Chinese Science Bulletin, Volume 64 , Issue 2 : 153-164(2019) https://doi.org/10.1360/N972018-00767

Progress of polymer chain structure regulation of alkaline anion-exchange membranes for fuel cells

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  • ReceivedJul 30, 2018
  • AcceptedSep 30, 2018
  • PublishedNov 2, 2018


Alkaline anion-exchange membrane fuel cells (AAEMFCs) have attracted worldwide interest due to their advantages including fast oxygen reduction kinetics, high compatibility with non-precious-metal catalyst and low cost. As one of the key components in AAEMFCs, the performance of alkaline anion exchange membranes (AAEMs) directly affects the power output and durability of the fuel cells. During fuel cell operating, AAEMs require high ionic conductivity, excellent dimensional and chemical stability to ensure high efficiency and outstanding durability. However, it is still difficult for any type of the AAEMs to meet all these requirements. This monograph summarizes recent development around the world for AAEMs, especially for the trade-off effect between ionic conductivity and stability of AAEMs as well as the proposed strategies for this issue. The charge carrier in AAEMs is OH-, and it has a lower transporting efficiency owing to its lower mobility, higher dependence on water molecular and the blocking of many hydrophobic domains in AAEMs. The improvement of ion-exchange capacity (IEC) by increasing the grafting degree (GD) of cationic functional groups can, to some extent, solve this issue. however, a high GD always bring the following negative issues: (1) Excessive swelling of AAEMs and significant reducing in the dimensional stability of membranes; (2) the increase of OH- concentration accelerates the kinetics of nucleophilic substitution and Hofmann elimination, leading to the degradation of cationic groups; (3) the enhanced polarization of the cationic groups and the hydrophilicity of the main chain enable the polymer backbone susceptible to nucleophilic attack by OH-, resulting in the degradation of the membrane, and even short-circuit of the fuel cells.

In order to solve these issues, various of polymer chain architectures have been designed and regulated. To balance the ionic conductivity and the dimensional stability in AAEMs, double, triple and multi-cations are grafted on one site of polymer backbone to achieve a sufficiently high IEC at relatively low GD. Another realistic strategy is constructing 3D anion channels by the segregated hydrophilic/hydrophobic phase. The alkali stability of the cationic groups is affected by many factors including field effects, steric effects and conformation of substituent groups, and so on. The improvement of chemical stability of AAEMs has been another formidable scientific challenge. Researchers reduce the kinetics of the nucleophilic substitution and elimination reactions, and improve the basic stability of the cationic groups by modulating the structure of substituent groups such as the introduction of electron-donating groups, increased steric hindrance, and adequate hydration of OH-. Among various cationic groups, the piperidinium-based cations show high resistance against both nucleophilic substitution and elimination in alkaline conditions and at elevated temperature. Furthermore, the polymer backbones without ether band and electron-withdrawing groups have been synthesized and exabit highly resistant to alkali hydrolysis. Recently, new strategy for constructing ordered ion channels in AAEMs by novel porous materials such as metal-organic frameworks (MOF), Tröger's base, and macrocyclic crown ether compounds, provide for efficient ionic transport. Additionally, highly stable metal complexes have been used as cationic group in AAEMs. These new trends will open up an exciting opportunity to design high-performance AAEMs.

The appearance of highly stable AAEMs enables the AAEMFCs to be operated at 80°C, and the cell works stably in a period of study over 100 h. Although this progress is encouraging, there still remains work for improving the cell performance and stability. A 1000 h of stable operation at elevated temperatures will be the next mission for AAEMFCs. In addition, there are some fundamental issues necessary to explore, such as the transport mechanism of OH- in the membrane, the molecular interaction of polyelectrolytes and their self-assembly mechanism in solution and film formation, the mechanism of the influence of morphology on the chemical stability of AAEMs, and the factors affecting the long-term stability of AAEMFCs. These scientific issues will be the focus of future research.

The development of AAEMFCs is on its way, and it calls for more efforts in fundamental study, polymer chain architectures and morphology designing, and fuel cell engineering to make it viable.

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表S1 常见阳离子基团的碱性稳定性

表S2 主链不含醚键的阴离子交换膜及其碱性稳定性

本文以上补充材料见网络版csb.scichina.com. 补充材料为作者提供的原始数据, 作者对其学术质量和内容负责.


