Preparation of Polybenzimidazole/Polyvinylpyrrolidone Proton Exchange Membranes for Vanadium Redox Flow Battery†

doi:10.7503/cjcu20180720

Abstract

Abstract:

A series of proton exchange membranes(PEMs), based on polybenzimidazole(PBI) with different mass ratios of polyvinyl pyrrolidone(PVP) loadings, was prepared and investigated in vanadium redox flow battery(VRFB). The results showed that the addition of PVP effectively increased the water absorption, acid doping level(ADL) and proton conductivity of the PBI membrane. All membranes exhibit lower vanadium permeability than that of Nafion115 membrane, which were widely used in VRFB. Especially, the PBI/PVP-5 membrane exhibited higher bonded acid level of 2.47 mmol/g and proton conductivity of 4.81 mS/cm than that of PBI/PVP-0, as a result, the selectivity(3.12×10⁵ S·min·cm^-3) of PBI/PVP-5 is twice as much as the original PBI membrane(1.12×10⁵ S·min·cm^-3). At the current of 120 mA/cm², the voltage efficiency(VE=71.60%) and energy efficiency(EE=70.9%) of the cell employing PBI/PVP-5 increased about 10% compared with the original PBI membrane, respectively. The self-discharge time of VRFB assembled with PBI/PVP-5 reached to 307 h. All experimental results reported in this paper indicate that incorporation of PVP can increased water update(WU), ADL and proton conductivity of the PBI membrane at the same time. PBI/PVP proton exchange membranes, especially PBI/PVP-5 show promising prospects for VRFB applications.

Key words: Vanadium redox flow battery, Polybenzimidazole, Polyvinyl pyrrolidone, Proton conductivity, Cell efficiency, Proton exchange membrane

CLC Number:

O633.5

TrendMD:

SONG Xipeng, LIU Jinyu, WANG Lihua, HAN Xutong, HUANG Qinglin. Preparation of Polybenzimidazole/Polyvinylpyrrolidone Proton Exchange Membranes for Vanadium Redox Flow Battery^†[J]. Chem. J. Chinese Universities, 2019, 40(7): 1543.

Figures/Tables 14

Scheme 1 Structure of PBI

Scheme 2 Diffusion cell for measuring VO2+ permeability

Scheme 3 Assembly diagram of battery structure

Fig.1 FTIR spectra of PBI/PVP membranesa. PBI; b. PBI/PVP-5; c. PBI/PVP-10; d. PBI/PVP-15; e. PBI/PVP-20.

Fig.2 SEM cross-sectional images of PBI(A), PBI/PVP-5(B), PBI/PVP-10(C), PBI/PVP-15(D) and PBI/PVP-20(E)

Fig.3 Oxidative stability of PBI/PVP membranes (tested by Fenton reagent)a. PBI; b. PBI/PVP-5; c. PBI/PVP-10;d. PBI/PVP-15; e. PBI/PVP-20.

Fig.4 Mechanical properties of PBI/PVP membranesa. Nafion 115; b. PBI; c. PBI/PVP-5; d. PBI/PVP-10;e. PBI/PVP-15; f. PBI/PVP-20.

Table 1 Physicochemical properties of PBI/PVP membranes

Membrane	WU(%)	WU_doped(%)	ADL/(mmol·g^-1)	Free acid content/ (mmol·g^-1)	Bonded acid content/ (mmol·g^-1)	Thickness/μm
PBI	14.39	5.6	4.35	3.14	1.21	30
PBI/PVP-5	15.92	6.86	5.07	2.60	2.47	31
PBI/PVP-10	16.67	7.34	5.59	3.61	1.98	30
PBI/PVP-15	17.23	7.83	5.70	3.89	1.81	31
PBI/PVP-20	18.64	8.42	5.78	3.98	1.80	32

Fig.5 Vanadium ions concentration versus PBI/PVP membranes and Nafion115

Fig.6 Area resistance() and proton conductivity()(A) vanadium permeability() and proton selectivity() (B) of PBI/PVP membranesa. PBI; b. PBI/PVP-5; c. PBI/PVP-10; d. PBI/PVP-15; e. PBI/PVP-20.

Table 2 VRB single cell performance of PBI/PVP membranes

Membrane	50 mA/cm²			100 mA/cm²
Membrane	CE(%)	VE(%)	EE(%)	CE(%)	VE(%)	EE(%)
PBI	99.84	81.46	81.33	99.92	64.09	64/04
PBI/PVP-5	98.34	85.57	84.14	99.26	74.15	74.79
PBI/PVP-10	99.61	84.96	84.62	99.98	71.19	71.17
PBI/PVP-15	99.20	84.50	83.81	100.00	70.62	70.63
PBI/PVP-20	99.64	81.17	80.88	99.75	68.03	67.85

Fig.7 VRB efficiency assembled with PBI and PBI/PVP-5 at different current density(A) Columbic efficiency; (B) voltage efficiency; (C) energy efficiency.

Fig.8 Cyclic performance of VRB with PBI and PBI/PVP-5 at 100 mA/cm2 for 100 cycles(A) Columbic efficiency; (B) voltage efficiency; (C) energy efficiency.

