羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能

doi:10.7503/cjcu20140989

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (4): 781.doi: 10.7503/cjcu20140989

羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能

陈康成, 白文馨, 赵之平(), 刘文芳, 杨智

北京理工大学化工与环境学院, 北京 100081

收稿日期:2014-11-07 出版日期:2015-04-10 发布日期:2015-03-18
作者简介:联系人简介: 赵之平, 男, 博士, 教授, 博士生导师, 主要从事功能膜与膜分离研究. E-mail: zhaozp@bit.edu.cn
基金资助:
国家自然科学基金青年基金(批准号: 21306010)、教育部博士点新教师基金(批准号: 20121101120037)和校基础研究基金(批准号: 20131042001)资助

Preparation and Fuel Cell Performance of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimide Proton Exchange Membranes^†

CHEN Kangcheng, BAI Wenxin, ZHAO Zhiping^*(), LIU Wenfang, YANG Zhi

School of Chemical Engineering and the Environment, Beijing Institute of Technology, Beijing 100081, China

Received:2014-11-07 Online:2015-04-10 Published:2015-03-18
Contact: ZHAO Zhiping E-mail:zhaozp@bit.edu.cn
Supported by:
† Supported by the Young Scientists Fund of the National Natural Science Foundation of China(No.21306010), the Specialized Research the Doctoral Program of Higher Education of China(New Teachers)(No.20121101120037) and the Fund for Foundation Sciences Beijing Institute of Technology, China(No.20131042001)

摘要/Abstract

摘要：

为提高磺化聚酰亚胺质子交换膜(SPI PEM)的高温耐水解稳定性及电池性能, 用3,5-双(4-氨基苯氧基)苯甲酸(BAPBa)制备了一系列六元环型SPI PEM, 利用甲磺酸/五氧化二磷溶液(PPMA)制备了羰基和砜基共交联的SPI PEM. 测定了SPI PEM的质子传导率、耐水解稳定性、机械性能及电池性能. 结果表明, 羰基和砜基共交联提高膜交联度的同时减少了磺酸基的消耗, 使SPI PEM保持较高的质子传导率. 在相对湿度为50%RH时, 羰基和砜基共交联SPI PEM的质子传导率为7.8 mS/cm, 比同样条件下砜基交联的SPI PEM提高28%. 羰基和砜基共交联的SPI PEM 在130 ℃ 水中老化500 h后断裂伸长率为18%, 质子传导率未明显降低. 羰基和砜基共交联SPI PEM作为电池时, 最大功率密度达到0.85 W/cm², 是砜基交联PEM的1.3倍.

关键词: 羰基和砜基共交联, 质子交换膜, 磺化聚酰亚胺, 燃料电池

Abstract:

A series of six-membered ring type SPI PEMs was synthesized with 3,5-bis(4-aminophenoxy) benzoic acid(BAPBa). Carbonyl and sulfone co-crosslinked SPI PEMs were prepared by methanesulfonic acid/phosphorus pentoxide solution(PPMA). Their properties including proton conductivity, hydrolysis resistance, mechanical properties and fuel cell performance were investigated. The results showed that the crosslinking degree of carbonyl and sulfone co-crosslinked SPI PEMs increased, while the consumption of sulfonic acid group decreased, which kept the SPI PEMs maintaining high proton conductivity when compared to the sulfone groups crosslinked ones. For example, the proton conductivity of the carbonyl and sulfone co-crosslinked SPI PEM was 7.8 mS/cm at 50%RH, which increased by 28%. After aging in water at 130 ℃ for 500 h, elongation at break of the carbonyl and sulfone co-crosslinked SPI PEM was 18% and no obvious reduction in proton conductivity. Fuel cell performance showed that, the maximum power output of the carbonyl and sulfone co-crosslinked SPI PEM reached 0.85 W/cm², which was 1.3 times higher than that of sulfone crosslinked one.

