氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征

doi:10.16085/j.issn.1000-6613.2018-0430

化工进展 ›› 2018, Vol. 37 ›› Issue (12): 4758-4764.DOI: 10.16085/j.issn.1000-6613.2018-0430

氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征

张琪¹, 潘丽燕¹, 徐荣¹, 周守勇², 钟璟¹

1 常州大学石油化工学院, 江苏省绿色催化材料与技术重点实验室, 江苏常州 213164;
2 淮阴师范学院化学化工学院, 江苏省低维材料化学重点实验室, 江苏淮安 223300

收稿日期:2018-03-02 修回日期:2018-08-28 出版日期:2018-12-05 发布日期:2018-12-05
通讯作者: 钟璟,教授,硕士生导师,研究方向膜分离技术。
作者简介:张琪(1978-),女,博士,副教授,研究方向膜分离技术。E-mail:zhangqi@cczu.edu.cn。
基金资助:
国家自然科学基金（21306012）、江苏省绿色催化材料与技术实验室开放课题（BM2012110）、江苏省高校优势学科建设项目（PAPD）、江苏省产学研前瞻性联合研究项目（BY2016029-01）及常州大学先进催化与绿色制造协同创新中心支持项目。

Preparation and characterization of graphene oxide/sulfonated polybenzimidazole high temperature proton exchange membrane

ZHANG Qi¹, PAN Liyan¹, XU Rong¹, ZHOU Shouyong², ZHONG Jing¹

1 Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China;
2 School of Chemistry and Chemical Engineering, Huaiyin Normal University, Jiangsu Key Lab for Chemistry of Low-Dimensional Materials, Huai'an 223300, Jiangsu, China

Received:2018-03-02 Revised:2018-08-28 Online:2018-12-05 Published:2018-12-05

摘要/Abstract

摘要： 通过共混法和原位聚合法成功制备氧化石墨烯（GO）/磺化聚苯并咪唑（SPBI）质子交换复合膜。用FTIR及TEM表征了复合膜的结构，并测试了复合膜的热稳定性、力学性能、尺寸稳定性、含水率、酸掺杂率、氧化稳定性及质子电导率，重点考察不同制备方法、GO的加入对GO/SPBI质子交换复合膜结构和性能的影响。实验结果表明，GO在Y-GO/SPBI-1%复合膜中呈薄片状并良好分散。添加GO后复合膜的力学性能大幅提高，拉伸强度相较于Nafion 117膜（26.65MPa）提高了2.5倍。Y-GO/SPBI-1%复合膜热稳定性稍高于G-GO/SPBI-1%复合膜。Y-GO/SPBI-1%复合膜拥有与SPBI膜相当的含水率，比G-GO/SPBI-1%复合膜的含水率提高了51.36%，表明原位聚合法制备的膜具有良好的保水能力。原位聚合法制备的复合膜具有更高的酸掺杂率和更低的酸溶胀度，提高了膜的尺寸稳定性。Y-GO/SPBI-1%质子交换复合膜在相对湿度40%、160℃下具有最高的质子电导率0.113S/cm。GO上的含氧官能团有助于复合膜中质子的跳跃，原位聚合法使GO更均匀地分散在SPBI基质中，对复合膜质子电导率的提高起到关键作用。

关键词: 氧化石墨烯, 磺化聚苯并咪唑, 原位聚合法, 质子电导率, 高温质子交换膜

Abstract: The graphene oxide (GO)/sulfonatedpolybenzimidazole (SPBI) proton exchange composite membranes were successfully prepared by blending and in situ polymerization,respectively. The structure of the composite membranes was characterized by FT-IR and TEM. The thermal stabilities,mechanical properties,dimensional stability,water uptake,acid doping level,oxidative stability and proton conductivities of composite membranes were investigated. The effects of different preparation methods and the addition of GO on the structure and properties of proton exchange composite membranes were studied. The results showed that the GO in Y-GO/SPBI-1% composite membrane presented thin sheet and was well dispersed. After addition of GO,the mechanical properties of the composite membranes increased significantly,and the tensile strength increases by 2.5 times compared with Nafion 117 membrane (26.65MPa). The thermal stability of Y-GO/SPBI-1% composite membrane was slightly higher than G-GO/SPBI-1% composite membrane. The water uptake of Y-GO/SPBI-1% composite membrane was similar to that of SPBI membrane,which was 51.36% higher than that of G-GO/SPBI-1% composite membrane. The result showed that the membrane prepared by in situ polymerization had good water retention capability. The composite membrane prepared by in situ polymerization had higher acid doping level and lower acid swelling ratio. The dimensional stability of the composite membrane was improved. The Y-GO/SPBI-1% composite membrane had the highest proton conductivity of 0.113S/cm at 40% RH,160℃. The oxygen-containing functional groups on GO contributed to proton hopping in the composite membrane. The in situ polymerization made GO more uniformly dispersed in SPBI matrix and played a key role in improving the proton conductivity of the composite membrane.

Key words: graphene oxide, sulfonated polybenzimidazole, in situ polymerization, proton conductivity, high temperature proton exchange membrane

中图分类号:

TM911.4

张琪, 潘丽燕, 徐荣, 周守勇, 钟璟. 氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征[J]. 化工进展, 2018, 37(12): 4758-4764.

ZHANG Qi, PAN Liyan, XU Rong, ZHOU Shouyong, ZHONG Jing. Preparation and characterization of graphene oxide/sulfonated polybenzimidazole high temperature proton exchange membrane[J]. Chemical Industry and Engineering Progress, 2018, 37(12): 4758-4764.

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氧化石墨烯/磺化聚苯并咪唑高温质子交换膜的制备和表征

Preparation and characterization of graphene oxide/sulfonated polybenzimidazole high temperature proton exchange membrane

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