Fig.9 Self-discharge curve of cell with PBI/PVP-5

References 30

[1]	Lü Z. Z., Hu S. L., Luo X. L., Wu Z. H., Chen L. Q., Qiu X. P., Chem. J. Chinese Universities, 2007, 28(1), 145—148
	(吕正中, 胡嵩林, 罗绚丽, 武增华, 陈立泉, 邱新平. 高等学校化学学报, 2007, 28(1), 145—148)
[2]	Skyllas-kazacos M., Rychcik M., Robins R. G., Fane A. G., Green M. A., Journal of Electrochem Society, 1986, 133(5), 1057—1058
[3]	Sum E., Rychcik M., Skyllas-Sazacos M., Journal of Power Sources, 1985, 16(2), 85—95
[4]	Sum E., Skyllas-Sazacos M., Journal of Power Sources, 1985, 15(2/3), 179—190
[5]	Ding C., Zhang H., Li X., Liu T., Xing F., The Journal of Physical Chemistry Letters, 2013, 4(8), 1281—1294
[6]	Faraji M., Hassanzadeh A., Mohseni M., Thin Solid Films, 2017, 642, 188—194
[7]	Wang Y., Wang S., Xiao M., Han D., Hickner M. A., Meng Y., RSC Advances, 2013, 3(35), 15467—15474
[8]	Nibel O., R ojek t., Schmidt T. J., Gubler L., Chem. Sus. Chem., 2017, 10(13), 2767—2777
[9]	Xiang Z., Zhao X.P., Ge J. J., Ma S. H., Zhang Y. W., Na H., Chem. Res. Chinese Universities, 2016, 32(2), 291—295
[10]	Xiao L., Zhang C., He M.Y., Chen K. C., Chem. J. Chinese Universities, 2018, 39(6), 1281—1289
	(肖磊, 张晨, 何美玉, 陈康成. 高等学校化学学报, 2018, 39(6), 1281—1289)
[11]	Huang L.H., He Y., Jin L. Y., Hou X. W., Miao L. Y., Lu C. L., Chem. Res. Chinese Universities, 2018, 34(2), 318—325
[12]	Qing S., Huang W., Yan D., Journal of Polymer Science Part A: Polymer Chemistry, 2005, 43(19), 4363—4372
[13]	Deimede V., Voyiatzis G.A., Kallitsis J. K., Qingfeng L., Bjerrum N. J., Macromolecules, 2000, 33(20), 7609—7617
[14]	Wang S., Zhao C.J., Ma W. J., Zhang N., Liu Z. G., Zhang G., Na H. Journal of Power Sources, 2013, 243, 102—109
[15]	Jang J.K., Kim T. H., Yoon S. J., Lee J. C., Hong Y. T., J. Mater. Chem. A, 2016, 4(37), 14342—14355
[16]	Lobato J., Canizares P., Rodrigo M.A., Linares J. J., Manjavacas G., Journal of Membrane Science, 2006, 280(1), 351—362
[17]	Xing B., Savadogo O., Journal of New Materials for Electrochemical Systems, 1999, 2(2), 95—102
[18]	Zhou X.L., Zhao T. S., An L., Wei L., Zhang C., Electrochimica Acta, 2015, 153, 492—498
[19]	Ding L.M., Song X. P., Wang L. H., Zhao Z. P., Journal of Membrane Science, 2019, 578, 126—139
[20]	Song X.P., Ding L. M, Wang L. H., He M. Han X. T., Electrochimica Acta, 2019, 295, 1034—1043
[21]	Ding L.M., Song X. P., Wang L. H., Zhao Z. P., He G. H., Electrochimica Acta, 2018, 292, 10—19
[22]	Yang S.H., Ahn Y. H., Kim D. J., Journal of Materials Chemistry A, 2017, 5(5), 2261—2270
[23]	Kim T.H., Kim S. K., Lim T. W., Lee J. C., Journal of Membrane Science, 2008, 323(2), 362—370
[24]	Kim S.K., Kim T. H., Jung J. W., Lee J. C., Polymer, 2009, 50(15), 3495—3502
[25]	Kumar V., Mondal S., Nandy A., Kundu P. P., Biochemical Engineering Journal, 2016, 111, 34—42
[26]	Pu H.T., Liu Q. Z., Qiao L., Yang Z. L., Polymer Engineering & Science, 2005, 45(10), 1395—1400
[27]	Liu S., Wang L.H., Li D., Liu B. Q., Wang J. J., Song Y. L., Journal of Materials Chemistry A, 2015, 3(34), 17590—17597
[28]	Qiu J.Y., Li M. Y., Ni J. F., Zhai M. L., Peng J., Xu L., Zhou H. H., Li J. Q., Wei G. S., Journal of Membrane Science, 2007, 297(1/2), 174—180
[29]	Xia Z.J., Ying L. B., Fang J. H., Du Y. Y., Zhang W. M., Guo X. X., Yin J., Journal of Membrane Science, 2017, 525, 229—239
[30]	Yuan Z.Z., Duan Y. Q., Zhang H. Z., Li X. F., Zhang H. M., Vankelecom I., Energy & Enviromental Science, 2016, 9, 441—447