高等学校化学学报

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (5): 1051.doi: 10.7503/cjcu20180785

• 高分子化学 • 上一篇    下一篇

填充型具有微孔结构的磺化聚芳醚砜/聚醚砜复合质子交换膜的制备及性能

朱雨昕, HARAGIRIMANA Alphonse, 陆瑶, BUREGEYA Ingabire Providence, 宁聪, 李娜, 胡朝霞(), 陈守文   

  1. 南京理工大学环境与生物工程学院, 南京 210094
  • 收稿日期:2018-11-21 出版日期:2019-05-06 发布日期:2019-05-09
  • 作者简介:

    联系人简介: 胡朝霞, 女, 博士, 副教授, 主要从事高分子电解质膜材料方面的研究. E-mail: huzhaoxia@njust.edu.cn

  • 基金资助:
    国家自然科学基金(批准号: 21276128, 21006052)和江苏省自然科学基金(批准号: BK20141398)资助.

Preparation and Properties of Filling-type Sulfonated Poly(arylene ether sulfone)/Poly(ether sulfone) Composite Membranes with Microporous Structures†

ZHU Yuxin, HARAGIRIMANA Alphonse, LU Yao, BUREGEYA Ingabire Providence, NING Cong, LI Na, HU Zhaoxia*(), CHEN Shouwen*   

  1. School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
  • Received:2018-11-21 Online:2019-05-06 Published:2019-05-09
  • Contact: HU Zhaoxia,CHEN Shouwen E-mail:huzhaoxia@njust.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21276128, 21006052) and the Natural Science Founation of Jiangsu Province, China(No.BK20141398)

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摘要：

制备了基于磺化聚芳醚砜(SPAES)及聚醚砜(PES)的填充型复合质子交换膜, 研究了其吸水率、 尺寸变化、 热-机械特性、 质子电导率、 甲醇透过性及稳定性等性能. 通过浸入沉淀相转化法, 采用磺化度分别为30%(S30), 40%(S40)及50%(S50)的SPAES与PES制备了系列微孔型复合质子交换膜 Sx-y(x为SPAES的磺化度, y为SPAES的质量分数); 然后利用真空抽滤法在微孔中填充S50制备了相应的填充型复合质子交换膜Sx-y+F50. 结果表明, 由于微孔的引入及皮层结构的存在, Sx-y膜在低离子交换容量(IEC)条件下仍具有较高的电导率、 优良的机械强度、 优异的化学稳定性及较低的甲醇透过性. 经S50填充后, Sx-y+F50膜的IEC及电导率明显提升, 甲醇透过率大幅下降, 但机械强度及化学稳定性未见劣化. 其中S30-40+F50膜(IEC=0.69 mmol/g)的综合性能最佳, 其质子电导率在90 ℃水中达到50.4 mS/cm; 经140 ℃水处理24 h后失重率仅为8.2%, 质子电导率降低仅9%; 经过芬顿试剂(3% H2O2, 20 mg/L FeSO4, 80 ℃, 1 h)处理后失重率仅为0.66%; 甲醇透过率仅为6.8×10-8 cm2/s.

关键词: 燃料电池, 浸入沉淀相转化, 填充型微孔复合质子交换膜, 磺化聚芳醚砜, 聚醚砜, 质子电导率

Abstract:

A series of filling-type composite polymer exchange membranes was prepared based on sulfonated poly(arylene ether sulfones)(SPAES) and poly(ether sulfone)s(PES), and the properties including water uptake, dimensional change, thermal-mechanical properties, proton conductivity, methanol permeability and chemical stability were evaluated. Firstly, a series of microporous composite proton exchange membranes(Sx-y, x refers to the sulfonation degree of the SPAES copolymers, y refers to the mass ratio(20%—40%) of SPAES copolymers) was fabricated via immersion phase inversion method from PES and SPAES copolymers with sulfonation degree of 30%(S30), 40%(S40) and 50%(S50). Then, the corresponding filling-type composite polymer exchange membranes(Sx-y+F50) were prepared by filling S50 in the Sx-y micropores by vacuum filtration. The results indicate that the Sx-y membranes, despite of the rather low ion exchange capacity(IEC), all display fairly high proton conductivity, fine mechanical strength, excellent chemical stability and rather low methanol permeability. After filling with S50, the corresponding Sx-y+F50 membranes exhibit improved IEC and proton conductivity, lowered methanol permeability, and maintain high mechanical strength and chemical stability. The S30-40+F50 membrane(IEC=0.69 mmol/g) shows the best comprehensive properties: proton conductivity of 50.4 mS/cm at 90 ℃ in water; mass loss of 8.2% and proton conductivity loss of 9% by aging in water at 140 ℃ for 24 h, and mass loss of 0.66% by soaking in Fenton reagent(3% H2O2, 20 mg/L FeSO4) at 80 ℃ for 1 h; methanol permeability of 6.8×10-8 cm2/s. The filling-type composite proton exchange membranes are promising candidates for fuel cell applications.

Key words: Fuel cell, Immersion phase transformation, Filling-type composite proton exchange membrane, Sulfonated poly(arylene ether sulfone), Poly(ether sulfone), Proton conductivity

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