[1] Lu S F, Peng S K, Xiang Y. Perspectives on the research progress of bipolar interfacial polyelectrolyte membrane fuel cell (in Chinese). Acta Phys Chim Sin, 2016, 32: 1859–1865 [卢善富, 彭思侃, 相艳. 双极界面聚合物膜燃料电池研究进展. 物理化学学报, 2016, 32: 1859–1865]. Google Scholar

[2] Peng S, Xu X, Zhang J, et al. Bipolar Interfacial Polyelectrolyte Membrane Fuel Cell I:Structure of Membrane Electrode Assembly (in Chinese). Acta Chim Sin, 2015, 73: 137-142 CrossRef Google Scholar

[3] Xu X, Peng S, Zhang J, et al. Bipolar Interfacial Polyelectrolyte Membrane Fuel Cell Ⅱ: Optimization of Cathode Catalyst Layer (in Chinese). Acta Chim Sin, 2016, 74: 271-276 CrossRef Google Scholar

[4] Lu S F, Xu X, Zhang J, et al. Progress of phosphoric acid doped high temperature proton exchange membrane for fuel cells (in Chinese). SSC, 2017, 47: 565-572 CrossRef Google Scholar

[5] Lu S, Pan J, Huang A, et al. Alkaline polymer electrolyte fuel cells completely free from noble metal catalysts. Proc Natl Acad Sci USA, 2008, 105: 20611-20614 CrossRef ADS Google Scholar

[6] Wang Y, Li L, Hu L, et al. A feasibility analysis for alkaline membrane direct methanol fuel cell: Thermodynamic disadvantages versus kinetic advantages. Electrochem Commun, 2003, 5: 662-666 CrossRef Google Scholar

[7] Varcoe J R, Slade R C T. Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells. Fuel Cells, 2005, 5: 187-200 CrossRef Google Scholar

[8] He G, Li Z, Zhao J, et al. Nanostructured ion-exchange membranes for fuel cells: Recent advances and perspectives. Adv Mater, 2015, 27: 5280-5295 CrossRef Google Scholar

[9] Wang Y, Wang G, Li G, et al. Pt-Ru catalyzed hydrogen oxidation in alkaline media: Oxophilic effect or electronic effect? Energy Environ Sci, 2015, 8: 177–181. Google Scholar

[10] Yuan Y, Shen C H, Chen J Q, et al. Research progress of alkaline anion exchange membranes (in Chinese). Chem Ind Eng Prog, 2017, 36: 3336–3342 [袁园, 沈春晖, 陈继钦, 等. 用于燃料电池的碱性阴离子交换膜研究进展. 化工进展, 2017, 36: 3336–3342]. Google Scholar

[11] Pan J, Chen C, Zhuang L, et al. Designing advanced alkaline polymer electrolytes for fuel cell applications. Acc Chem Res, 2011, 45: 473-481 CrossRef Google Scholar

[12] Ge X, He Y, Guiver M D, et al. Alkaline anion-exchange membranes containing mobile ion shuttles. Adv Mater, 2016, 28: 3467-3472 CrossRef Google Scholar

[13] Yang Z, Guo R, Malpass-Evans R, et al. Highly conductive anion-exchange membranes from microporous tröger's base polymers. Angew Chem Int Ed, 2016, 55: 11499-11502 CrossRef Google Scholar

[14] Dang H S, Jannasch P. High-performing hydroxide exchange membranes with flexible tetra-piperidinium side chains linked by alkyl spacers. ACS Appl Energy Mater, 2018, 1: 2222-2231 CrossRef Google Scholar

[15] Wang L, Brink J J, Liu Y, et al. Non-fluorinated pre-irradiation-grafted (peroxidated) LDPE-based anion-exchange membranes with high performance and stability. Energy Environ Sci, 2017, 10: 2154-2167 CrossRef Google Scholar

[16] Wang L, Brink J J, Varcoe J R. The first anion-exchange membrane fuel cell to exceed 1 W cm−2 at 70 °C with a non-Pt-group (O2 ) cathode. Chem Commun, 2017, 53: 11771-11773 CrossRef Google Scholar

[17] Yang Z, Ran J, Wu B, et al. Stability challenge in anion exchange membrane for fuel cells. Curr Opin Chem Eng, 2016, 12: 22-30 CrossRef Google Scholar

