高稳定碱性离子膜分子设计研究进展

doi:10.11949/0438-1157.20210020

摘要/Abstract

摘要：

以阴离子交换膜（碱性离子膜）为基础的能量转化与储能过程十分重要，包括碱性膜燃料电池、碱性膜电解水制氢等，该类电膜过程对未来能源结构会产生深远影响。现有阴离子交换膜存在耐碱性差、性能衰减显著的问题，严重制约高效能源储存及转化技术发展。为了获得高稳定的碱性离子膜，近年来，围绕耐碱高分子材料的分子设计开展大量工作。本综述从碱性膜材料的高分子骨架和阳离子基团两个角度出发，针对膜材料耐碱性，重点阐述聚烯烃和聚芳基的主链结构，以及非金属中心、金属中心，两类阳离子的分子结构设计策略，展望高稳定碱性膜的结构设计规律及主要挑战，为设计与合成高性能碱性离子膜，满足清洁能源转化与储能膜过程提供新思路。

关键词: 碱性离子膜, 耐碱稳定性, 高分子骨架, 阳离子基团, 燃料电池, 电解水

Abstract:

Energy conversion and energy storage processes based on anion exchange membranes (alkaline ion membranes) are very important, including alkaline membrane fuel cells, alkaline membrane electrolysis of water to produce hydrogen, etc. This type of electrical membrane process will have a profound impact on the future energy structure influences. Existing anion exchange membranes often suffered from problems of poor alkali resistance and short life span, which severely restrict the development of efficient energy storage and conversion technologies. Recently, researchers have carried out a lot of novel molecular design for alkaline membrane materials of highly chemical stability. This review is based on the two perspectives of alkaline anion exchange membranes and the polymer backbone and cationic groups, focusing on the molecular design strategies including polyolefin and poly-aryl backbone structure, as well as non-metal or metal cationic groups. Moreover, regular methods and current deficiencies of high-stability alkaline anion exchange membranes structural design is summarized, and new ideas for synthesis of next generation high-performance materials for energy conversion processes is also proposed.

Key words: alkaline anion exchange membrane, alkali resistance, polymer backbone, cationic group, fuel cell, water electrolysis

中图分类号:

O 658.6⁺8

徐子昂, 万磊, 刘凯, 王保国. 高稳定碱性离子膜分子设计研究进展[J]. 化工学报, 2021, 72(8): 3891-3906.

Zi'ang XU, Lei WAN, Kai LIU, Baoguo WANG. Recent progress of molecular design for highly stable alkaline anion exchange membranes[J]. CIESC Journal, 2021, 72(8): 3891-3906.

图/表 16

图1 碱性膜燃料电池(a)与碱性膜电解水(b)原理图

Fig.1 Schematic of anion exchange membrane fuel cell (a) and anion exchange membrane water electrolysis(b)

图2 2006~2020年相关领域被Web of Science收录的文章数量。关键词：(a)“Anion Exchange Membrane”&“Fuel Cell”；(b)“Anion Exchange Membrane”&“Water Electrolysis”。相关数据统计截至2020年10月

Fig.2 Annual journal article publications included by Web of Science from 2006 to 2020. Keywords: (a) “Anion Exchange Membrane” & “Fuel Cell”；(b)“Anion Exchange Membrane” & “Water Electrolysis”. The total number of articles for 2018—2020 is statistics until October 2020

图3 影响阴离子交换膜稳定性设计的因素

Fig.3 Factors affecting the design of stable anion exchange membranes

图4 Z-N配位聚合制备FxC9N[29](a) 材料合成方法;(b) AEMFC稳定性测试

Fig.4 FxC9N based on Z-N coordination polymerization[29](a) synthesis route;(b) AEMFC durability test

图5 开环聚合制备AAEM-17[30](a) 材料合成方法;(b) 基于电导率变化的耐碱性测试

Fig.5 AAEM-17 based on ring opening metathesis polymerization[30](a) synthesis route;(b) stability test based on conductivity variety according to time

