<strong>SPES-C/MIL-53(Al)-SO<sub>3</sub>H</strong>杂化质子交换膜的制备和性能

doi:10.11901/1005.3093.2019.140

材料研究学报

2019, Vol. 33

Issue (9): 691-698 DOI: 10.11901/1005.3093.2019.140

研究论文

本期目录 | 过刊浏览

SPES-C/MIL-53(Al)-SO₃H杂化质子交换膜的制备和性能

韩光鲁(

),陈哲,蔡立芳,田俊峰,张学波,马环环

郑州轻工业大学材料与化学工程学院郑州 450001

Preparation and Properties of Hybrid Proton Exchange Membranes of SPES-C/MIL-53(Al)-SO₃H

HAN Guanglu(

),CHEN Zhe,CAI Lifang,TIAN Junfeng,ZHANG Xuebo,MA Huanhuan

School of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450001, China

引用本文:

韩光鲁,陈哲,蔡立芳,田俊峰,张学波,马环环. SPES-C/MIL-53(Al)-SO₃H杂化质子交换膜的制备和性能[J]. 材料研究学报, 2019, 33(9): 691-698.
Guanglu HAN, Zhe CHEN, Lifang CAI, Junfeng TIAN, Xuebo ZHANG, Huanhuan MA. Preparation and Properties of Hybrid Proton Exchange Membranes of SPES-C/MIL-53(Al)-SO₃H[J]. Chinese Journal of Materials Research, 2019, 33(9): 691-698.

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摘要:

用水热合成法制备MIL-53(Al)，然后用后磺化法在其笼状结构中引入磺酸基团得到MIL-53(Al)-SO₃H纳米级金属有机框架(MOF)多孔晶体材料，最后将MIL-53(Al)-SO₃H掺杂到磺化酚酞侧基聚芳醚砜(SPES-C)高分子相中制备出一系列SPES-C/MIL-53(Al)-SO₃H燃料电池用杂化质子交换膜(PEM)。扫描电镜观测结果表明，杂化质子交换膜内没有缺陷，MIL-53(Al)-SO₃H在膜内分散均匀且两相的相容性好。热重分析结果证实，杂化膜具有优良的热稳定性。MIL-53(Al)-SO₃H的加入，提高了杂化膜的吸水率、尺寸稳定性和质子传导率。在温度为80℃时填充量为5%（质量分数）的杂化膜其M-5的质子传导率达到0.15 S·cm^-1，比纯SPES-C膜提高了32.5%且优于商用Nafion膜的质子传导率(0.134 S·cm^-1)。

关键词 ：复合材料, 质子交换膜, 磺化酚酞侧基聚芳醚砜, 磺化金属-有机框架

Abstract：

MIL-53(Al) was synthesized through hydrothermal synthesis, then sulfonic groups were introduced into MIL-53(Al) cages by sulfonation reaction to obtain MIL-53(Al)-SO₃H with proton conduction property. The post-synthetic MIL-53(Al)-SO₃H was incorporated into sulfonated polyarylethersulfone with cardo (SPES-C) polymer matrix to form hybrid PEMs. SEM results show that MIL-53(Al)-SO₃H dispersed uniformly in SPES-C phase and no obvious interfacial defects in membranes could be observed. The TGA analysis confirmed that the membranes of PEMs have excellent thermal stability. The water uptake was enhanced with embedding MIL-53(Al)-SO₃H and it presented positive correlation with composition. The incorporation of MIL-53(Al)-SO₃H also inhibited the swelling ratio, indicating the excellent dimensional stability of the as-prepared hybrid PEMs. The hybrid PEMs also showed encouraging proton conductivity. The proton conductivity of the hybrid PEMs with incorporation amount of 5% (in mass fraction) MIL-53(Al)-SO₃H reached to 0.15 S·cm^-1, which was 32.5% higher than that of the pristine SPES-C membrane, and exceeded that of the ordinary commercial Nafion membrane (0.134 S·cm^-1).

Key words： composite proton exchange membrane sulfonated polyarylethersulfone sulfonated MOF

收稿日期: 2019-03-06

ZTFLH:

TB 332

基金资助:国家自然科学基金(21606211);河南省科技计划基础与前沿技术研究计划(152300410127);郑州轻工业学院博士科研基金(2014BSJJ056)

作者简介: 韩光鲁，男，1985年生，博士

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https://www.cjmr.org/CN/10.11901/1005.3093.2019.140 或 https://www.cjmr.org/CN/Y2019/V33/I9/691

图1 MIL-53(Al)和MIL-53(Al)-SO3H的红外光谱

图2 MIL-53(Al)和MIL-53(Al)-SO3H的XRD谱

图3 MIL-53(Al) 和MIL-53(Al)-SO3H 的SEM图

图4 MIL-53(Al)-SO3H和MIL-53(Al)的粒度分布

图5 SPES-C、M-1、M-3、M-5的表面和截面SEM照片以及M-5截面Al元素的EDS谱

图6 SPES-C, M-1，M-3和M-5的TGA曲线

图7 SPES-C膜和杂化膜的力学性能

图8 SPES-C膜和杂化膜在不同温度下的吸水率

图9 SPES-C膜和杂化膜的空穴半径和自由体积分数

图10 SPES-C膜和杂化膜在不同温度下的溶胀度

图11 SPES-C膜和杂化膜在不同温度下的质子传导率

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