咪唑接枝交联型磺化聚醚醚酮质子交换膜的制备及在直接甲醇燃料电池中的应用

doi:10.7503/cjcu20180084

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (9): 2046.doi: 10.7503/cjcu20180084

咪唑接枝交联型磺化聚醚醚酮质子交换膜的制备及在直接甲醇燃料电池中的应用

朱星烨^1,², 钱汇东¹(), 蒋晶晶¹, 乐舟莹¹, 徐建峰¹, 邹志青¹, 杨辉¹()

1. 中国科学院上海高等研究院, 上海 201210
2. 中国科学院大学, 北京 100049

收稿日期:2018-01-25 出版日期:2018-09-07 发布日期:2018-03-26
作者简介:
联系人简介: 钱汇东, 男, 博士, 副研究员, 主要从事高分子膜材料研究. E-mail: qianhd@sari.ac.cn; 杨辉, 男, 博士, 研究员, 主要从事燃料电池和纳米电催化研究. E-mail: yangh@sari.ac.cn
基金资助:
国家自然科学基金(批准号: 21703280, 21706272)和中国科学院青年创新促进会(会员号: 2015233)资助.

Cross-linking of Imidazole-grafted Sulfonated Poly(ether ether ketone) as Proton Exchange Membranes for Direct Methanol Fuel Cells^†

ZHU Xingye^1,², QIAN Huidong^1,^*(), JIANG Jingjing¹, YUE Zhouying¹, XU Jianfeng¹, ZOU Zhiqing¹, YANG Hui^1,^*()

1. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-01-25 Online:2018-09-07 Published:2018-03-26
Contact: QIAN Huidong,YANG Hui E-mail:qianhd@sari.ac.cn;yangh@sari.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21703280, 21706272) and the Youth Innovation Promotion Association, Chinese Academy of Sciences(No.2015233).

摘要/Abstract

摘要：

通过咪唑接枝、共价交联制备出交联型咪唑改性磺化聚醚醚酮(SPEEK)质子交换膜. 通过接枝咪唑可以大幅提高质子电导率, 25 ℃下电导率可达0.14 S/cm, 高于Nafion膜(0.086 S/cm), 并随着交联度的增加, 质子电导率逐渐降低, 但交联膜的致密网络结构使得甲醇渗透明显降低, 当交联度为20%时膜的电导率和甲醇选择性分别高达0.105 S/cm和4.57×10⁵ S·s/cm³, 实现了质子电导和甲醇阻隔的均衡. 通过共价交联, 膜的氧化稳定性和尺寸稳定性大幅提升. 采用交联度为20%的改性SPEEK膜, 被动式直接甲醇燃料电池(DMFC)在25 ℃下的最大输出功率密度达29.7 mW/cm², 可与商业化Nafion 115膜相媲美, 展现出良好的应用前景.

关键词: 磺化聚醚醚酮, 质子交换膜, 咪唑接枝, 共价交联, 直接甲醇燃料电池

Abstract:

Sulfonated poly(ether ether ketone)(SPEEK) membrane is considered as a promising candidate to replace the Nafion membrane for the direct methanol fuel cell(DMFC) due to its high proton conductivity and excellent methanol resistance. However, the SPEEK always suffers the poor chemical stability. Herein, a novel imidazole functionalized cross-linked SPEEK membrane was synthesized via covalently cross-linked method. The results show that the modified SPEEK membrane exhibits greatly enhanced proton conductivity(0.14 S/cm at 25 ℃) in comparison with the Nafion 115 membrane(0.086 S/cm) by introducing the imidazole groups. Increasing the cross-linking degree of the membranes leads to a decrease in proton conductivity and a great reduction in methanol permeability due to the more compact network structure. When the cross-linking degree reaches 20%, the proton conductivity and methanol selectivity are 0.105 S/cm and 4.57×10⁵ S·s/cm³, respectively, demonstrating a good balance between proton conductor and methanol separator. Importantly, the oxidative and dimensional stabilities of cross-linked SPEEK membrane are significantly improved. A passive DMFC incorporated with the optimized Im-C-SPEEK-20 membrane delivers a peak power density of 29.7 mW/cm² at room temperature, close to that with Nafion 115(31.8 mW/cm²), suggesting a promising application potential in DMFCs.