[18] Cheng J, He G, Zhang F. A mini-review on anion exchange membranes for fuel cell applications: Stability issue and addressing strategies. Int J Hydrogen Energy, 2015, 40: 7348-7360 CrossRef Google Scholar

[19] Varcoe J R, Atanassov P, Dekel D R, et al. Anion-exchange membranes in electrochemical energy systems. Energy Environ Sci, 2014, 7: 3135-3191 CrossRef Google Scholar

[20] Gottesfeld S, Dekel D R, Page M, et al. Anion exchange membrane fuel cells: Current status and remaining challenges. J Power Sources, 2018, 375: 170-184 CrossRef ADS Google Scholar

[21] Dekel D R. Review of cell performance in anion exchange membrane fuel cells. J Power Sources, 2018, 375: 158-169 CrossRef ADS Google Scholar

[22] Fu X C, Shen W X, Yao T Y, et al. Physical Chemistry. 5th Ed, Volume II. (in Chinese). Beijing: Higher Education Press, 2006 [傅献彩, 沈文霞, 姚天扬, 等. 物理化学(第五版)下册. 北京: 高等教育出版社, 2006]. Google Scholar

[23] Xiang Y, Si J J. Strategies for reconciling tradeoff between conductivity and swelling in alkaline polymer electrolytes membrane (in Chinese). J Beijing Univ Aeron Astron, 2015, 41: 961–968 [相艳, 司江菊. 高电导率、低溶胀的碱性聚电解质膜的实现策略. 北京航空航天大学学报, 2015, 41: 961–968]. Google Scholar

[24] Pan J, Li Y, Han J, et al. A strategy for disentangling the conductivity–stability dilemma in alkaline polymer electrolytes. Energy Environ Sci, 2013, 6: 2912-2915 CrossRef Google Scholar

[25] Si J, Lu S, Xu X, et al. A gemini quaternary ammonium poly (ether ether ketone) anion-exchange membrane for alkaline fuel cell: Design, synthesis, and properties. ChemSusChem, 2014, 7: 3389-3395 CrossRef Google Scholar

[26] Lin C X, Wu H Y, Li L, et al. Anion conductive triblock copolymer membranes with flexible multication side chain. ACS Appl Mater Interfaces, 2018, 10: 18327-18337 CrossRef Google Scholar

[27] Li Q, Liu L, Miao Q, et al. A novel poly(2,6-dimethyl-1,4-phenylene oxide) with trifunctional ammonium moieties for alkaline anion exchange membranes. Chem Commun, 2014, 50: 2791-2793 CrossRef Google Scholar

[28] Ran J, Wu L, Wei B, et al. Simultaneous enhancements of conductivity and stability for anion exchange membranes (AEMs) through precise structure design. Sci Rep, 2014, 4: 6486 CrossRef ADS Google Scholar

[29] Pan J. A study of alkaline polymer electrolytes for fuel cell application (in Chinese). Doctor Dissertation. Wuhan: Wuhan University, 2012 [潘婧. 燃料电池用碱性聚合物电解质研究. 博士学位论文. 武汉: 武汉大学, 2012]. Google Scholar

[30] Peng Y, Lyu K, Wang Y, et al. Effect of H2O on the phase seperation of PEEK. Wuhan: Beijing Forum 2016 on Electrochemical Frontier, 2016. 6–9. Google Scholar

[31] Mauritz K A, Moore R B. State of understanding of Nafion. Chem Rev, 2004, 104: 4535-4586 CrossRef Google Scholar

[32] He S S, Frank C W. Facilitating hydroxide transport in anion exchange membranes via hydrophilic grafts. J Mater Chem A, 2014, 2: 16489-16497 CrossRef Google Scholar

[33] Li N, Yan T, Li Z, et al. Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes. Energy Environ Sci, 2012, 5: 7888-7892 CrossRef Google Scholar

[34] Li N, Leng Y, Hickner M A, et al. Highly stable, anion conductive, comb-shaped copolymers for alkaline fuel cells. J Am Chem Soc, 2013, 135: 10124-10133 CrossRef Google Scholar

[35] Lin C X, Zhuo Y Z, Lai A N, et al. Comb-shaped phenolphthalein-based poly(ether sulfone)s as anion exchange membranes for alkaline fuel cells. RSC Adv, 2016, 6: 17269-17279 CrossRef Google Scholar

