离子液体在质子交换膜中的应用研究进展
作者:石倩茹,陶慷,章勤,薛立新,张尧剑
单位: 中国科学院宁波材料技术与工程研究所,315201
关键词: 质子交换膜;离子液体;质子传递
出版年,卷(期):页码: 2013,33(3):113-120

摘要:
质子交换膜是质子交换膜燃料电池(PEMFC)的核心元件之一,以Nafion为代表的全氟磺酸膜的电导率强烈依赖于水含量,而以磺化聚醚醚酮(SPEEK)为代表的磺化芳香族聚合物膜电导率依然有需要改善的空间,这些限制了PEMFC进一步的发展。离子液体具有较高的电导率,优异的热稳定性、电化学稳定性,且不挥发,因此可以替代水在高温下作为质子传递介质,应用于传统质子交换膜性能提升的改性,提高膜的质子电导率和使用温度。本文对近年来离子液体在SPEEK、PS、PBI、PI、PVDF、Nafion等树脂中的应用及质子传递机理做了综述,阐述了应用中存在的问题及对策,并对研究前景做了展望。
Proton exchange membrane is a crucial part of proton exchange membrane fuel cell (PEMFC). Perfluorosulphonic acid based membranes such as NafionTM (Dupont), which has been mainly used for polymer electrolyte of PEMFCs, failed to maintain its high ionic conductivity when used in non-humid and high temperature conditions. Sulfonated aromatic polymer membranes such as sulfonated poly(ether-ether ketone) (SPEEK) suffers from relatively low ionic conductivity. Ionic liquids (ILs) show high ionic conductivity, excellent thermal and electrochemical stability, as well as negligible vapor pressure, which make them attractive to be introduced to polymer electrolyte membranes as proton transporting media to replace water for elevated temperature operation. This review covers the application of ILs in SPEEK, PS, PBI, PI, PVDF and Nafion, and the proton transfer mechanism. Finally, the problems and developmental direction are suggested.
石倩茹(1990-),女,江苏盐城人,硕士生,从事膜材料制备及应用研究。通讯联系人*,Email: taokang@nimte.ac.cn, xuelx@nimte.ac.cn,