Key words: Sulfonated poly(ether ether ketone), Proton exchange membrane, Imidazole grafting, Covalently cross-linking, Direct methanol fuel cell

中图分类号:

O631

TrendMD:

朱星烨, 钱汇东, 蒋晶晶, 乐舟莹, 徐建峰, 邹志青, 杨辉. 咪唑接枝交联型磺化聚醚醚酮质子交换膜的制备及在直接甲醇燃料电池中的应用. 高等学校化学学报, 2018, 39(9): 2046.

ZHU Xingye,QIAN Huidong,JIANG Jingjing,YUE Zhouying,XU Jianfeng,ZOU Zhiqing,YANG Hui. Cross-linking of Imidazole-grafted Sulfonated Poly(ether ether ketone) as Proton Exchange Membranes for Direct Methanol Fuel Cells^†. Chem. J. Chinese Universities, 2018, 39(9): 2046.

图/表 7

Scheme 1 Synthetic procedure of Im-C-SPEEK-x

Fig.1 1H NMR spectrum of Im-SPEEK in DMSO-d6

Fig.2 X-Ray diffraction patterns of various polymers

Table 1 Mechanical properties and oxidative stability of different PEMs

Sample	Tensile strength/MPa	Young's modulus/MPa	Elongation at break(%)	Residual weight, R_w(%)
SPEEK78	16.1	510.4	56.0	30.1
Im-SPEEK	11.9	308.0	203.1	93.6
Im-C-SPEEK-10	14.7	582.7	87.6	99.0
Im-C-SPEEK-20	15.4	626.9	76.0	99.2
Im-C-SPEEK-30	26.1	774.4	68.7	99.5
Nafion 115	27.8	41.2	304.4	99.9

Fig.3 Water uptake(A) and swelling ratio(B) of various membranes at the temperature range from 25 ℃ to 80 ℃

Table 2 Methanol permeability, proton conductivity at 25 ℃ and the corresponding methanol selectivity of PEMs

Sample	Methanol permeability/(cm²·s^-1)	Proton conductivity/(S·cm^-1)	Selectivity/(S·s·cm^-3)
Im-SPEEK	6.01×10^-7	0.140	2.33×10⁵
Im-C-SPEEK-10	3.33×10^-7	0.116	3.48×10⁵
Im-C-SPEEK-20	2.30×10^-7	0.105	4.57×10⁵
Im-C-SPEEK-30	2.08×10^-7	0.076	3.65×10⁵
SPEEK-78	6.84×10^-7	0.059	8.62×10⁴
Nafion 115	1.80×10^-6	0.086	4.78×10⁴

Fig.4 Polarization and power density curves of the passive DMFCs with Nafion 115 and Im-C-SPEEK-20 membrane(A) and transient discharging curves of the passive DMFCs with Im-C-SPEEK-20 and Nafion 115 at a constant voltage of 350 mV fueled with 5 mL of 4 mol/L MeOH at 25 ℃(B)

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咪唑接枝交联型磺化聚醚醚酮质子交换膜的制备及在直接甲醇燃料电池中的应用

Cross-linking of Imidazole-grafted Sulfonated Poly(ether ether ketone) as Proton Exchange Membranes for Direct Methanol Fuel Cells^†

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咪唑接枝交联型磺化聚醚醚酮质子交换膜的制备及在直接甲醇燃料电池中的应用

Cross-linking of Imidazole-grafted Sulfonated Poly(ether ether ketone) as Proton Exchange Membranes for Direct Methanol Fuel Cells†

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Cross-linking of Imidazole-grafted Sulfonated Poly(ether ether ketone) as Proton Exchange Membranes for Direct Methanol Fuel Cells^†