[36] Rao A H N, Nam S Y, Kim T H. Comb-shaped alkyl imidazolium-functionalized poly(arylene ether sulfone)s as high performance anion-exchange membranes. J Mater Chem A, 2015, 3: 8571-8580 CrossRef Google Scholar

[37] Chen Y, Tao Y, Wang J, et al. Comb-shaped guanidinium functionalized poly(ether sulfone)s for anion exchange membranes: Effects of the spacer types and lengths. J Polym Sci Part A-Polym Chem, 2017, 55: 1313-1321 CrossRef ADS Google Scholar

[38] Pan J, Chen C, Li Y, et al. Constructing ionic highway in alkaline polymer electrolytes. Energy Environ Sci, 2014, 7: 354-360 CrossRef Google Scholar

[39] Dang H S, Jannasch P. Exploring different cationic alkyl side chain designs for enhanced alkaline stability and hydroxide ion conductivity of anion-exchange membranes. Macromolecules, 2015, 48: 5742-5751 CrossRef ADS Google Scholar

[40] Lee K H, Cho D H, Kim Y M, et al. Highly conductive and durable poly(arylene ether sulfone) anion exchange membrane with end-group cross-linking. Energy Environ Sci, 2017, 10: 275-285 CrossRef Google Scholar

[41] Si J, Wang H, Lu S, et al. In situ construction of interconnected ion transfer channels in anion-exchange membranes for fuel cell application. J Mater Chem A, 2017, 5: 4003-4010 CrossRef Google Scholar

[42] Lin C X, Wang X Q, Li L, et al. Triblock copolymer anion exchange membranes bearing alkyl-tethered cycloaliphatic quaternary ammonium-head-groups for fuel cells. J Power Sources, 2017, 365: 282-292 CrossRef ADS Google Scholar

[43] Zhang X, Li S, Chen P, et al. Imidazolium functionalized block copolymer anion exchange membrane with enhanced hydroxide conductivity and alkaline stability via tailoring side chains. Int J Hydrogen Energy, 2018, 43: 3716-3730 CrossRef Google Scholar

[44] Strasser D J, Graziano B J, Knauss D M. Base stable poly(diallylpiperidinium hydroxide) multiblock copolymers for anion exchange membranes. J Mater Chem A, 2017, 5: 9627-9640 CrossRef Google Scholar

[45] Cha M S, Lee J Y, Kim T H, et al. Preparation and characterization of crosslinked anion exchange membrane (AEM) materials with poly(phenylene ether)-based short hydrophilic block for use in electrochemical applications. J Membrane Sci, 2017, 530: 73-83 CrossRef Google Scholar

[46] Xue B, Dong X, Li Y, et al. Synthesis of novel guanidinium-based anion-exchange membranes with controlled microblock structures. J Membrane Sci, 2017, 537: 151-159 CrossRef Google Scholar

[47] Zhu M, Zhang X, Wang Y, et al. Novel anion exchange membranes based on quaternized diblock copolystyrene containing a fluorinated hydrophobic block. J Membrane Sci, 2018, 554: 264-273 CrossRef Google Scholar

[48] Dong X, Xue B, Qian H, et al. Novel quaternary ammonium microblock poly (p-phenylene-co-aryl ether ketone)s as anion exchange membranes for alkaline fuel cells. J Power Sources, 2017, 342: 605-615 CrossRef ADS Google Scholar

[49] Kim E, Lee S, Woo S, et al. Synthesis and characterization of anion exchange multi-block copolymer membranes with a fluorine moiety as alkaline membrane fuel cells. J Power Sources, 2017, 359: 568-576 CrossRef ADS Google Scholar

[50] Mohanty A D, Ryu C Y, Kim Y S, et al. Stable Elastomeric Anion Exchange Membranes Based on Quaternary Ammonium-Tethered Polystyrene- b-poly(ethylene- co-butylene)- b-polystyrene Triblock Copolymers. Macromolecules, 2015, 48: 7085-7095 CrossRef ADS Google Scholar

[51] Zhu M, Zhang M, Chen Q, et al. Synthesis of midblock-quaternized triblock copolystyrenes as highly conductive and alkaline-stable anion-exchange membranes. Polym Chem, 2017, 8: 2074-2086 CrossRef Google Scholar

