用于燃料电池的碱性阴离子交换膜研究进展

doi:10.16085/j.issn.1000-6613.2016-2357

摘要/Abstract

摘要： 针对当前碱性阴离子交换膜离子电导率低和高温耐碱性较差的问题，本文综述了碱性功能基团和聚合物主链结构对阴离子交换膜离子电导率、碱性稳定性等主要性能的影响，主要介绍了季铵盐型、胍型、季盐型、咪唑盐型、锍盐型碱性功能基团以及嵌段共聚物、侧链型聚合物为基体材料的阴离子交换膜的研究进展，重点分析了上述因素对离子电导率的影响机理。综合分析表明，为了制备高电导率且强耐碱性的阴离子交换膜，进一步改性研究提高碱性功能基团离子电导率和碱性稳定性，优化聚合物主链结构，构建高效、有序的离子传输通道是未来的主要研究方向。

关键词: 电化学, 碱性燃料电池, 阴离子交换膜, 离子电导率, 碱性功能基团, 聚合物结构

Abstract: Aiming at the low ionic conductivity and poor alkaline resistance of anion exchange membranes at elevated temperature,we make an overview on the effects of alkaline functional groups and polymer backbone structure on their main properties such as ionic conductivity and alkaline stability. The research progress of using functional groups of quaternary ammonium salt,guanidine,quaternary phosphonium salt,imidazole salt,and sulfonium salt,and block copolymer,side chain polymer as polymer matrix materials are mainly introduced. What's more,the influence mechanisms of various factors on the ionic conductivity are analyzed emphatically. The results show that,in order to prepare anion exchange membranes with high ionic conductivity and excellent alkaline resistance,further study on improving the ionic conductivity and alkaline stability of functional groups,and optimizing the polymer backbone structures to construct efficient and orderly ion transport channel are the main research directions in the future.

Key words: electrochemistry, alkaline fuel cells, anion exchange membranes, ionic conductivity, alkaline functional groups, polymer chain structures

中图分类号:

TM911.4

袁园, 沈春晖, 陈继钦, 任学超. 用于燃料电池的碱性阴离子交换膜研究进展[J]. 化工进展, 2017, 36(09): 3336-3342.

YUAN Yuan, SHEN Chunhui, CHEN Jiqin, REN Xuechao. Research progress of alkaline anion exchange membranes[J]. Chemical Industry and Engineering Progress, 2017, 36(09): 3336-3342.

