High Tempreture Fuel Cell Performance and Anisotropy of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimides Proton Exchange Membranes†

doi:10.7503/cjcu20150950

Abstract

Abstract:

Anisotropic properties of membrane swelling and proton conductivity of carbonyl and sulfone groups co-crosslinked sulfonated polyimides(SPI) proton exchange membranes(M1C, M2C) were reported in this paper. Fuel cell performance and durability under high temperature and relative low humidification were investigated in detail. The results showed that dimensional changes of M1C and M2C were lower than that of sulfone group crosslinked R1C in thickness and no obviously change in plane direction. The through-plane proton conductivities of M1C and M2C were significantly larger than that of R1C. The operation conditions of temperature, back pressureand relative humidity largely affected the proton exchange membrames of fuel cell(PEMFC) performance in connection with each other. The PEMFC performance of M1C was better than that of R1C in the similar conditions. At 90 ℃ and relatively high humidification of 82%RH, the crosslinked PEMs showed high fuel cell performances which were comparable to NR212. As the humidification reduced to 27% RH, the fuel cell performance of M1C largely decreased, but still kept in a reasonably high level and higher than that of R1C. With the operation temperature increased from 90 ℃ to 110 ℃, cell performances of all the SPI PEMs decreasedlargely. At 0.2 MPa and 49%RH, the maximum output of M1C was 21% higher than R1C. The maximum output of M1C largely increased from 0.17 W/cm² at 0.2 MPa to 0.38 W/cm² at 0.3 MPa. The PEMFC with M1C operated at 110 ℃ for 330 h without obviously degradation in cell performance. The result indicated that carbonyl and sulfone groups co-crosslinked SPI PEMs have high temperature fuel cell durability.

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

CLC Number:

O631

TrendMD:

CHEN Kangcheng, JI Mengdie. High Tempreture Fuel Cell Performance and Anisotropy of Carbonyl and Sulfone Groups Co-crosslinked Sulfonated Polyimides Proton Exchange Membranes^†[J]. Chem. J. Chinese Universities, 2016, 37(5): 989.

Figures/Tables 8

Table 1 Anisotropic properties of SPIs and Nafion(NR212) membranes

Sample	IEC^a/(meq·g^-1)	Δ $t c b$ (%)	Δ $l c b$ (%)	Δt/l	$σ / / c$ /(mS·cm^-1)	$σ ⊥ c$ /(mS·cm^-1)	σ_⊥///
M1	2.10	55	6.3	8.7	208	140	0.67
M1C	1.94	39	6.4	6.1	164	123	0.75
M2	1.99	41	5.6	7.3	183	130	0.71
M2C	1.87	34	6.2	5.5	160	119	0.74
R1	1.86	58	4.3	13	178	119	0.67
R1C	1.77	43	5.0	8.6	148	105	0.71
NR212	0.89	16	14	1.1	141	136	0.98

Table 1 Anisotropic properties of SPIs and Nafion(NR212) membranes

Sample	IEC^a/(meq·g^-1)	Δ $t c b$ (%)	Δ $l c b$ (%)	Δt/l	$σ / / c$ /(mS·cm^-1)	$σ ⊥ c$ /(mS·cm^-1)	σ_⊥///
M1	2.10	55	6.3	8.7	208	140	0.67
M1C	1.94	39	6.4	6.1	164	123	0.75
M2	1.99	41	5.6	7.3	183	130	0.71
M2C	1.87	34	6.2	5.5	160	119	0.74
R1	1.86	58	4.3	13	178	119	0.67
R1C	1.77	43	5.0	8.6	148	105	0.71
NR212	0.89	16	14	1.1	141	136	0.98

Fig.1 Stress-strain curves of M1C before(a) and after(b, c) aging in water at 140 ℃Time/h: b. 200; c. 500.

Table 2 Physical properties of M1C before and after aging in water

Time/h	Y^a/GPa	S^b/MPa	E^c(%)
	2.8	107	31
200	2.1	76	19
500	2.0	77	18

Table 3 PEFC performances of M1C, R1C and NR212 membranes

Conditions^a(℃/MPa/%RH)	Code	OCV/V	V_0.5/V	V_1.0/V	W_max/(W·cm^-2)	$σ ⊥ FC b$ /(mS·cm^-1)
90/0.2/82	M1C	0.96	0.70	0.62	0.87	61
	R1C	0.95	0.66	0.56	0.74	40
	NR 212	0.93	0.69	0.61	0.86	90
90/0.2/48	M1C	0.97	0.67	0.55	0.66	29
	R1C	0.95	0.59	0.44	0.46	22
	NR 212	0.94	0.68	0.69	0.75	70
90/0.2/27	M1C	0.95	0.51	0.38	0.39	20
	R1C	0.96	0.47	0.28	0.28	14
	NR 212	0.93	0.66	0.64	0.57	58
110/0.2/49	M1C	0.95	0.32		0.17	9
	R1C	0.92	0.23		0.14	6
110/0.3/49	M1C	0.96	0.62		0.38	17
	R1C	0.95	0.55		0.28	13

Table 3 PEFC performances of M1C, R1C and NR212 membranes

Conditions^a(℃/MPa/%RH)	Code	OCV/V	V_0.5/V	V_1.0/V	W_max/(W·cm^-2)	$σ ⊥ FC b$ /(mS·cm^-1)
90/0.2/82	M1C	0.96	0.70	0.62	0.87	61
	R1C	0.95	0.66	0.56	0.74	40
	NR 212	0.93	0.69	0.61	0.86	90
90/0.2/48	M1C	0.97	0.67	0.55	0.66	29
	R1C	0.95	0.59	0.44	0.46	22
	NR 212	0.94	0.68	0.69	0.75	70
90/0.2/27	M1C	0.95	0.51	0.38	0.39	20
	R1C	0.96	0.47	0.28	0.28	14
	NR 212	0.93	0.66	0.64	0.57	58
110/0.2/49	M1C	0.95	0.32		0.17	9
	R1C	0.92	0.23		0.14	6
110/0.3/49	M1C	0.96	0.62		0.38	17
	R1C	0.95	0.55		0.28	13

Fig.2 Cell volatage(a, b) and power output(c, d) of M1C(a, c) and R1C(b, d) membranes at 90 ℃ and gas pressure of 0.2 MPa under different relative humidities of 82%RH(A), 48%RH(B) and 27%RH(C)

Fig.3 Cell volcotage(a, b) and power output(c, d) of M1C(a, c) and R1C(b, d) membranes at 110 ℃ under relative humidities of 49% and gas pressure of 0.2(A) and 0.3 MPa(B)

Fig.4 Durability test of PEFC with SO2- and CO-crosslinked SPI membranes(M1C) at 110 ℃, 0.3 MPa, relative humidities of 50%

Table 4 Durability of PEMFC

Code No.	T/℃	RH(%)	P/MPa	I/(A·cm^-2)	Time/h	v/(μV·h^-1)	Ref.
SPI-8	80	100	0.1	0.2	5000	12	[25]
M1A	90	82	0.3	0.5	1600	69	[26]
BT2	90	50	0.2	0.5	283	106	[27]
MX2	110	49	0.2	0^*	1000	180	[28]
CMB2	110	50	0.3	0.2	200	133	[29]
M1C	110	49	0.3	0.2	330	91	This paper

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