[52] Meek K M, Sun R, Willis C, et al. Hydroxide conducting polymerized ionic liquid pentablock terpolymer anion exchange membranes with methylpyrrolidinium cations. Polymer, 2018, 134: 221-226 CrossRef Google Scholar

[53] Zhang X, Shi Q, Chen P, et al. Block poly(arylene ether sulfone) copolymers tethering aromatic side-chain quaternary ammonium as anion exchange membranes. Polym Chem, 2018, 9: 699-711 CrossRef Google Scholar

[54] Xiao Lin C, Qin Wang X, Ning Hu E, et al. Quaternized triblock polymer anion exchange membranes with enhanced alkaline stability. J Membrane Sci, 2017, 541: 358-366 CrossRef Google Scholar

[55] Gao X, Lu F, Liu Y, et al. The facile construction of an anion exchange membrane with 3D interconnected ionic nano-channels. Chem Commun, 2017, 53: 767-770 CrossRef Google Scholar

[56] Tsai T H, Maes A M, Vandiver M A, et al. Synthesis and structure-conductivity relationship of polystyrene- block-poly(vinyl benzyl trimethylammonium) for alkaline anion exchange membrane fuel cells. J Polym Sci Part B-Polym Phys, 2013, 51: 1751-1760 CrossRef ADS Google Scholar

[57] Hsu W Y, Barkley J R, Meakin P. Ion percolation and insulator-to-conductor transition in nafion perfluorosulfonic acid membranes. Macromolecules, 1980, 13: 198-200 CrossRef ADS Google Scholar

[58] Sun Z, Lin B, Yan F. Anion-exchange membranes for alkaline fuel-cell applications: The effects of cations. ChemSusChem, 2018, 11: 58-70 CrossRef Google Scholar

[59] Gu L, Sun Z, Xu D, et al. Progress of alkaline anion exchange membranes (in Chinese). J Funct Polym, 2016, 29: 153–162 [顾梁, 孙哲, 徐丹, 等. 碱性阴离子交换聚合物膜研究进展. 功能高分子学报, 2016, 29: 153–162]. Google Scholar

[60] Si Z, Qiu L, Dong H, et al. Effects of substituents and substitution positions on alkaline stability of imidazolium cations and their corresponding anion-exchange membranes. ACS Appl Mater Interfaces, 2014, 6: 4346-4355 CrossRef Google Scholar

[61] Gu F, Dong H, Li Y, et al. Highly stable N3-substituted imidazolium-based alkaline anion exchange membranes: Experimental studies and theoretical calculations. Macromolecules, 2013, 47: 208-216 CrossRef ADS Google Scholar

[62] Lin B, Dong H, Li Y, et al. Alkaline stable C2-substituted imidazolium-based anion-exchange membranes. Chem Mater, 2013, 25: 1858-1867 CrossRef Google Scholar

[63] Marino M G, Kreuer K D. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids. ChemSusChem, 2015, 8: 513-523 CrossRef Google Scholar

[64] Mohanty A D, Bae C. Mechanistic analysis of ammonium cation stability for alkaline exchange membrane fuel cells. J Mater Chem A, 2014, 2: 17314-17320 CrossRef Google Scholar

[65] Price S C, Williams K S, Beyer F L. Relationships between structure and alkaline stability of imidazolium cations for fuel cell membrane applications. ACS Macro Lett, 2014, 3: 160-165 CrossRef Google Scholar

[66] Wright A G, Holdcroft S. Hydroxide-stable ionenes. ACS Macro Lett, 2014, 3: 444-447 CrossRef Google Scholar

[67] Fan J, Wright A G, Britton B, et al. Cationic Polyelectrolytes, Stable in 10 M KOHaq at 100 °C. ACS Macro Lett, 2017, 6: 1089-1093 CrossRef Google Scholar

[68] Long H, Kim K, Pivovar B S. Hydroxide degradation pathways for substituted trimethylammonium cations: A DFT study. J Phys Chem C, 2012, 116: 9419-9426 CrossRef Google Scholar

[69] Chempath S, Einsla B R, Pratt L R, et al. Mechanism of tetraalkylammonium headgroup degradation in alkaline fuel cell membranes. J Phys Chem C, 2008, 112: 3179-3182 CrossRef Google Scholar

