业应用的关键问题之一。
PEMFC运行过程中,电解质隔膜不可避免地会受到自由基的攻击而发生降解,导致膜的质子解离减少,水团簇的连通性降低,从而影响膜的质子电导率。为了减少膜的化学降解,可以在膜中添加自由基清除剂,以消除或抑制氧化自由基的产生。常规的金属氧化物自由基添加剂能有效改善膜的耐久性问题,但是这些金属氧化物的阳离子可能会在膜内迁移,从而降低燃料电池的自由基清除效率。
一些含有还原性官能团的有机化合物是良好的自由基清除剂,它们不会损害膜的质子传导性能,同时还能应用于提高质子交换膜的耐久性,具有很好的应用前景。然而,有机分子在膜中的固定是一个重要问题。由于有机分子可能迁移到催化层并吸附在催化剂表面,这可能会导致电池的性能损失。此外,由于质子和有机自由基清除剂的碱性基团之间的静电引力,电池的性能会略有损失。氧化石墨烯(GO)是一种底部和边缘带有亲水官能团的片状材料,是一种良好的膜添加剂,可以提高质子交换膜的质子传导率,但是对于电解质膜的耐久性的提升作用有限。
发明内容
因此,针对现有有机物自由清除剂的缺点,为了保证电解质膜耐久性提升的同时增强质子传导性能,通过重氮化反应将有机物自由基清除剂固定在氧化石墨烯表面,再将其掺杂到电解质膜中得到所需的复合膜结构。本发明制得的苯甲酸官能化氧化石墨烯复合膜具有较高的质子传导率和良好的耐久性。
本发明提到的上述基于苯甲酸官能化氧化石墨烯和聚合物膜的复合质子交换膜的制备方法,具体步骤为:
(1)将一定质量的氧化石墨烯放入一定比例的蒸馏水中,超声波震荡3 h,使氧化石墨烯完全分散在蒸馏水中备用;将合适配比的对氨基苯甲酸和NaOH溶液搅拌溶解,并在搅拌状态下,加入合适配比的NaNO2、冰水和浓盐酸,并在3-5 ℃下搅拌一定时间,形成重氮盐反应;将重氮盐和制备好的氧化石墨烯溶液充分搅拌并反应;最后通过洗涤、离心等步骤得到苯甲酸官能化氧化石墨烯;
(2)在聚合物膜溶液中加入适量的苯甲酸官能化石墨烯,超声波分散均匀后得到复合膜溶液;将复合膜溶液浇铸成膜后,置于真空干燥箱内,温度保持在80-120 ℃,时间保持为12-24 h;最后将复合膜经过酸浸和洗涤,得到苯甲酸官能化氧化石墨烯改性的复合质子交换膜;
本发明中,步骤(1)中的氧化石墨烯选取为单层氧化石墨烯或者易于剥离的多层氧化石墨烯,氧化石墨烯和蒸馏水的比例为1:3~3:1,氧化石墨烯表面官能团为羟基、环氧基和羧基中的一种或者多种,其含氧量为0~75%。
本发明中,步骤(1)中的对氨基苯甲酸和NaOH的质量比例为1:5~5:1,对氨基苯甲酸和NaNO2的质量分数比例为1:4~4:1,对氨基苯甲酸和冰水的质量分数比例为1:20~1:60,冰水和浓盐酸的体积比例为1:5~5:1。
本发明中,步骤(2)中聚合物膜溶液为全氟磺酸树脂、磺化聚芳醚、磺化聚芳醚酮及其衍生物的单一溶液或者混合溶液。
与传统的有机物自由基清除剂和聚合物膜制备的复合质子交换膜相比,本发明首先将有机物自由基清除剂-对苯二甲酸用重氮化反应固定到氧化石墨烯的表面,并将其掺杂到聚合物膜中制备苯甲酸官能化石墨烯复合质子交换膜。由于苯甲酸采用化学键的方式固定到氧化石墨烯表面,氧化石墨烯是具有大分子结构的层状物体,和聚合物膜有很好的相容性和分散性,提高了苯甲酸作为自由基清除剂在聚合物膜中的存在时间。进一步,由于氧化石墨烯表面的羟基、环氧基和羧基等官能团的存在,增强了聚合物膜的质子传导性,解决了常规有机物自由基清除剂带来的聚合物膜质子传导性下降的问题。
此外,本发明操作过程简单,成产所需成本低、制备条件温和,易于大量的、规模化和模块化成产,具有很好的工业生产基础和广阔的应用前景。
附图说明
图1苯甲酸官能化氧化石墨烯复合膜、氧化石墨烯复合膜、纯SPEEK膜在加速降解后的质子传导率。
具体实施方式
