羰基和砜基共交联磺化聚酰亚胺质子交换膜的高温燃料电池性能及各向异性

doi:10.7503/cjcu20150950

摘要/Abstract

摘要：

研究了羰基和砜基共交联聚酰亚胺膜M1C和M2C的膜溶胀和质子传导的各向异性, 以及在高温和低湿度条件下燃料电池的发电和耐久性能. 研究结果表明, M1C和M2C膜厚方向溶胀比砜基交联质子交换膜(R1C)的小, 且无显著的膜面方向尺寸变化. M1C和M2C的膜厚方向质子传导率明显大于R1C. 温度、压力和相对湿度在很大程度上影响了燃料电池的性能. 在相同条件下, M1C的燃料电池发电性能优于R1C. 90 ℃时, 较高的相对湿度(RH)82%下, M1C和R1C具有与Nafion相近的发电性能; 随着相对湿度降低到27%, M1C的电池性能显著降低, 但仍高于R1C. 随着操作温度从90 ℃提高到110 ℃, 所有质子交换膜的性能都大幅下降. 在0.2 MPa及RH为49%时, M1C的最大输出功率比R1C高21%. 当电池压力上升至0.3 MPa后, M1C的最大输出功率从0.2 MPa时的0.17 W/cm²提高到0.38 W/cm². M1C在110℃下连续运行330 h后性能未见明显下降, 说明羰基和砜基共交联的磺化聚酰亚胺质子交换膜具有良好的高温燃料电池耐久性能.

关键词: 羰基和砜基共交联, 磺化聚酰亚胺, 各向异性, 质子交换膜, 燃料电池性能

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

中图分类号:

O631

TrendMD:

陈康成, 纪梦蝶. 羰基和砜基共交联磺化聚酰亚胺质子交换膜的高温燃料电池性能及各向异性. 高等学校化学学报, 2016, 37(5): 989.

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

图/表 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

参考文献 29

[1]	Yi B.L., Fuel Cell, Chemical Industry Press, Beijing, 2000, 56—100
	(衣宝廉. 燃料电池, 北京:化学工业出版社, 2000, 56—100)
[2]	Song Y., Jin Y. H., Liang Q. J., Li K. C., Zhang Y. H., Hu W., Jiang Z. H., Liu B., J. Power Sources,2013, 238, 236—244
[3]	Tang W. F., Ling Y., Chen S. S., Hu Z. X., Chen S. W., Chem. J. Chinese Universities,2013, 34(11), 2661—2666
	(唐卫芬, 凌瑛, 陈珊珊, 胡朝霞, 陈守文. 高等学校化学学报, 2013, 34(11), 2661—2666)
[4]	Elabd Y. A., Napadensky E., Walker C. W., Winey K. I., Macromol., 2006, 39(1), 399—407
[5]	Chen K. C., Chen X. B., Yaguchi K., Endo N., Higa M., Okamoto K., Polym., 2009, 50(2), 510—518
[6]	Yin Y., Fang J. H., Cui Y. F., Tanaka K., Kita H., Okamoto K., Polym., 2003, 44(16), 4509—4518
[7]	Hu Z. X., Yin Y., Yaguchi K., Endo N., Higa M., Okamoto K., Polym., 2009, 50(13), 2933—2943
[8]	Yamada O., Yin Y., Tanaka K., Kita H., Okamoto K., Electrochim.Acta,2005, 50(13), 2655—2659
[9]	Mauriz K. A., Moore R. B., Chem. Rev., 2004, 104(10), 4535—4585
[10]	Chen K. C., Bai W. X., Zhao Z. P., Liu W. F., Yang Z., Chem. J. Chinese Universities,2015, 36(4), 781—787
	(陈康成, 白文馨, 赵之平, 刘文芳, 杨智. 高等学校化学学报, 2015, 36(4), 781—787)
[11]	Guo X. X., Fang J. H., Watari T., Tanaka K., Kita H., Okamoto K., Macromol., 2002, 35(17), 6707—6713
[12]	Yin Y., Suto Y., Sakabe T., Chen S. W., Hayashi S., Mishima T., Yamada O., Tanaka K., Kita H., Kamoto K., Macromol., 2006, 39(3), 1189—1198
[13]	Genies C., Mercier R., Sillion B., Petiaud R., Cornet N., Gebel G., Pineri M., Polym., 2001, 42(12), 5097—5105
[14]	Chen X. B., Chen P., An Z. W., Chen K. C., Okamoto K., J. Power Sources,2011, 196, 1694—1703
[15]	Yao H. Y., Feng P. J., Liu P., Liu B. J., Zhang Y. H., Guan S. W., Jiang Z. H., Polym. Chem, 2015, 6(14), 262—269
[16]	Kreitmeier S., Schuler G. A., Wokaun A., Büchi F. N., J. Power Sources,2012, 212, 139—147
[17]	Okamoto K., Yaguchi K., Yamamoto H., Chen K. C., Endo N., Higa M., Kita H., J. Power Sources,2010, 195, 5856—5861
[18]	Cleghorn S. J., Mayfield D. K., Moore D. A., Moore J. C., Rusch G., Sherman T. W., Sisofo N. T., Beuscher U., J.Power Sources,2006, 158, 446—454
[19]	Hu Z. X., Yin Y., Okamoto K., Moriyama Y., Morikawa A., J. Membrane Sci, 2009, 329(1), 146—152
[20]	Samms S. R., Wasmus S., Savinell R. F., J. Electrochem. Soc., 1996, 143(5), 1498—1504
[21]	Aoki M., Chikashige Y., Miyatake K., Uchida H., Watanabe M., Electrochem. Com, 2006, 8(9), 1412—1416
[22]	Chen K.C., Han D. B., Zhao Z. P., Liu W. F.,Acta Polymerica Sinica, 2015, (6), 633—640
	(陈康成, 韩丁波, 赵之平, 刘文芳. 高分子学报, 2015, (6), 633—640)
[23]	Aoki M., Asano N., Miyatake K., Uchida H., Watanabe M., J.Electrochem. Soc., 2006, 153(6), A1154—A1158
[24]	Zhang X., Hua Z. X., Pu Y. L., Chen S. S., Ling J. N., Bi H. P., Chen S. W., Wang L. J., Okamoto K., J. Power Sources,2012, 216, 261—268
[25]	Kabasawa A., Saito J., Miyatake K., Uchida H., Watanabe M., Electrochim. Acta,2009, 54(10), 2754—2760
[26]	Endo N., Matsuda K., Yaguchi K., Hu Z. X., Chen K. C., Higa M., Okamoto K., J. Electrochem. Soc., 2009, 156(5), B628—633
[27]	Chen S. W., Hara R., Chen K. C., Zhang X., Endo N., Higa M., Okamoto K., Wang L. J., J. Mater. Chem. A,2013, 1(28), 8178—8189
[28]	Yaguchi K., Chen K. C., Endo N., Higa M., Okamoto K., J. Power Sources,2010, 195(15), 4676—4684
[29]	Chen S. W., Zhang X., Chen K. C., Endo N., Higa M., Okamoto K., Wang L. J., J. Power Sources,2011, 196, 9946—9954