磺化聚芳醚酮砜/聚芳醚砜噁二唑复合型质子交换膜的制备与性能

doi:10.7503/cjcu20130897

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 639.doi: 10.7503/cjcu20130897

磺化聚芳醚酮砜/聚芳醚砜噁二唑复合型质子交换膜的制备与性能

马丽¹, 程海龙¹, 徐晶美¹, 王哲^1,²()

1. 长春工业大学化学工程学院
2. 材料科学高等研究院, 长春 130012

收稿日期:2013-09-13 出版日期:2014-03-10 发布日期:2019-08-01
作者简介:联系人简介: 王哲, 男, 博士, 教授, 主要从事燃料电池用质子交换膜的制备与性能研究. E-mail: wzccut@126.com
基金资助:
国家自然科学基金(批准号: 51273024, 51303015)和吉林省教育厅基金(批准号: 2012103)资助

Preparation and Performance of Sulfonated Poly(aryl ether ketone sulfone)/Poly(aryl ether sulfone oxadiazole) Composite Proton-exchange Membranes^†

MA Li¹, CHENG Hailong¹, XU Jingmei¹, WANG Zhe^1,^2,^*()

1. School of Chemical Engineering
2. Advanced Institute of Materials Science, Changchun University of Technology, Changchun 130012, China

Received:2013-09-13 Online:2014-03-10 Published:2019-08-01
Contact: WANG Zhe E-mail:wzccut@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51273024, 51303015) and the Foundation of Jilin Provincial Science & Technology Department, China(No.2012103)

摘要/Abstract

摘要：

为了降低质子交换膜(PEM)的甲醇渗透系数和改善PEM在中高温(80~120 ℃)时的质子传导率, 以自制的磺化度(SD)为100%的磺化聚芳醚酮砜(SPAEKS)与聚芳醚砜噁二唑(PAESO)为原料, 采用溶液共混法制备了SPAEKS/PAESO复合膜, 并用傅里叶变换红外光谱(FTIR)和热重分析(TGA)对其进行了表征. 结果表明, 该复合膜具有较好的化学稳定性和热稳定性. 扫描电子显微镜(SEM)照片显示, 复合膜具有较好的致密结构, 其甲醇渗透系数为3.9×10^-7~6.6×10^-7 cm²/s, 低于SPAEKS的8.7×10^-7 cm²/s. 在100 ℃时复合膜的质子传导率达到0.074 S/cm, 高于SPAEKS膜的0.066 S/cm.

关键词: 氮杂环, 噁二唑, 复合膜, 质子传导率

Abstract:

A serious of sulfonated poly(aryl ether ketone sulfone)/poly(aryl ether sulfone oxadiazole) composite membranes were prepared by solution blended method, to improve the performance of membranes for using in the condition of high-middle temperature(80—120 ℃). These prepared membranes were characte-rized by FTIR spectroscopy and thermo gravimetric analysis(TGA), and exhibited high thermal stability and good chemical stability. The SEM images showed that the composite membranes had compact structure. The composite membranes had low methanol diffusion coefficient properties(3.9×10^-7—6.6×10^-7 cm²/s), which were better than 8.7×10^-7 cm²/s of SPAEKS. Although the composite membranes displayed lower proton conductivities than the pure copolymer membranes at room temperature, the presence of nitrogen heterocyclic led to an improvement in high-temperature conductivity. The proton conductivity of SPAEKS/PAESO was found to be 0.074 S/cm at 100 ℃, which was higher than 0.066 S/cm of SPAEKS.

Key words: Nitrogen heterocyclic, Oxadiazole, Composite membrane, Proton conductivity

中图分类号:

O631

TrendMD:

马丽, 程海龙, 徐晶美, 王哲. 磺化聚芳醚酮砜/聚芳醚砜噁二唑复合型质子交换膜的制备与性能. 高等学校化学学报, 2014, 35(3): 639.

MA Li, CHENG Hailong, XU Jingmei, WANG Zhe. Preparation and Performance of Sulfonated Poly(aryl ether ketone sulfone)/Poly(aryl ether sulfone oxadiazole) Composite Proton-exchange Membranes^†. Chem. J. Chinese Universities, 2014, 35(3): 639.

图/表 12

Fig.1 Chemical formula of SPAEKS and BFO

Scheme 1 Synthetic route of PAESO

Scheme 2 Preparation process of SPAEKS/PAESO composite membranes

Fig.2 FTIR spectra of SPAEKS(a), PAESO(b) and S/P-2 composite membranes(c)

Fig.3 TGA curves of membranes a. S/P-0; b. S/P-1; c. S/P-2; d. S/P-3.

Table 1 Analytical data of SPAEKS membrane and S/P composite membranes

Sample	Oxidative stability(%)	10⁷Methanol diffusion coefficient/(cm²·s^-1)	10⁸Water diffusion coefficient at 80 ℃/(cm²·s^-1)	Proton conductivity/(S·cm^-1)
Sample	Oxidative stability(%)	10⁷Methanol diffusion coefficient/(cm²·s^-1)	10⁸Water diffusion coefficient at 80 ℃/(cm²·s^-1)	40 ℃	100 ℃
S/P-0	80	8.7	6.9	0.062	0.066
S/P-1	89	6.6	2.1	0.055	0.070
S/P-2	90	5.3	1.3	0.047	0.072
S/P-3	95	3.9	0.4	0.041	0.074

Fig.4 SEM images of SPAEKS membrane(A) and S/P-2 membrane(B)

Fig.5 Water desorption curves of membranes at 80 ℃ a. S/P-0; b. S/P-1; c. S/P-2; d. S/P-3.

Fig.6 Water uptake of membranes at different temperatures a. S/P-0; b. S/P-1; c. S/P-2; d. S/P-3.

Fig.7 Swelling ratio of membranes at different temperatures a. S/P-0; b. S/P-1; c. S/P-2; d. S/P-3.

Fig.8 Arrhenius plot for proton conductivity

Scheme 3 Proton conductivities principle of composite membranes

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磺化聚芳醚酮砜/聚芳醚砜噁二唑复合型质子交换膜的制备与性能

Preparation and Performance of Sulfonated Poly(aryl ether ketone sulfone)/Poly(aryl ether sulfone oxadiazole) Composite Proton-exchange Membranes^†

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磺化聚芳醚酮砜/聚芳醚砜噁二唑复合型质子交换膜的制备与性能

Preparation and Performance of Sulfonated Poly(aryl ether ketone sulfone)/Poly(aryl ether sulfone oxadiazole) Composite Proton-exchange Membranes†

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Preparation and Performance of Sulfonated Poly(aryl ether ketone sulfone)/Poly(aryl ether sulfone oxadiazole) Composite Proton-exchange Membranes^†