参考文献:
[1] Devanathan R. Recent developments in proton exchange membranes for fuel cells[J]. Energy Environ Sci, 2008. 1(1): 101-119.
[2] Li Qingfeng, He Ronghuan, Jensen J O, et al. Approaches and recent development of polymer electrolyte membranes for fuel cells operating above 100℃[J]. Chem Mater, 2003, 15(26): 4896-4915.
[3] Bosea S, Kuila T, Nguyenb T X H, et al. Polymer membranes for high temperature proton exchange membrane fuel cell: Recent advances and challenges[J]. Prog Polym Sci, 2011, 36(6):813-843.
[4] Hickner M A, Ghassemi H, Kim Y S, et al. Alternative polymer systems for proton exchange membranes (PEMs)[J]. Chem Rev, 2004, 104(10): 4587-4612.
[5] 浦鸿汀, 罗浩川, 常志宏, 袁俊杰. 离子液体在聚合物质子导电材料中的应用研究展[J]. 高分子材料科学与工程, 2009, 25(10):153-156.
[6] Padilha J C, Basso J, da Trindade L G, et al. Ionic liquids in proton exchangemembrane fuel cells: Efficient systems for energy generation [J]. J Power Sources, 2010, 195 (19): 6483-6485.
[7] Schäfer T, Paolo R E D, Franco R, et al. Elucidating interactions of ionic liquids with polymer films using confocal Raman spectroscopy[J]. Chem Commun, 2005, (20): 2594-2596.
[8] Angell C A, Byrne N, Belieres J P. Parallel developments in aprotic and protic ionic liquids: physical chemistry and applications[J]. Acc Chem Res, 2007, 40(11):1228–1236.
[9] Doyle M, Choi S K, Proulx G. High-temperature proton conducting membranes based on perfluorinated ionomer membrane-ionic liquid composites [J]. J Electrochem Soc, 2000, 147 (1): 34-37 .
[10] Martinez M, Molmeret Y, Cointeauxa L, et al. Proton-conducting ionic liquid-based proton exchange membrane fuel cell membranes: The key role of ionomer–ionic liquid interaction [J]. J Power Sources, 2010, 195 (18): 5829-5839.
[11] Baek J S, Park J S, Sekhon S S, et al. Preparation and characterisation of non-aqueous proton-conducting membranes with the low content of ionic liquids [J]. Fuel Cells, 2010, 10(5):762-769.
[12] Yang Jingshuai, Che Quantong, Zhou Lu, et al. Studies of a high temperature proton exchange membrane based on incorporating an ionic liquid cation 1-butyl-3-methylimidazolium into a Nafion matrix [J]. Electrochim Acta, 2011, 56 (17): 5940-5946.
[13] Yi Shizheng, Zhang Fangfang, Li Wei, et al. Anhydrous elevated-temperature polymer electrolyte membranes based on ionic liquids[J]. J Membr Sci, 2011, 366 (1-2): 349-355.
[14] Che Quantong, He Ronghuan, Yang Jingshuai, et al. Phosphoric acid doped high temperature proton exchange membranes based on sulfonated polyetheretherketone incorporated with ionic liquids[J]. Electrochem Commun, 2010, 12 (5): 647-649.
[15] Mondal A N, Tripathi B P, Shahi V K. Highly stable aprotic ionic-liquid doped anhydrous proton-conducting polymer electrolyte membrane for high-temperature applications[J]. J Mater Chem, 2011, 21(12): 4117-4124.
[16] Yan Feng, Yu Shaomei, Zhang Xingwang, et al. Enhanced proton conduction in polymer electrolyte membranes as synthesized by polymerization of protic ionic liquid-based microemulsions[J]. Chem Mater, 2009, 21(8): 1480-1484.
[17] Kim S Y, Yoon E, Joo T, et al. Morphology and conductivity in ionic liquid incorporated sulfonated block copolymers[J]. Macromolecules, 2011, 44(13):5289-5298.
[18] Kim S Y, Kim S, Park M J. Enhanced proton transport in nanostructured polymer electrolyte/ionic liquid membranes under water-free conditions [J]. Nat Commun, 2010(1):88.
[19] Ye H , Huang J, Xua J J, et al. New membranes based on ionic liquids for PEM fuel cells at elevated temperatures[J]. J Power Sources, 2008, 178 (2): 651-660.
[20] Wang J T W, Hsu S L C. Enhanced high-temperature polymer electrolyte membrane for fuel cells based on polybenzimidazole and ionic liquids[J]. Electrochim Acta, 2011, 56 (7): 2842-2846.
[21] Ye Yunsheng, Tseng Chiyung, Shen Chiyung, et al. A new graphene-modified protic ionic liquid-based composite membrane for solid polymer electrolytes[J]. J Mater Chem, 2011, 21(28) :10448-10453.
[22] Lee S Y, Yasuda T, Watanabe M. Fabrication of protic ionic liquid/sulfonated polyimide composite membranes for non-humidified fuel cells [J]. J Power Sources, 2010, 195 (18): 5909-5914.
[23] Fernicola A, Panero S, Scrosati B. Proton-conducting membranes based on protic ionic liquids [J]. J Power Sources, 2008, 178 (2): 591-595.
[24] Sekhon S S, Lalia B S, Park J S, et al. Physicochemical properties of proton conducting membranes based on ionic liquid impregnated polymer for fuel cells[J]. J Mater Chem, 2006, 16(23):2256-2265.
[25] 伍艳辉,邵一凡,张惠敏,张海峰. 质子交换膜中质子传递机理研究进展[J]. 电源技术, 2010, 21(11):1206-1209.
[26] Martinelli A, Matic A, Jacobsson P, et al. Physical properties of proton conducting membranes based on a protic ionic liquid [J]. J Phys Chem B, 2007, 111(43):12462-12467.
[27] Agmon N. The Grotthuss mechanism [J]. Chem Phys Lett, 1995, 244(5-6): 456-462.
[28] Belieres J P , Angell C A. Protic ionic liquids: preparation, characterization, and proton free energy level representation [J]. J Phys Chem B, 2007, 111(18):4926-4937.
[29] Luo Jiangshui, Hu Jin, Saak W, et al. Protic ionic liquid and ionic melts prepared from methanesulfonic acid and 1H-1,2,4-triazole as high temperature PEMFC electrolytes [J]. J Mater Chem, 2011, 21(28): 10426-10436.
[30] Ueki T, Watanabe M. Macromolecules in ionic liquids: progress, challenges, and opportunities [J]. Macromolecules, 2008, 41(11):3739-3749.
[31] Mistry M K, Subianto S, Choudhury N R, et al. Interfacial interactions in aprotic ionic liquid based protonic membrane and its correlation with high temperature conductivity and thermal properties [J]. Langmuir, 2009, 25(16):9240-9251.
[32] Schauera J, Sikora A, Plíškováb M, et al. Ion-conductive polymer membranes containing 1-butyl-3-methylimidazolium trifluoromethanesulfonate and 1-ethylimidazolium trifluoromethanesulfonate[J]. J Membr Sci, 2011, 367 (1-2): 332-339.
[33] Deligöz H, Y?lmazo?lu M. Development of a new highly conductive and thermomechanically stable complex membrane based on sulfonated polyimide/ionic liquid for high temperature anhydrous fuel cells [J]. J Power Sources, 2011, 196 (7):3496-3502.
[34] Ye Yunsheng, Cheng Mingyao, Tseng Jiyong, et al. New proton conducting membranes with high retention of protic ionic liquids[J]. J Mater Chem, 2011, 21(8): 2723-2732.
[35] Lin Bencai, Yan Feng, et al. Protic ionic liquid-based hybrid proton-conducting membranes for anhydrous proton exchange membrane application [J]. Chem Mater, 2010, 22(5): 1807-1813.
[36] Ye Yunsheng, Liang Gaowei, Qiu Lihua, et al. Effect of morphology of mesoporous silica on characterization of protic ionic liquid-based composite membranes [J]. J  Power Sources, 2011, 196 (13): 5408-5415.
[37] Diao Hanbin, Yan Feng, Qiu Lihua, et al. High performance cross-linked poly(2-acrylamido-2- methylpropanesulfonic acid)-based proton exchange membranes for fuel cells [J]. Macromolecules, 2010, 43(15): 6398-6405.
[38] Chu Fuqiang, Lin Bencai, Yan Feng, et al. Macromolecular protic ionic liquid-based proton-conducting membranes for anhydrous proton exchange membrane application [J]. J Power Sources, 2011, 196 (19): 7979-7984.
 

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