Key words: Carbonyl and sulfone co-crosslinked, Proton exchange membrane, Sulfonated polyimide, Fuel cell

中图分类号:

O631

TrendMD:

陈康成, 白文馨, 赵之平, 刘文芳, 杨智. 羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能. 高等学校化学学报, 2015, 36(4): 781.

CHEN Kangcheng, BAI Wenxin, ZHAO Zhiping, LIU Wenfang, YANG Zhi. Preparation and Fuel Cell Performance of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimide Proton Exchange Membranes^†. Chem. J. Chinese Universities, 2015, 36(4): 781.

图/表 7

Fig.1 Chemical structure of SPI

Fig.2 Carbonyl and sulfone groups co-crosslinked SPIs

Fig.3 FTIR spectra of M1(a) and M1C(b)

Table 1 Physical properties of BSPOB-based SPIs

Code	IEC^a/(mmol·g^-1)		$η r b$ /(dL·g^-1)	WU^c (%)	λ^d	Dimensional change^c(%)
Code	—SO₃H		$η r b$ /(dL·g^-1)	WU^c (%)	—COOH	Δt_c	Δl_c
M1	1.95(1.83)	0. 24(0.23)	7.4	96	29	55	6.3
M1C	(1.78)	(0.12)		82	25	39	6.4
M2	1.95(1.83)	0.12(0.11)	8.9	83	25	41	5.6
M2C	(1.77)	(0.04)		72	23	34	6.2
R1	1.96(1.86)		7.5	76	23	58	4.3
R1C	(1.77)			72	22	43	5.0
NR212	0.91(0.89)			39	24	16	14

Table 1 Physical properties of BSPOB-based SPIs

Code	IEC^a/(mmol·g^-1)		$η r b$ /(dL·g^-1)	WU^c (%)	λ^d	Dimensional change^c(%)
Code	—SO₃H		$η r b$ /(dL·g^-1)	WU^c (%)	—COOH	Δt_c	Δl_c
M1	1.95(1.83)	0. 24(0.23)	7.4	96	29	55	6.3
M1C	(1.78)	(0.12)		82	25	39	6.4
M2	1.95(1.83)	0.12(0.11)	8.9	83	25	41	5.6
M2C	(1.77)	(0.04)		72	23	34	6.2
R1	1.96(1.86)		7.5	76	23	58	4.3
R1C	(1.77)			72	22	43	5.0
NR212	0.91(0.89)			39	24	16	14

Table 2 Physical properties of BSPOB-based SPIs before and after aging in water

Code	Time/h	ML^a(%)	σ^b/(mS·cm^-1)			Y^c/GPa	S^d/MPa	E^e(%)
Code	Time/h	ML^a(%)	50%RH			Y^c/GPa	70%RH	in water
M1			12	44	208	2.8	112	65
	200	14	11	46	199	2.3	68	6.5
M1C			7.8	34	163	2.8	113	31
	500	12	6.4	29	160	2.1	76	18
M2			9.5	37	183	2.9	107	44
	200	15	7.6	32	168	2.3	59	7
M2C			7.1	31	163	2.4	76	20
	500	14	5.6	28	158	2.1	67	13
R1			7.2	33	165	2.6	128	51
	500	12	7.0	32	160	1.5	52	10
R1C			6.1	27	148	2.5	103	26
	500	12	5.7	24	141	1.8	80	14
NR212			30	59	141	0.24	40	380

Fig.4 Relative humidity dependence of proton conductivity of M1(a), M1C(b), R1C(c) and NR212(d) membranes at 60 ℃

Fig.5 PEMFC performances for M1C(■ □), R1C(● ○),NR212(▲ △) membranes at 90 ℃, 0.1 MPa, 82%RH

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羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能

Preparation and Fuel Cell Performance of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimide Proton Exchange Membranes^†

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羰基和砜基共交联磺化聚酰亚胺质子交换膜的制备及燃料电池性能

Preparation and Fuel Cell Performance of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimide Proton Exchange Membranes†

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Preparation and Fuel Cell Performance of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimide Proton Exchange Membranes^†