参考文献

[1] 唐卫芬. 燃料电池用季铵化聚芳醚砜类阴离子交换膜的制备及性能[D]. 南京:南京理工大学,2014. TANG W F. Preparation and properties of anion exchange membranes based on quarternary ammonium poly(arylene ether sulfone)s for fuel cell applications[D]. Nanjing:Nanjing University of Science & Technology,2014.
[2] 冉瑾. 面向碱性燃料电池应用的阴离子交换膜的设计与制备[D]. 合肥:中国科学技术大学,2015. RAN J. Design and preparation of anion exchange membranes for alkaline fuel cells[D]. Hefei:University of Science and Technology of China,2015.
[3] CHENG J,HE G,ZHANG F. A mini-review on anion exchange membranes for fuel cell applications:stability issue and addressing strategies[J]. International Journal of Hydrogen Energy,2015,40(23):7348-7360.
[4] 董锐,李远兵,张建勋,等. 季铵化羟乙基纤维素/季铵化聚乙烯醇共混阴离子交换膜的制备与表征[J]. 化工进展,2012,31(3):612-616. DONG R,LI Y B,ZHANG J X,et al. Preparation and characterization of blend anion-exchange membrane from quarternized hydroxyethylcellulose/quaternized poly(vinyl alcohol)[J]. Chemical Industry and Engineering Progress,2012,31(3):612-616.
[5] 王吉林. 燃料电池用季铵类阴离子交换膜的制备及改性研究[D]. 沈阳:东北大学,2013. WANG J L. Studies on preparation and modification of quaternized ammonium based anion exchange membranes for fuel cells[D]. Shenyang:Northeastern University,2013.
[6] 李庆. 新型碱性阴离子交换膜的制备及表征[D]. 合肥:中国科学技术大学,2015. LI Q. Synthesis and characterization of novel alkaline anion exchange membranes[D]. Hefei:University of Science and Technology of China,2015.
[7] GOPI K H,PEERA S G,BHAT S D,et al. Preparation and characterization of quaternary ammonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) as anion exchange membrane for alkaline polymer electrolyte fuel cells[J]. International Journal of Hydrogen Energy,2014,39(6):2659-2668.
[8] WANG C,SHEN B,XU C,et al. Side-chain-type poly(arylene ether sulfone)s containing multiple quaternary ammonium groups as anion exchange membranes[J]. Journal of Membrane Science,2015,492:281-288.
[9] WANG J,WANG J,ZHANG S. Synthesis and characterization of cross-linked poly(arylene ether ketone) containing pendant quaternary ammonium groups for anion-exchange membranes[J]. Journal of Membrane Science,2012,415:205-212.
[10] TUAN C M,KIM D. Anion-exchange membranes based on poly(arylene ether ketone) with pendant quaternary ammonium groups for alkaline fuel cell application[J]. Journal of Membrane Science,2016,511:143-150.
[11] VARCOE J R,ATANASSOV P,DEKEL D R,et al. Anion-exchange membranes in electrochemical energy systems[J]. Energy & Environmental Science,2014,7(10):3135-3191.
[12] 王文晓,尚玉明,王要武,等. 氟化聚芳醚/PVDF复合阴离子交换膜的制备[J]. 化工进展,2012,31(s1):363-366. WANG W X,SHANG Y M,WANG Y W,et al. Composite anion exchange membranes based on fluorinated poly(aryl ether oxadiazole) and poly(vinylidene fluoride)[J]. Chemical Industry and Engineering Progress,2012,31(s1):363-366.
[13] LIU L,LI Q,DAI J,et al. A facile strategy for the synthesis of guanidinium-functionalized polymer as alkaline anion exchange membrane with improved alkaline stability[J]. Journal of Membrane Science,2014,453:52-60.
[14] QU C,ZHANG H,ZHANG F,et al. A high-performance anion exchange membrane based on bi-guanidinium bridged polysilsesquioxane for alkaline fuel cell application[J]. Journal of Materials Chemistry,2012,22(17):8203-8207.
[15] KIM D S,LABOURIAU A,GUIVER M D,et al. Guanidinium-functionalized anion exchange polymer electrolytes via activated fluorophenyl-amine reaction[J]. Chemistry of Materials,2011,23(17):3795-3797.
[16] ARGES C G,PARRONDO J,JOHNSON G,et al. Assessing the influence of different cation chemistries on ionic conductivity and alkaline stability of anion exchange membranes[J]. Journal of Materials Chemistry,2012,22(9):3733-3744.
[17] GU S,CAI R,LUO T,et al. A soluble and highly conductive ionomer for high-performance hydroxide exchange membrane fuel cells[J]. Angewandte Chemie International Edition,2009,48(35):6499-6502.
[18] GU S,CAI R,YAN Y. Self-crosslinking for dimensionally stable and solvent-resistant quaternary phosphonium based hydroxide exchange membranes[J]. Chemical Communications,2011,47(10):2856-8.
[19] YE Y,STOKES K K,BEYER F L,et al. Development of phosphonium-based bicarbonate anion exchange polymer membranes[J]. Journal of Membrane Science,2013,443:93-99.
[20] NOONAN K J T,HUGAR K M,KOSTALIK IV H A,et al. Phosphonium-functionalized polyethylene:a new class of base-stable alkaline anion exchange membranes[J]. Journal of the American Chemical Society,2012,134(44):18161-18164.
[21] RAN J,WU L,VARCOE J R,et al. Development of imidazolium-type alkaline anion exchange membranes for fuel cell application[J]. Journal of Membrane Science,2012,415:242-249.
[22] MORANDI C G,PEACH R,KRIEG H M,et al. Novel imidazolium-functionalized anion-exchange polymer PBI blend membranes[J]. Journal of Membrane Science,2015,476:256-263.
[23] GUO M,FANG J,XU H,et al. Synthesis and characterization of novel anion exchange membranes based on imidazolium-type ionic liquid for alkaline fuel cells[J]. Journal of Membrane Science,2010,362(1):97-104.
[24] HOSSAIN M A,JANG H,SUTRADHAR S C,et al. Novel hydroxide conducting sulfonium-based anion exchange membrane for alkaline fuel cell applications[J]. International Journal of Hydrogen Energy,2016,41(24):10458-10465.
[25] JANG H,HOSSAIN M A,SUTRADHAR S C,et al. Anion conductive tetra-sulfonium hydroxides poly(fluorenylene ether sulfone) membrane for fuel cell application[J]. International Journal of Hydrogen Energy,2017,42(17):12759-12767.
[26] 顾梁,孙哲,徐丹,等. 碱性阴离子交换聚合物膜研究进展[J]. 功能高分子学报,2016,29(2):153-162. GU L,SUN Z,XU D,et al. Progress of alkaline anion exchange membranes[J]. Journal of Functional Polymer,2016,29(2):153-162.
[27] PAN J,CHEN C,LI Y,et al. Constructing ionic highway in alkaline polymer electrolytes[J]. Energy & Environmental Science,2014,7(1):354-360.
[28] DONG X,HOU S,MAO H,et al. Novel hydrophilic-hydrophobic block copolymer based on cardo poly(arylene ether sulfone)s with bis-quaternary ammonium moieties for anion exchange membranes[J]. Journal of Membrane Science,2016,518:31-39.
[29] DANKS T N,SLADE R C T,VARCOE J R. Alkaline anion-exchange radiation-grafted membranes for possible electrochemical application in fuel cells[J]. Journal of Materials Chemistry,2003,13(4):712-721.
[30] LIN C X,ZHUO Y Z,LAI A N,et al. Side-chain-type anion exchange membranes bearing pendent imidazolium-functionalized poly(phenylene oxide) for fuel cells[J]. Journal of Membrane Science,2016,513:206-216.
[31] GAO L,HE G,PAN Y,et al. Poly (2,6-dimethyl-1,4-phenylene oxide) containing imidazolium-terminated long side chains as hydroxide exchange membranes with improved conductivity[J]. Journal of Membrane Science,2016,518:159-167.
[32] ZHANG Z,WU L,VARCOE J,et al. Aromatic polyelectrolytes via polyacylation of pre-quaternized monomers for alkaline fuel cells[J]. Journal of Materials Chemistry A,2013,1(7):2595-2601.
[33] ARGES C G,RAMANI V. Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes[J]. Proceedings of the National Academy of Sciences,2013,110(7):2490-2495.
[34] PAN J,LI Y,HAN J,et al. A strategy for disentangling the conductivity-stability dilemma in alkaline polymer electrolytes[J]. Energy & Environmental Science,2013,6(10):2912-2915.
[35] HE Y,PAN J,WU L,et al. A novel methodology to synthesize highly conductive anion exchange membranes[J]. Scientific Reports,2015,5. DOI:10.1038/srep13417.