磺化聚乙烯醇/侧链交联型磺化聚芳醚酮复合质子交换膜的制备与性能
Preparation and properties of sulfonated poly(vinyl alcohol)/sulfonated poly(aryl ether ketone)copolymer with pendant crosslinked structure composite membranes
程海龙 1郑锐 1孙娇娇 1韩康辉 1李奥 1管丹丹 1栾立伟 1陶璐静1
作者信息
- 1. 吉林化工学院 材料科学与工程学院,吉林 132022
- 折叠
摘要
磺化芳香类聚合物质子交换膜(PEM)为了达到较好的质子传导性能就必需具有较高的磺化度,然而较高的磺化度就会增加PEM的溶胀率、降低PEM的尺寸稳定性及增加PEM的甲醇渗透率等一系列问题.为此,通过直接缩聚的方法合成了含有羧基的聚芳醚酮共聚物(PAEK-x),利用刚果红作为交联剂并引入磺酸基团,与磺化聚乙烯醇(SPVA)复合制备磺化聚乙烯醇/磺化聚芳醚酮交联复合膜(Cr-SPAEK-x),通过红外光谱对交联复合膜进行了表征.对膜的性能测试发现,该系列交联复合膜表现出了良好的热性能、力学性能、氧化稳定性和适度的吸水性.交联结构形成于PAEK-x的羧基与刚果红的氨基及SPVA的羟基之间,不消耗膜中的传导基团磺酸基,因此该系列交联复合膜表现出了较高的质子传导率,酚酞啉(PPL)摩尔含量为100mol%的磺化聚乙烯醇/磺化聚芳醚酮交联复合膜Cr-SPAEK-100在 25℃和 80℃分别达到了 0.053 S·cm-1和 0.109 S·cm-1.交联网络结构的形成,抑制了膜的水溶胀性,提高了膜的尺寸稳定性,即使是吸水率最高的Cr-SPAEK-100膜的溶胀率室温下也只有 5.26%,同时由于致密的交联网络结构的形成及具有高阻醇性能的SPVA的引入,有效地降低了该系列交联复合膜的甲醇渗透系数,最高也只有 3.92×10-7 cm2·s-1,可见该系列交联复合膜有望在直接甲醇燃料电池中得到应用.
Abstract
A high degree of sulfonation is necessary for sulfonated aromatic polymer proton exchange membranes to achieve high proton conductivity.Nevertheless,an elevated sulfonation level will give rise to a range of complica-tions,including heightened swelling ratio,reduced dimensional stability,and greater methanol permeability.To address this challenge,the poly(aryl ether ketone)containing carboxyl group(PAEK-x)was synthesized using the direct condensation method.Subsequently,the sulfonated poly(vinyl alcohol)(SPVA)/crosslinked sulfonated poly(aryl ether ketone)proton exchange membranes(Cr-SPAEK-x)were prepared with Congo red as the crosslink-ing agent.The crosslinked composite membranes were characterized by infrared spectroscopy.It is found that these series of crosslinked composite membranes show excellent thermal properties,mechanical properties,oxida-tion stability and appropriate water absorption.The crosslinked structure formed between the carboxyl group of PAEK-x and the amidogen of Congo red,along with the hydroxyl of SPVA.Notably,the crosslinking reaction does not consume the sulfonic acid groups in the crosslinked composite membrane.Therefore,these series of cross-linked composite membranes show a high proton conductivity.The sulfonated poly(vinyl alcohol)/sulfonated poly(aryl ether ketone)crosslinked composite membrane with a phenolphthalin content of 100mol%(Cr-SPAEK-100)demonstrated a proton conductivity of 0.053 S·cm-1 at 25℃and 0.109 S·cm-1 at 80℃.The crosslinked network structure effectively inhibits the water swelling of the membrane and improves the dimensional stability of the crosslinked composite membrane.At 20℃,the Cr-SPAEK-100 membrane with the highest water uptake exhibits a minimal swelling ratio of only 5.26%.Moreover,the dense crosslinked network structure and the inclusion of SPVA with excellent methanol barrier properties significantly reduce the methanol diffusion coefficients in the cross-linked membranes,with the highest methanol diffusion coefficients being only 3.92×10-7 cm2·s-1.These series cross-linked composite membranes hold promise for applications in direct methanol fuel cells.
关键词
侧链交联型磺化聚芳醚酮/磺化聚乙烯醇/交联复合质子交换膜/尺寸稳定性/阻醇性能Key words
sulfonated poly(aryl ether ketone)copolymer with pendant crosslinked structure/sulfonated poly(vinyl alcohol)/crosslinked composite membranes/dimensional stability/methanol barrier properties引用本文复制引用
基金项目
吉林省教育厅科学技术研究项目(JJKH20220238KJ)
吉林省自然科学基金(YDZJ202301ZYTS299)
出版年
2024
NETL
NSTL
万方数据