图6 基于侧链修饰方法的QB-g-F[40](a) 材料合成方法及分子结构;(b) 2 mol·L-1 OH-,60℃, 基于电导率变化的耐碱性测试

Fig.6 Chemical stable QB-g-F based on side chain engineering[40](a) synthesis route & chemical structure;(b) stability test based on conductivity variety according to time under 2 mol·L-1 OH-, 60℃

图7 超酸催化方法制备聚芳基主链型PAP-BP-x和PAP-TP-x[46](a) 聚合物分子结构;(b) 基于NMR方法的耐碱性测试;(c) 1 mol·L-1 KOH、100℃下的电导率随时间的变化

Fig.7 PAP-BP-x & PAP-TP-x with poly-aryl backbone prepared by superacid catalysis[46](a) structure of polymer; (b) alkaline durability based on NMR change; (c) conductivity variety according to time under 1 mol·L-1 KOH, 100℃

图8 Yamamoto耦合聚合方法制备聚芳基主链型PAImXY[48](a) 材料合成方法;(b) 6 mol·L-1 KOH下水电解稳定性测试

Fig.8 Yamamoto coupling polymerization for poly-aryl backbone PAImXY[48](a) synthesis route; (b) water electrolysis stability test under 6 mol·L-1 KOH

图9 已报道的AEMs阳离子基团化学结构

Fig.9 Reported cationic groups for AEMs applications

图10 烷基链季铵盐在OH-进攻下可能发生的降解机理

Fig.10 Possible degradation mechanism of quaternary ammonium salt of alkyl chain under OH- attacking

图11 奎宁盐阳离子基团PDPF-Qui[56](a) 聚合物分子结构;(b) 基于NMR检测的耐碱稳定性

Fig.11 PDPF-Qui based on quinuclidium cation groups[56](a) chemical structure; (b) alkaline durability monitored by NMR

图12 螺环型季铵盐型AEMs[60](a) 分子结构及膜材料;(b),(c) 碱性稳定性测试下的NMR变化情况

Fig.12 Spiro-ionenes AEMs based on N?spirocyclic quaternary ammonium group[60](a) chemical structure & photographs of AEM; (b),(c) alkaline stability under different condition monitored by NMR

图13 基于咪唑系列模型分子的耐碱稳定性[66]

Fig.13 Alkaline stability based on model structure of imidazolium cations[66]

图14 交联吡唑型PXm-Tn构筑OH-高速传导通道[67](a) 分子结构及合成方法;(b) 1 mol·L-1 KOH,80℃下基于电导率变化的耐碱稳定性测试;(c) AEMFC稳定性测试

Fig.14 Pyrazolium cross-linked PXm-Tn for OH- transportation highway[67](a) chemical structure & synthesis route; (b) chemical stability test based on conductivity variety under 1 mol·L-1 KOH, 80℃; (c) AEMFC durability test

图15 二茂钴金属中心型H-AEM-OH[32](a) 分子结构及合成方法;(b) 1 mol·L-1 KOH, 80℃下基于电导率变化的耐碱稳定性测试

Fig.15 H-AEM-OH based on cobaltocenium center[32](a) chemical structure & synthesis route; (b) chemical stability test based on conductivity variety under 1 mol·L-1 KOH, 80℃

表1 不同阳离子基团AEMs电导率及耐碱稳定性

Table 1 Conductivity and alkali resistance of AEMs with different cationic groups

