高质子传导率及尺寸稳定性复合质子交换膜制备及性能研究

doi:10.19491/j.issn.1001-9278.2022.08.010

中国塑料 ›› 2022, Vol. 36 ›› Issue (8): 62-68.DOI: 10.19491/j.issn.1001-9278.2022.08.010

高质子传导率及尺寸稳定性复合质子交换膜制备及性能研究

王倩¹(), 杨康宁², 翟绍雄², 尹立坤¹, 何少剑²(), 林俊²

^1.中国长江三峡集团有限公司科学技术研究院，北京 100038
^2.华北电力大学新能源学院，北京 102206

收稿日期:2022-04-02 出版日期:2022-08-26 发布日期:2022-08-22
通讯作者: 何少剑（1984—），男，副教授，从事高分子复合材料研究，heshaojian@ncepu.edu.cn
E-mail:wang_qian8@ctg.com.cn;heshaojian@ncepu.edu.cn
作者简介:王倩（1992—），女，博士，从事电解水制氢技术及固态电池关键技术研究，wang_qian8@ctg.com.cn
基金资助:
中国长江三峡集团有限公司科研项目(202103003)

Preparation and properties of composite proton exchange membranes with high proton conductivity and dimensional stability

WANG Qian¹(), YANG Kangning², ZHAI Shaoxiong², YIN Likun¹, HE Shaojian²(), LIN Jun²

^1.Institute of Science and Technology，China Three Gorges Corporation，Beijing 100038，China
^2.School of New Energy，North China Electric Power University，Beijing 102200，China

Received:2022-04-02 Online:2022-08-26 Published:2022-08-22
Contact: HE Shaojian E-mail:wang_qian8@ctg.com.cn;heshaojian@ncepu.edu.cn

摘要/Abstract

摘要：

通过2?丙烯酰胺?2?甲基丙磺酸（AMPS）在1种具有多孔结构的金属有机骨架（MOF）UiO?66?NH₂中聚合，获得UiO?66?NH₂/PAMPS杂化填料后将其加入磺化聚醚醚酮（SPEEK）中制备纳米复合质子交换膜，并对纳米填料和膜性能进行了测试和表征。其中，UiO?66?NH₂/PAMPS中MOF组分的有序孔洞能够为质子提供较为快速的传输通道，同时PAMPS组分上的磺酸基团则为这些通道提供了额外的质子传输位点，从而促进了复合膜中的质子传导。结果表明，填料与基体之间的强静电相互作用使复合膜的溶胀率有所下降；当填料含量达到6 %（质量分数，下同）时，复合膜的质子电导率（σ）从0.040 S/cm 提升到0.057 S/cm，比纯SPEEK高42.5 %，而溶胀率由29 %下降到23 %。

关键词: 质子交换膜, 磺化聚醚醚酮, 金属有机骨架, 2?丙烯酰胺?2?甲基丙磺酸

Abstract:

A UiO?66?NH₂/PAMPS hybrid filler was prepared through the in?situ polymerization of 2?acrylamide?2?methylpropanesulfonic acid in a porous metal organic framework （UiO?66?NH₂）. The resultant filler was then added to the sulfonated poly（ether ether ketone）（SPEEK） to fabricate nanocomposite membranes. The properties of the nanofillers and membranes were investigated. The ordered pore networks of metal organic framework components in UiO?66?NH₂/PAMPS provided fast proton diffusion pathways， and the sulfonic acid groups in PAMPS offered additional sites for proton transfer. This resulted in a significant improvement in proton conductivity of the nanocomposite membranes. The experimental results indicated that there is a strong electrostatic interaction between the filler and matrix， preventing the swelling of the nanocomposite membranes. When the filler content was 6 wt%， the proton conductivity of the nanocomposite membrane containing 6 wt% filler increased from 0.040 S/cm to 0.057 S/cm in water， which was 42.5 % higher than that of SPEEK as a control. Its swelling ratio decreased from 29 % to 23 %.

Key words: proton exchange membrane, sulfonated poly（ether ether ketone）, metal organic framework, 2?acrylamide?2?methylpropanesulfonic acid

中图分类号:

TQ325

王倩, 杨康宁, 翟绍雄, 尹立坤, 何少剑, 林俊. 高质子传导率及尺寸稳定性复合质子交换膜制备及性能研究[J]. 中国塑料, 2022, 36(8): 62-68.

WANG Qian, YANG Kangning, ZHAI Shaoxiong, YIN Likun, HE Shaojian, LIN Jun. Preparation and properties of composite proton exchange membranes with high proton conductivity and dimensional stability[J]. China Plastics, 2022, 36(8): 62-68.

图/表 10

图1 UiO?66?NH2和UiO?66?NH2/PAMPS的FTIR谱图

Fig.1 FTIR spectra of UiO?66?NH2 and UiO?66?NH2/PAMPS

图2 UiO?66?NH2和UiO?66?NH2/PAMPS的XRD谱图

Fig.2 XRD patterns of UiO?66?NH2 and UiO?66?NH2/PAMPS

图3 UiO?66?NH2和UiO?66?NH2/PAMPS的XPS 谱图

Fig.3 XPS spectra of UiO?66?NH2 and UiO?66?NH2/PAMPS

图4 纳米粒子的SEM照片

Fig.4 SEM images of the nano?particles

图5 膜的SEM照片

Fig.5 SEM images of the membranes

图6 纯SPEEK及复合膜的IEC

Fig.6 IEC of SPEEK and nanocomposite membranes

图7 纯SPEEK及复合膜的吸水率

Fig.7 Water absorption rate of SPEEK and composite membranes

图8 纯SPEEK及复合膜的溶胀率

Fig.8 Swelling ratio of SPEEK and composite membranes

图9 纯SPEEK及复合膜的σ

Fig.9 σ of SPEEK and composite membranes

图10 SPEEK和SPEEK/UiO?66?NH2/PAMPS?6膜的活化能

Fig.10 Activation energy of SPEEK and SPEEK/UiO?66?NH2/PAMPS?6 membrane

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高质子传导率及尺寸稳定性复合质子交换膜制备及性能研究

Preparation and properties of composite proton exchange membranes with high proton conductivity and dimensional stability

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