以下通过实施例来详细地说明本发明的苯甲酸官能化氧化石墨烯和聚合物膜的复合质子交换膜在耐久性和质子传导性方面的性能,该实例仅是作为提供说明而不是限定本发明。
实施例
取0.45g GO粉放入300ml蒸馏水中,超声振荡3 h将GO分散在水溶液中备用。将1.2g对氨基苯甲酸和40ml NaOH(wt=2%)加入瓶中,然后搅拌直至固体完全溶解。 在搅拌状态下加入0.6g NaNO2、50ml冰水、10ml浓盐酸,在3-5 ℃搅拌30分钟,形成重氮盐。 然后,将重氮盐添加到制备好的GO溶液中并搅拌6小时。 通过离心和去离子水多次洗涤得到苯甲酸官能化氧化石墨烯。 最后在60 ℃真空干燥72 h得到苯甲酸官能化氧化石墨烯固体。
取240 mg的磺化聚醚醚酮(磺化度为59%),加入14mlN,N-二甲基甲酰胺,经过超声波分散和机械搅拌溶解形成SPEEK聚合物溶液,而后向聚合物溶液中加入2.5 wt%的苯甲酸官能化石墨烯,超声波3 h和机械搅拌6 h使其分散均匀;将得到的溶液浇铸在干净的玻璃板上,并用涂布器将其涂布均匀,而后将其放入80 ℃的真空干燥箱中12 h;而后,升温至120 ℃并保持12 h。
该实施例制备的苯甲酸官能化氧化石墨烯复合膜在3wt% H2O2中浸泡6 h后,温度25 ℃-75 ℃,60%相对湿度下质子传导率为0.013-0.083 S/cm,高于未掺杂的SPEEK质子交换膜,以及掺杂GO的SPEEK质子交换膜,表明了苯甲酸官能化氧化石墨烯在提升质子交换膜耐久性和质子传导性方面的突出作用。
Claims (10)
1.一种基于苯甲酸官能化的氧化石墨烯改性的复合质子交换膜的制备方法,其特征在于,具体步骤为:
(1)将一定质量的氧化石墨烯(GO)放入一定比例的的蒸馏水中,超声波震荡3 h,使氧化石墨烯完全分散在蒸馏水中备用;将合适配比的对氨基苯甲酸和NaOH溶液搅拌溶解,并在搅拌状态下,加入合适配比的NaNO2、冰水(0-4 ℃)和浓盐酸,并在3~5 ℃下搅拌一定时间,形成重氮盐反应;将重氮盐和制备好的氧化石墨烯溶液充分搅拌并反应;最后通过洗涤、离心等步骤得到苯甲酸官能化氧化石墨烯(BAF-GO);
(2)在聚合物膜溶液中加入适量的苯甲酸官能化氧化石墨烯,超声波分散均匀后得到复合膜溶液;将复合膜溶液浇铸成膜后,置于真空干燥箱内,温度保持在80-120 ℃,时间保持为12-24 h;最后将复合膜经过酸浸和洗涤,得到苯甲酸官能化氧化石墨烯改性的复合质子交换膜。
2.根据权利要求1所述的制备方法,其特征在于步骤(1)中的氧化石墨烯选取为单层氧化石墨烯或者易于剥离的多层氧化石墨烯。
3.根据权利要求1所述的制备方法,其特征在于步骤(1)中的氧化石墨烯和蒸馏水的比例为1:3~3:1。
4.根据权利要求1所述的制备方法,其特征在于步骤(1)中的氧化石墨烯表面氧原子含量为0~75%。
5.根据权利要求1所述的制备方法,其特征在于步骤(1)中的NaOH溶液的质量分数为1~20%。
6.根据权利要求1所述的制备方法,其特征在于步骤(1)中的对氨基苯甲酸和NaOH的质量比例为1:5~5:1。
7.根据权利要求1所述的制备方法,其特征在于步骤(1)中的对氨基苯甲酸和NaNO2的质量分数比例为1:4~4:1。
8.根据权利要求1所述的制备方法,其特征在于步骤(1)中对氨基苯甲酸和冰水的质量分数比例为1:20~1:60。
9.根据权利要求1所述的制备方法,其特征在于步骤(1)中的冰水和浓盐酸的体积比例为1:5~5:1。
10.根据权利要求1所述的制备方法,其特征在于步骤(2)中聚合物膜溶液为全氟磺酸树脂、磺化聚芳醚、磺化聚芳醚酮及其衍生物的单一溶液或者混合溶液。
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