类别	阳离子基团	AEMs名称	聚合物主链	IEC/ (mmol·g^-1)	电导率/(mS·cm^-1)	稳定性	文献
非芳香型季铵盐	DBACO型	CL-QDPEEKOH	聚醚醚酮	1.2	51(55℃)	50%电导率保持(2 mol·L^-1 KOH， 60℃，120 h)	[54]
	奎宁型	PDPF-Qui	超酸催化聚芳基	1.99	100(80℃)	91.2%电导率保持(5 mol·L^-1 NaOH，90℃，168 h)	[56]
	哌啶型	PAP-TP	超酸催化聚芳基	2.37	193(95℃)	97%电导率保持(1 mol·L^-1 KOH，100℃，2000 h)	[46]
	吡咯型	PyrPIB	超酸催化聚芳基	1.79	49.08(80℃)	64.8%电导率保持(1 mol·L^-1 NaOH，80℃，1050 h)	[59]
	螺环型	Spiro-ionenes	螺环-阳离子聚合物	4	120(90℃)(与聚苯并咪唑共混后)	NMR谱图无变化(1 mol·L^-1 KOH，80℃，1800 h)	[60]
芳香型季铵盐	胍型	M-PAES-TMG	含氟聚芳醚	1.03	36（80℃）	63.9%电导率保持（0.5 mol·L^-1 NaOH，80℃， 382 h）	[75]
	咪唑型	Syne-IM PPO	聚苯醚	1.60	34（80℃）	95%电导率保持（1 mol·L^-1 KOH，80℃，48 h）	[64]
	吡唑型	PXm-Tn	全交联聚芳基	0.91	111.6（80℃）	76%电导率保持（1 mol·L^-1 KOH， 80℃,720 h）	[67]
季盐	氨基季型	AAEM-17	聚烯烃	0.67±0.1	22±1（22℃）	81.8%电导率保持（1 mol·L^-1 KOH，80℃，22 d）	[30]
季盐	芳基季型	TPQPOH	聚醚砜	1.09	27（20℃）	100%电导率保持（1 mol·L^-1 KOH，80℃，48 h）	[69]
金属盐	二茂钴型	H-AEM-OH	聚烯烃	1.86	90（90℃）	95%电导率保持（1 mol·L^-1 NaOH， 1个月）	[32]
金属盐	配位金属型	DCPD AEMs	聚烯烃	1.4	28.6（30℃）	7%质量损失（1 mol·L^-1 NaOH，80℃，24 h）	[33]