[70] Dekel D R, Amar M, Willdorf S, et al. Effect of water on the stability of quaternary ammonium groups for anion exchange membrane fuel cell applications. Chem Mater, 2017, 29: 4425-4431 CrossRef Google Scholar

[71] Liu X, Chen X, Pei S, et al. Evaluation of water in perfluorinated anion exchange membranes with different iec values. J Phys Chem C, 2017, 121: 17546-17551 CrossRef Google Scholar

[72] Chen N, Long C, Li Y, et al. Ultrastable and high ion-conducting polyelectrolyte based on six-membered n-spirocyclic ammonium for hydroxide exchange membrane fuel cell applications. ACS Appl Mater Interfaces, 2018, 10: 15720-15732 CrossRef Google Scholar

[73] Olsson J S, Pham T H, Jannasch P. Poly(arylene piperidinium) hydroxide ion exchange membranes: Synthesis, alkaline stability, and conductivity. Adv Funct Mater, 2018, 28: 1702758 CrossRef Google Scholar

[74] Pham T H, Olsson J S, Jannasch P. N-Spirocyclic Quaternary Ammonium Ionenes for Anion-Exchange Membranes. J Am Chem Soc, 2017, 139: 2888-2891 CrossRef Google Scholar

[75] Arges C G, Ramani V. Two-dimensional nmr spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes. Proc Natl Acad Sci USA, 2013, 110: 2490-2495 CrossRef ADS Google Scholar

[76] Fujimoto C, Kim D S, Hibbs M, et al. Backbone stability of quaternized polyaromatics for alkaline membrane fuel cells. J Membrane Sci, 2012, 423-424: 438-449 CrossRef Google Scholar

[77] Mohanty A D, Tignor S E, Krause J A, et al. Systematic alkaline stability study of polymer backbones for anion exchange membrane applications. Macromolecules, 2016, 49: 3361-3372 CrossRef ADS Google Scholar

[78] 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 Membrane Sci, 2016, 518: 159-167 CrossRef Google Scholar

[79] Nuñez S A, Hickner M A. Quantitative1 H NMR Analysis of Chemical Stabilities in Anion-Exchange Membranes. ACS Macro Lett, 2013, 2: 49-52 CrossRef Google Scholar

[80] Miyanishi S, Fukushima T, Yamaguchi T. Synthesis and property of semicrystalline anion exchange membrane with well-defined ion channel structure. Macromolecules, 2015, 48: 2576-2584 CrossRef ADS Google Scholar

[81] Lee W H, Park E J, Han J, et al. Poly(terphenylene) anion exchange membranes: The effect of backbone structure on morphology and membrane property. ACS Macro Lett, 2017, 6: 566-570 CrossRef Google Scholar

[82] Olsson J S, Pham T H, Jannasch P. Poly( N , N-diallylazacycloalkane)s for Anion-Exchange Membranes Functionalized with N-Spirocyclic Quaternary Ammonium Cations. Macromolecules, 2017, 50: 2784-2793 CrossRef ADS Google Scholar

[83] Park E J, Kim Y S. Quaternized aryl ether-free polyaromatics for alkaline membrane fuel cells: synthesis, properties, and performance – a topical review. J Mater Chem A, 2018, 6: 15456-15477 CrossRef Google Scholar

[84] Lee W H, Kim Y S, Bae C. Robust hydroxide ion conducting poly(biphenyl alkylene)s for alkaline fuel cell membranes. ACS Macro Lett, 2015, 4: 814-818 CrossRef Google Scholar

[85] Lee W H, Mohanty A D, Bae C. Fluorene-based hydroxide ion conducting polymers for chemically stable anion exchange membrane fuel cells. ACS Macro Lett, 2015, 4: 453-457 CrossRef Google Scholar

[86] Nawn G, Vezzù K, Cavinato G, et al. Opening doors to future electrochemical energy devices: The anion-conducting polyketone polyelectrolytes. Adv Funct Mater, 2018, 28: 1706522 CrossRef Google Scholar

[87] Zhang M, Liu J, Wang Y, et al. Highly stable anion exchange membranes based on quaternized polypropylene. J Mater Chem A, 2015, 3: 12284-12296 CrossRef Google Scholar

[88] Zhang M, Shan C, Liu L, et al. Facilitating anion transport in polyolefin-based anion exchange membranes via bulky side chains. ACS Appl Mater Interfaces, 2016, 8: 23321-23330 CrossRef Google Scholar

