磺化聚乙烯醇/侧链磺化聚芳醚酮交联复合膜的制备与性能  

Preparation and Properties of Sulfonated Poly(vinyl alcohol)/Poly(aryl ether ketone)with Pendant Sulfoalkyl Groups Crosslinked Composite Proton Exchange Membrane

作　　者：程海龙 韩康辉 孙娇娇 郑锐 李奥 栾立伟 管丹丹 陶璐静 Hailong Cheng;Kanghui Han;Jiaojiao Sun;Rui Zheng;Ao Li;Liwei Luan;Dandan Guan;Lujing Tao(School of Materials Science and Engineering,Jilin Institute of Chemical Technology,Jilin 132022,China)

机构地区：[1]吉林化工学院材料科学与工程学院,吉林吉林132022

出　　处：《高分子材料科学与工程》2024年第4期147-156,共10页Polymer Materials Science & Engineering

基　　金：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)。

摘　　要：通过溶液共混热处理方法,制备了磺化聚乙烯醇(SPVA)含量不同的SPVA/侧链磺化聚芳醚酮交联复合膜(Cr-SSPxx)。交联网络结构有效增强了交联复合膜的力学性能、热稳定性、氧化稳定性及尺寸稳定性,扫描电镜显示,交联复合膜呈现了更好的相容性和均一性。随交联度增加,交联复合膜的溶胀率呈现明显下降趋势,在25℃和80℃时,Cr-SSP30膜的溶胀率分别仅有3.7%和7.6%。由于SPVA对醇有阻碍作用,以及交联网络结构增加了膜的致密性,故该系列Cr-SSPxx膜展现出非常优秀的阻醇性能,交联复合膜的甲醇渗透率明显低于纯S-SPAEK膜和磺化聚乙烯醇/侧链型磺化聚芳醚酮复合膜,Cr-SSP30膜的甲醇渗透率仅为9.4×10^(-8) cm^(2)/s。虽然与磺化聚乙烯醇/侧链型磺化聚芳醚酮复合膜相比,交联复合膜的质子传导率有所降低,但由于独特的侧链磺化结构能够促进质子传导,质子传导率最低的Cr-SSP30膜的传导率在25℃和80℃时也都分别达到了0.034 S/cm和0.065 S/cm,同时表现出了更高的质子选择性,能够满足直接甲醇燃料电池(DMFC)的使用要求,有望在DMFC中得到应用。The sulfated poly(vinyl alcohol)(SPVA)/sulfonated poly(aryl ether ketone)with pendant sulfonic acid groups(S-SPAEK)crosslinked composite membranes(Cr-SSPxx)with different contents of SPVA were prepared by solution blend method.The Cr-SSPxx crosslinked composite membranes were obtained by heating reaction at 140℃.Fourier transform infrared spectroscopy(FT-IR)spectra show that the covalent band crosslinked structure is formed between the sulfonic acid groups on S-SPAEK and hydroxyl groups on SPVA.The scanning electron microscope(SEM)images show that the crosslinked composite membranes present better compatibility and uniformity.Through the performance research of the series of membranes,it is found that the crosslinked network structure effectively enhances the mechanical properties,thermal stability,oxidation stability and dimensional stability of the crosslinked composite membranes.The swelling rate of the crosslinked membranes shows an obvious decreasing trend with the increase of crosslinking degree.The swelling rate of Cr-SSP30 membrane is only 3.7%and 7.6%at 25℃and 80℃,respectively.The Cr-SSPxx membranes exhibit excellent methanol resistance due to the hindering effect on methanol of SPVA and the cross-linked network structure increasing the density of membrane.The methanol permeability of the crosslinked composite membranes is significantly lower than that of the S-SPAEK membrane and SPVA/S-SPAEK composite membrane.The methanol permeability of the Cr-SSP30 membrane is only 9.4×10^(-8) cm^(2)/s.Although the proton conductivity of the crosslinked composite membranes is lower than that of SPVA/S-SPAEK composite membrane,this series of membranes show lower proton selectivity.The proton conductivity of Cr-SSP30 membrane is 0.034 S/cm at 25℃and 0.065 S/cm at 80℃,which can meet the requirements of direct methanol fuel cell(DMFC),and expected to be applied in DMFC.

关 键 词：侧链型磺化聚芳醚酮 磺化聚乙烯醇 交联复合质子交换膜 

分 类 号：TM911.4[电气工程—电力电子与电力传动]