参考文献 75

13	王培灿, 雷青, 刘帅, 等. 电解水制氢MoS₂催化剂研究与氢能技术展望[J]. 化工进展, 2019, 38(1): 278-290.
	Wang P C, Lei Q, Liu S, et al. MoS₂-based electrocatalysts for hydrogen evolution and the prospect of hydrogen energy technology[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 278-290.
14	Lee W H, Kim Y S, Bae C. Robust hydroxide ion conducting poly(biphenyl alkylene)s for alkaline fuel cell membranes[J]. ACS Macro Letters, 2015, 4(8): 814-818.
15	You W, Noonan K J T, Coates G W. Alkaline-stable anion exchange membranes: a review of synthetic approaches[J]. Progress in Polymer Science, 2020, 100: 101-177.
16	Marino M G, Kreuer K D. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids[J]. ChemSusChem, 2015, 8(3): 513-523.
17	Hu J, Zhang C X, Cong J, et al. Plasma-grafted alkaline anion-exchange membranes based on polyvinyl chloride for potential application in direct alcohol fuel cell[J]. Journal of Power Sources, 2011, 196(10): 4483-4490.
18	Ran J, Wu L, Lin X C, et al. Synthesis of soluble copolymers bearing ionic graft for alkaline anion exchange membrane[J]. RSC Advances, 2012, 2(10): 4250-4257.
19	Olsson J S, Pham T H, Jannasch P. Functionalizing polystyrene with N-alicyclic piperidine-based cations via Friedel–Crafts alkylation for highly alkali-stable anion-exchange membranes[J]. Macromolecules, 2020, 53(12):4722-4732.
20	Danks T N, Slade R C T, Varcoe J R. Comparison of PVDF- and FEP-based radiation-grafted alkaline anion-exchange membranes for use in low temperature portable DMFCs[J]. Journal of Materials Chemistry, 2002, 12(12): 3371-3373.
21	Fang J, Yang Y X, Lu X H, et al. Cross-linked, ETFE-derived and radiation grafted membranes for anion exchange membrane fuel cell applications[J]. International Journal of Hydrogen Energy, 2012, 37(1): 594-602.
22	Willdorf-Cohen S, Mondal A N, Dekel D R, et al. Chemical stability of poly(phenylene oxide)-based ionomers in an anion exchange-membrane fuel cell environment[J]. Journal of Materials Chemistry A, 2018, 6(44): 22234-22239.
23	Liu M Y, Wang Z, Mei J, et al. A facile functionalized routine for the synthesis of imidazolium-based anion-exchange membrane with excellent alkaline stability[J]. Journal of Membrane Science, 2016, 505: 138-147.
1	Varcoe J R, Atanassov P, Dekel D R, et al. Anion-exchange membranes in electrochemical energy systems[J]. Energy Environ. Sci., 2014, 7(10): 3135-3191.
2	Ran J, Wu L, Ru Y F, et al. Anion exchange membranes (AEMs) based on poly(2, 6-dimethyl-1, 4-phenylene oxide) (PPO) and its derivatives[J]. Polymer Chemistry, 2015, 6(32): 5809-5826.
3	Strathmann H. Electrodialysis, a mature technology with a multitude of new applications[J]. Desalination, 2010, 264(3): 268-288.
4	Ran J, Wu L, He Y B, et al. Ion exchange membranes: new developments and applications[J]. Journal of Membrane Science, 2017, 522: 267-291.
5	Strathmann H, Grabowski A, Eigenberger G. Ion-exchange membranes in the chemical process industry[J]. Industrial & Engineering Chemistry Research, 2013, 52(31): 10364-10379.
6	Varcoe J R, Slade R C T. Prospects for alkaline anion-exchange membranes in low temperature fuel cells[J]. Fuel Cells, 2005, 5(2): 187-200.
24	Kim D J, Lee B N, Nam S Y. Synthesis and characterization of PEEK containing imidazole for anion exchange membrane fuel cell[J]. International Journal of Hydrogen Energy, 2017, 42(37): 23759-23767.
25	Jeon J Y, Park S, Han J, et al. Synthesis of aromatic anion exchange membranes by Friedel–Crafts bromoalkylation and cross-linking of polystyrene block copolymers[J]. Macromolecules, 2019, 52(5): 2139-2147.
26	Chen X L, Xiu Q W, En N H, et al. Quaternized triblock polymer anion exchange membranes with enhanced alkaline stability[J]. Journal of Membrane Science, 2017, 541: 358-366.
27	Varcoe J R, Slade R C T, Lam How Yee E, et al. Poly(ethylene-co-tetrafluoroethylene)-derived radiation-grafted anion-exchange membrane with properties specifically tailored for application in metal-cation-free alkaline polymer electrolyte fuel cells[J]. Chemistry of Materials, 2007, 19(10): 2686-2693.