[89] You W, Hugar K M, Coates G W. Synthesis of alkaline anion exchange membranes with chemically stable imidazolium cations: Unexpected cross-linked macrocycles from ring-fused romp monomers. Macromolecules, 2018, 51: 3212-3218 CrossRef ADS Google Scholar

[90] Graha H P R, Ando S, Miyanishi S, et al. Development of a novel durable aromatic anion exchange membrane using a thermally convertible precursor. Chem Commun, 2018, 54: 10820-10823 CrossRef Google Scholar

[91] Xu F, Yuan W S, Zhu Y Y, et al. Preparation and properties of anion exchange membranes based on spirocyclic quaternary ammonium salts (in Chinese). Chin Sci Bull, 2018, 64: 165–171 [徐斐, 袁文森, 朱媛媛, 等. 基于螺环季铵盐的阴离子交换膜的制备与性能. 科学通报, 2018, 64: 165–171]. Google Scholar

[92] Dang H S, Jannasch P. A comparative study of anion-exchange membranes tethered with different hetero-cycloaliphatic quaternary ammonium hydroxides. J Mater Chem A, 2017, 5: 21965-21978 CrossRef Google Scholar

[93] Hu E N, Lin C X, Liu F H, et al. Poly(arylene ether nitrile) anion exchange membranes with dense flexible ionic side chain for fuel cells. J Membrane Sci, 2018, 550: 254-265 CrossRef Google Scholar

[94] Liu C, Feng S, Zhuang Z, et al. Towards basic ionic liquid-based hybrid membranes as hydroxide-conducting electrolytes under low humidity conditions. Chem Commun, 2015, 51: 12629-12632 CrossRef Google Scholar

[95] Liu C, Zhang G, Zhao C, et al. MOFs synthesized by the ionothermal method addressing the leaching problem of IL–polymer composite membranes. Chem Commun, 2014, 50: 14121-14124 CrossRef Google Scholar

[96] Zha Y, Disabb-Miller M L, Johnson Z D, et al. Metal-cation-based anion exchange membranes. J Am Chem Soc, 2012, 134: 4493-4496 CrossRef Google Scholar

[97] Zhu T, Xu S, Rahman A, et al. Cationic metallo-polyelectrolytes for robust alkaline anion-exchange membranes. Angew Chem Int Ed, 2018, 57: 2388-2392 CrossRef Google Scholar

[98] Gu S, Wang J, Kaspar R B, et al. Permethyl cobaltocenium (Cp*2Co+) as an ultra-stable cation for polymer hydroxide-exchange membranes. Sci Rep, 2015, 5: 11668 CrossRef ADS Google Scholar

[99] Wu B, Ge L, Yu D, et al. Cationic metal–organic framework porous membranes with high hydroxide conductivity and alkaline resistance for fuel cells. J Mater Chem A, 2016, 4: 14545-14549 CrossRef Google Scholar

[100] Peng H, Li Q, Hu M, et al. Alkaline polymer electrolyte fuel cells stably working at 80 °C. J Power Sources, 2018, 390: 165-167 CrossRef ADS Google Scholar

[101] Liu L, Chu X, Liao J, et al. Tuning the properties of poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes and their performance in H2 /O2 fuel cells. Energy Environ Sci, 2018, 11: 435-446 CrossRef Google Scholar

  • Figure 1

    (Color online) Schematic illustration of single (a), double (b) and triple (c) cations grafted on one site of polymer backbone

  • Figure 2

    (Color online) 2D nuclear overhauser effect spectroscopy (NOESY) for quaternary ammonium Poly (ether ether ketone) (MQ-PEEK) with phase-segregated morphology (a) and schematic of MQ-PEEK aggregation structure (b)

  • Figure 3

    A two-dimensional illustration for percolation theory. The shaded and crossed areas correspond respectively to sites that were previously occupied and sites that have just been occupied whereas those marked L in (b) are some empty sites that must be occupied before the onset of ion transport. The percentages of occupancy of the grid for cases (a) to (d) are 18%, 31%, 45%, and 53%, respectively[57]

  • Figure 4

    (Color online) Durability of AAEMFCs using QAPPT[100] (a), pristine E-Imds and cross-linked XE-Imds (b) membranes under a constant current density of 0.2 A cm-2 at 80°C[40]

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