Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes†

doi:10.7503/cjcu20180049

Abstract

Abstract:

A polymerized ionic liquid copolymer composed of two ionic liquid precursors, 1-allyl-2-methylimidazole and 1-butyl-2-methylimidazole, and a poly(ionic liquid) main chain p(St-co-VBC) were synthesized via quaternization reaction to prepare anion exchange membranes(AEMs). The two ionic liquid precursors were synthesized from 2-methylimidazole. The poly(ionic liquid) main chain was prepared from styene(St) and p-chloromethylstyrene(VBC). The prepared membranes possessed crosslinked and comb shaped side-chain structure. Fourier transform infrared, scanning electron microscopy and thermogravimetry were used to investigate the molecule structure, morphology, hydroxide conductivity, thermal stability, alkaline stability and other properties of the membranes. The results showed that the AEMs had quite low water uptake, 36.7%—93.4%, and the ion exchange capacity was 1.61—2.16 mmol/g. The conductivity of p(St-co-VBC)-3 AEMs was as high as 68.4 mS/cm at 80 ℃. The AEMs displayed excellent alkaline stability and the hydroxide conductivity of p(St-co-VBC)-3 AEMs was still as high as 52.2 mS/cm after immersing in 1 mol/L NaOH solution for 240 h.

Key words: Bis-functional cross-linked, Comb-shaped structure, Anion exchange membrane, Hydroxide conductivity, Alkaline stability

CLC Number:

O631.5

TrendMD:

GUAN Mingming,CHEN Jia,TANG Shaokun. Synthesis and Performance of Novel Bis-functional Cross-linked Anion Exchange Membranes^†[J]. Chem. J. Chinese Universities, 2018, 39(9): 2054.

Figures/Tables 13

Scheme 1 Synthesis of 1-butyl-2-methylimidazole

Scheme 2 Preparation of 1-allyl-2-methylimidazole

Scheme 3 Synthetic procedure for bis-functional cross-linked AEMs

Fig.1 GPC chromatograms of synthesized p(St-co-VBC)-x[x=3(a), 4(b), 5(c)]

Fig.2 TGA curves of p(St-co-VBC)-x [x=3(a), 4(b), 5(c)]

Fig.3 Photograph of the AEMs(A), low(B) and high(C) magnification cross-sectional SEM images of AEMs

Fig.4 FTIR spectra of p(St-co-VBC)-x co-polymers(a) and AEMs(b)

Fig.5 Water uptake of p(St-co-VBC)-x AEMs

Fig.6 Ion exchange capacities of p(St-co-VBC)-x AEMs

Fig.7 Mechanical properties of p(St-co-VBS) AEMs

Fig.8 Temperature dependence of the hydroxyl conductivities of p(St-co-VBC)-x AEMs

Fig.9 Alkaline stability of p(St-co-VBC)-x AEMs

Table 1 Comparison of hydroxide conductivity with similar AEM materials

AEM material	Conductivity/(mS·cm^-1)	Ref.
AEMs containing mobile ion shuttles	189.0(90 ℃)	[20]
Imidazolium-functionalized poly(ether sulfone)	78.5(80 ℃)	[21]
Poly(2,6-dimethyl-1,4-phenyleneoxide) containing1,2,4,5-tetramethylimidazolium	60.0(80 ℃)	[22]
Imidazolium-poly(2,6-dimethyl-1,4-phenyleneoxide) blended with polyvinylalcohol	49.1(80 ℃)	[23]
Poly(styrene-co-vinylbenzylmethylimidazolium)	17.1(80 ℃)	[24]
p(St-co-VBC)-3 AEMs	68.4(80 ℃)	This work