28	Zhang M, Shan C R, Liu L, et al. Facilitating anion transport in polyolefin-based anion exchange membranes via bulky side chains[J]. ACS Applied Materials & Interfaces, 2016, 8(35): 23321-23330.
29	Zhu L, Peng X, Shang S L, et al. High performance anion exchange membrane fuel cells enabled by fluoropoly(olefin) membranes[J]. Advanced Functional Materials, 2019, 29(26): 1902059.
7	Ursua A, Gandia L M, Sanchis P. Hydrogen production from water electrolysis: current status and future trends[J]. Proceedings of the IEEE, 2012, 100(2): 410-426.
8	Hickner M A, Ghassemi H, Kim Y S, et al. Alternative polymer systems for proton exchange membranes (PEMs)[J]. Chemical Reviews, 2004, 104(10): 4587-4612.
9	Siracusano S, Baglio V, Briguglio N, et al. An electrochemical study of a PEM stack for water electrolysis[J]. International Journal of Hydrogen Energy, 2012, 37(2): 1939-1946.
10	Varcoe J R, Slade R C T, Lam How Yee E. An alkaline polymer electrochemical interface: a breakthrough in application of alkaline anion-exchange membranes in fuel cells[J]. Chemical Communications, 2006, (13): 1428-1429.
11	Leng Y J, Chen G, Mendoza A J, et al. Solid-state water electrolysis with an alkaline membrane[J]. Journal of the American Chemical Society, 2012, 134(22): 9054-9057.
12	万磊, 赖忆铭, 王保国. 离子交换膜界面结构对膜电极性能影响的研究进展[J]. 膜科学与技术, 2019, 39(4): 132-141, 147.
30	Noonan K J, Hugar K M, Kostalik 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.
31	Kostalik H A, Clark T J, Robertson N J, et al. Solvent processable tetraalkylammonium-functionalized polyethylene for use as an alkaline anion exchange membrane[J]. Macromolecules, 2010, 43(17): 7147-7150.
12	Wan L, Lai Y M, Wang B G. Recent progress in patterning ion exchange membrane interface for membrane electrode assembly[J]. Membrane Science and Technology, 2019, 39(4): 132-141, 147.
32	Zhu T, Xu S C, Rahman A, et al. Cationic metallo-polyelectrolytes for robust alkaline anion-exchange membranes[J]. Angewandte Chemie International Edition, 2018, 57(9): 2388-2392.
33	Zha Y P, Disabb-Miller M L, Johnson Z D, et al. Metal-cation-based anion exchange membranes[J]. Journal of the American Chemical Society, 2012, 134(10): 4493-4496.
34	Li Y F, Liu Y, Savage A M, et al. Polyethylene-based block copolymers for anion exchange membranes[J]. Macromolecules, 2015, 48(18): 6523-6533.
35	Gu F L, Dong H L, Li Y Y, et al. Base stable pyrrolidinium cations for alkaline anion exchange membrane applications[J]. Macromolecules, 2014, 47(19): 6740-6747.
36	Nuñez S A, Hickner M A. Quantitative ¹H NMR analysis of chemical stabilities in anion-exchange membranes[J]. ACS Macro Letters, 2013, 2(1): 49-52.
37	Zhang S L, Wu C M, Xu T W, et al. Synthesis and characterizations of anion exchange organic-inorganic hybrid materials based on poly(2, 6-dimethyl-1, 4-phenylene oxide) (PPO)[J]. Journal of Solid State Chemistry, 2005, 178(7): 2292-2300.
38	Xu T W, Liu Z M, Li Y, et al. Preparation and characterization of Type Ⅱ anion exchange membranes from poly(2, 6-dimethyl-1, 4-phenylene oxide) (PPO)[J]. Journal of Membrane Science, 2008, 320(1/2): 232-239.
39	Mohanty A D, Tignor S E, Krause J A, et al. Systematic alkaline stability study of polymer backbones for anion exchange membrane applications[J]. Macromolecules, 2016, 49(9): 3361-3372.
40	Ran J, Ding L, Yu D B, et al. A novel strategy to construct highly conductive and stabilized anionic channels by fluorocarbon grafted polymers[J]. Journal of Membrane Science, 2018, 549: 631-637.
41	Dang H S, Weiber E A, Jannasch P. Poly(phenylene oxide) functionalized with quaternary ammonium groups via flexible alkyl spacers for high-performance anion exchange membranes[J]. Journal of Materials Chemistry A, 2015, 3(10): 5280-5284.
42	Cruz A R, Zolotukhin M G, Morales S L, et al. Use of 4-piperidones in one-pot syntheses of novel, high-molecular-weight linear and virtually 100%-hyperbranched polymers[J]. Chemical Communications, 2009, (29): 4408-4410.
43	Cruz A R, Hernandez M C G, Guzmán-Gutiérrez M T, et al. Precision synthesis of narrow polydispersity, ultrahigh molecular weight linear aromatic polymers by A2 + B2 nonstoichiometric step-selective polymerization[J]. Macromolecules, 2012, 45(17): 6774-6780.
