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

doi:10.7503/cjcu20140989

Abstract

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

CLC Number:

O631

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(4): 781.

Figures/Tables 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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