References 27

[1]	Yi B.L., Fuel Cells-Principle, Technology, Application, Chemical Industry Press, Beijing, 2003
	(衣宝廉. 燃料电池-原理、技术、应用, 北京: 化学工业出版社, 2003)
[2]	Pan J., Chen C., Zhuang L., Lu J.T., Acc. Chem. Res., 2011, 45(3), 473—481
[3]	Zhang H., Shen P.K., Chem. Soc. Rev., 2012, 41(6), 2382—2394
[4]	Varcoe J. R., Atanassov P., Dekel D. R., Herring A. M., Hickner M. A., Kohl P. A., Kucernak A. R., Mustain W. E., Nijmeijer K., Scott K., Xu T. W., Zhuang L., Energy Environ. Sci., 2014, 7(10), 3135—3191
[5]	Zhou T., Shao R., Chen S., He X., Qiao J., Zhang J., J. Power Sources, 2015, 293, 946—975
[6]	Chen K. C., Ji M. D., Chem. J. Chinese Universities, 2016, 37(5), 989—995
	(陈康成, 纪梦蝶. 高等学校化学学报, 2016, 37(5), 989—995)
[7]	He G., Li Z., Zhao J., Wang S., Wu H., Guiver M. D., Jiang Z., Adv. Mater., 2015, 27(36), 5280—5295
[8]	Gil M., Ji X., Li X., Na H., Hampsey J. E., Lu Y. F., J. Membr Sci., 2010, 234(1), 75—81
[9]	Li N., Yan T., Li Z., Thurnalbrecht T., Binder W.H., Energy Environ. Sci., 2012, 5(7), 7888—7892
[10]	Li N., Zhang Q., Wang C., Lee Y. M., Guiver M. D., Macromolecules, 2012, 45(5), 2411—2419
[11]	Taylor L. D., Laughlin P. M., J. Appl. Polym. Sci., 1976, 20(8), 2225—2228
[12]	Thomas O. D., Soo K. J. W. Y., Peckham T. J., Kulkarni M. P., Holdcroft S., J. Am. Chem. Soc., 2012, 134(26), 10753—10756
[13]	Ran J., Wu L., He Y., Yang Z. J., Wang Y. M., Jiang C. X., Ge L., Bakangura E., Xu T. W., J. Membr. Sci., 2017, 522, 267—291
[14]	Peckham T. J., Holdcroft S., Adv. Mater., 2010, 22(42), 4667—4690
[15]	Wang L. M., Dou L. Y., Xin P., Chem. J. Chinese Universities, 2016, 37(7), 1408—1414
	(汪丽梅, 窦立岩, 辛鹏. 高等学校化学学报, 2016, 37(7), 1408—1414)
[16]	Jasti A., Shahi V.K., RSC Adv., 2014, 4(37), 19238—19241
[17]	Vengatesan S., Santhi S., Jeevanantham S., Sozhan G., J. Power Sources, 2015, 284, 361—368
[18]	Blair A., Kazerouni N., Cancer Causes and Control, 1997, 8(3), 473—490
[19]	Hugar K. M., Kostalik I. H. A., Coates G. W., J. Am. Chem. Soc., 2015, 137(27), 8730—8737
[20]	Wu L., Zhou G., Liu X., Zhang Z. H., Li C., Xu T. W., J. Membr. Sci., 2011, 371(1/2), 155—162
[21]	Yang J., Zheng J., Zhang J., Sun L., Chen F., Fan P., Zhong M., RSC Adv., 2015, 5(41), 32853—32861
[22]	Ge X., He Y., Guiver M. D., Wu L., Ran J., Yang Z., Xu T. W., Adv. Mater., 2016, 28(18), 3467—3472
[23]	Huang X. L., Lin C. X., Hu E. N., Soyekwo F., Zhang Q. G., Zhu A. M., Liu Q. L., RSC Adv., 2017, 7(44), 27342—27353
[24]	Zhu Y., He Y., Ge X., Liang X., Shehzad M.A., Hu M., Liu Y. Z., Wu L., Xu T. W., J. Mater. Chem. A., 2018, 6(2), 527—534
[25]	Han K. F., Yang Q. T., Yu S. P., Yu J. H., Zhu H., Wang Z. M., Chem. J. Chinese Universities, 2013, 34(10), 2437—2444
	(韩克飞, 杨起涛, 于书平, 于景华, 朱虹, 汪中明. 高等学校化学学报, 2013, 34(10), 2437—2444)
[26]	Jheng L. C., Tai C. K., Hsu L. C., Lin B. Y., Chen L., Wang B. C., Chiang L. K., Ko W. C., Int. J. Hydrogen Energy, 2017, 42(8), 5315—5326
[27]	Xu Y. X., Zhang J. C., Ye N. Y., Yang J. S., He R. H., Chem. J. Chinese Universities, 2017, 38(10), 1872—1879
	(徐一鑫, 张登骥, 叶妮雅, 杨景帅, 何荣桓. 高等学校化学学报, 2017, 38(10), 1872—1879)