用于甲醇燃料电池的聚砜阳离子交换膜的构⁃效关系

doi:10.19491/j.issn.1001-9278.2022.05.011

中国塑料 ›› 2022, Vol. 36 ›› Issue (5): 62-67.DOI: 10.19491/j.issn.1001-9278.2022.05.011

用于甲醇燃料电池的聚砜阳离子交换膜的构⁃效关系

乔宗文¹(), 邓嘉琪¹, 冀威²

^1.陕西国防工业职业技术学院，西安 710300
^2.西南科技大学化工学院，四川绵阳 621010

收稿日期:2022-01-07 出版日期:2022-05-26 发布日期:2022-05-26
作者简介:乔宗文（1987—），男，副教授，从事功能高分子的合成及性能研究，qiaozongwen@126.com
基金资助:
陕西省自然科学基金项目(2019JQ?927);陕西省教育厅自然科学研究计划项目(18JK0069);陕西国防学院自然科学研究计划(Gfy21?01)

Structure⁃activity relationship of polysulfone cation exchange membrane for methanol fuel cells

QIAO Zongwen¹(), DENG Jiaqi¹, JI Wei²

^1.Shaanxi Institute of Technology，Xi’an 710300，China
^2.Department of Chemical Engineering，Southwest University of Science and Technology，Mianyang 621010，China

Received:2022-01-07 Online:2022-05-26 Published:2022-05-26

摘要/Abstract

摘要：

基于酰基化反应制备了氯丁基化聚砜（BPS）和氯戊酰基化聚砜（VPS），再以8?羟基?1，3，6?芘三磺酸三钠（TS）为试剂经过亲核取代反应制备了侧链长度不同的芘磺酸型聚砜4PS?SA和5PS?SA，并采用注膜法制备了4PS?SA和5PS?SA系列阳离子交换膜；通过红外光谱仪（FTIR）、紫外?可见分光光度计、核磁共振仪（¹H?NMR）和原子力显微镜（AFM）测试和表征了其结构和磺酸基团含量，并探究了柔性侧链对其性能的影响。研究表明，4PS?SA和5PS?SA阳离子交换膜表现出良好的尺寸稳定性和阻醇性能；随着温度的升高，膜的吸水率、吸水溶胀率和质子传导率增加；在相同离子交换容量（IEC）下，具有较长侧链的5PS?SA尺寸稳定性和质子传导率更好，其中5PS?SA?3在室温和85 ℃下的溶胀率仅为23.7 %和39.1 %，质子传导率为0.093 S/cm和0.142 S/cm，甲醇扩散系数仅为7.09×10^-7 cm²/s，表现出很好的综合性能，有望用于阳离子交换膜燃料电池的实际生产应用。

关键词: 柔性侧链, 酰基化反应, 阳离子交换膜, 尺寸稳定性

Abstract:

Chloroprene polysulfone and chloroprene polysulfone were prepared through an acylation reaction， and then pyrene sulfonic acid polysulfones with different side chain lengths （4PS?SA and 5PS?SA） were prepared through a nucleophilic substitution reaction with 8?hydroxy?1，3，6?pyrene trisodium as a reagent. A series of 4PS?SA and 5PS?SA cation exchange membranes were prepared using a solution?casting method. The chemical structures， bonding amount of sulfo?nic acid groups， and effect of flexible side chains on the performance of pyrene sulfonic acid polysulfone cation exchange membranes were investigated using an infrared spectrometer， a UV?visible spectrophotometer， a nuclear magnetic resonance instrument， and an atomic force microscope. The result indicated that 4PS?SA and 5PS?SA cation exchange membranes exhibited an excellent dimensional stability and methanol resistance， and their water absorption rate， water swe?lling rate， and proton conductivity increased with an increase in temperature. The 5PS?SA with a longer side chain exhibi?ted a better dimensional stability and proton conductivity at the same ion exchange capacity. The 5PS?SA?3 showed water sorption rates of only 23.7 % and 39.1 % at room temperature and 85 oC， respectively. Its proton conductivities were 0.093 S/cm at room temperature and 0.142 S/cm at 85 oC， and its methanol permeability was only 7.09×10^-7cm²/s. These results indicated that the polysulfone cation exchange membranes had good comprehensive performance and were expected to be used for cation exchange membrane fuel cells.

Key words: flexible side chain, acylation reaction, cation exchange membrane, dimensional stability

中图分类号:

TQ326.55

乔宗文, 邓嘉琪, 冀威. 用于甲醇燃料电池的聚砜阳离子交换膜的构⁃效关系[J]. 中国塑料, 2022, 36(5): 62-67.

QIAO Zongwen, DENG Jiaqi, JI Wei. Structure⁃activity relationship of polysulfone cation exchange membrane for methanol fuel cells[J]. China Plastics, 2022, 36(5): 62-67.

图/表 8

图1 制备4PS?SA和5PS?SA的化学反应方程式

Fig.1 Reaction equation for preparation of 4PS?SA and 5PS?SA

图2 样品的FTIR谱图

Fig.2 FTIR spectra of the samples

图3 样品的1H?NMR谱图

Fig.3 1H?NMR spectra of the samples

图4 样品的吸水率?温度曲线

Fig.4 Water absorption rate?temperature curves of the samples

样品	BA/ mmol·g^-1	IEC/ mmol·g^-1	质量保留率/ %	甲醇扩散系数/ ×10⁷cm²·s^-1
4PS⁃SA⁃1	0.97	0.97	99.2	4.13
4PS⁃SA⁃2	1.27	1.27	98.6	6.31
4PS⁃SA⁃3	1.42	1.42	98.1	7.89
5PS⁃SA⁃1	0.98	0.97	99.5	4.07
5PS⁃SA⁃2	1.28	1.28	98.9	5.28
5PS⁃SA⁃3	1.42	1.42	98.3	7.09
Nafion115	—	0.90	98.0	16.80

表1 4PS?SA和5PS?SA阳离子交换膜的性能

Tab.1 Properties of 4PS?SA and 5PS?SA cation exchange membranes

图5 样品的溶胀率?温度曲线

Fig.5 Swelling rate?temperature curve of the samples

图6 样品的AFM照片（500 nm×500 nm）

Fig.6 AFM images of the samples（500 nm×500 nm）

图7 样品的质子传导率?温度曲线

Fig.7 Proton conductivity?temperature curve of the samples

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用于甲醇燃料电池的聚砜阳离子交换膜的构⁃效关系

Structure⁃activity relationship of polysulfone cation exchange membrane for methanol fuel cells

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