44	Chen N J, Hu C, Wang H H, et al. Poly(alkyl-terphenyl piperidinium) ionomers and membranes with an outstanding alkaline-membrane fuel-cell performance of 2.58 W·cm^-2[J]. Angewandte Chemie International Edition, 2021, 60(14): 7710-7718.
45	Olsson J S, Pham T H, Jannasch P. Poly(arylene piperidinium) hydroxide ion exchange membranes: synthesis, alkaline stability, and conductivity[J]. Advanced Functional Materials, 2018, 28(2): 1702758.
46	Wang J H, Zhao Y, Setzler B P, et al. Poly(aryl piperidinium) membranes and ionomers for hydroxide exchange membrane fuel cells[J]. Nature Energy, 2019, 4(5): 392-398.
47	Miyanishi S, Yamaguchi T. Highly durable spirobifluorene-based aromatic anion conducting polymer for a solid ionomer of alkaline fuel cells and water electrolysis cells[J]. Journal of Materials Chemistry A, 2019, 7(5): 2219-2224.
48	Fan J T, Willdorf-Cohen S, Schibli E M, et al. Poly(bis-arylimidazoliums) possessing high hydroxide ion exchange capacity and high alkaline stability[J]. Nature Communications, 2019, 10: 2306.
49	Wright A G, Weissbach T, Holdcroft S. Poly(phenylene) and m-terphenyl as powerful protecting groups for the preparation of stable organic hydroxides[J]. Angewandte Chemie International Edition, 2016, 55(15): 4818-4821.
50	Luo T, Abdu S, Wessling M. Selectivity of ion exchange membranes: a review[J]. Journal of Membrane Science, 2018, 555: 429-454.
51	Merle G, Wessling M, Nijmeijer K. Anion exchange membranes for alkaline fuel cells: a review[J]. Journal of Membrane Science, 2011, 377(1/2): 1-35.
52	Lu W T, Zhang G, Li J, et al. Polybenzimidazole-crosslinked poly(vinylbenzyl chloride) with quaternary 1, 4-diazabicyclo (2.2.2) octane groups as high-performance anion exchange membrane for fuel cells[J]. Journal of Power Sources, 2015, 296: 204-214.
53	Wang X, Li M Q, Golding B T, et al. A polytetrafluoroethylene-quaternary 1, 4-diazabicyclo-[2.2.2]-octane polysulfone composite membrane for alkaline anion exchange membrane fuel cells[J]. International Journal of Hydrogen Energy, 2011, 36(16): 10022-10026.
54	Wang J J, He G H, Wu X M, et al. Crosslinked poly (ether ether ketone) hydroxide exchange membranes with improved conductivity[J]. Journal of Membrane Science, 2014, 459: 86-95.
55	Das G, Park B J, Yoon H H. A bionanocomposite based on 1, 4-diazabicyclo-[2.2.2]-octane cellulose nanofiber cross-linked-quaternary polysulfone as an anion conducting membrane[J]. Journal of Materials Chemistry A, 2016, 4(40): 15554-15564.
56	Allushi A, Pham T H, Olsson J S, et al. Ether-free polyfluorenes tethered with quinuclidinium cations as hydroxide exchange membranes[J]. Journal of Materials Chemistry A, 2019, 7(47): 27164-27174.
57	Strasser D J, Graziano B J, Knauss D M. Base stable poly(diallylpiperidinium hydroxide) multiblock copolymers for anion exchange membranes[J]. Journal of Materials Chemistry A, 2017, 5(20): 9627-9640.
58	Olsson J S, Pham T H, Jannasch P. Poly(N,N-diallylazacycloalkane)s for anion-exchange membranes functionalized with N-spirocyclic quaternary ammonium cations[J]. Macromolecules, 2017, 50(7): 2784-2793.
59	Zhang S, Zhu X L, Jin C H. Development of a high-performance anion exchange membrane using poly(isatin biphenylene) with flexible heterocyclic quaternary ammonium cations for alkaline fuel cells[J]. Journal of Materials Chemistry A, 2019, 7(12): 6883-6893.
60	Pham T H, Olsson J S, Jannasch P. N-spirocyclic quaternary ammonium ionenes for anion-exchange membranes[J]. Journal of the American Chemical Society, 2017, 139(8): 2888-2891.
61	Xiao L, Zhang H, Jana T, et al. Synthesis and characterization of pyridine-based polybenzimidazoles for high temperature polymer electrolyte membrane fuel cell applications[J]. Fuel Cells, 2005, 5(2): 287-295.
62	Li W, Fang J, Lv M, et al. Novel anion exchange membranes based on polymerizable imidazolium salt for alkaline fuel cell applications[J]. Journal of Materials Chemistry, 2011, 21(30): 11340.
63	Lin B C, Dong H L, Li Y Y, et al. Alkaline stable C2-substituted imidazolium-based anion-exchange membranes[J]. Chemistry of Materials, 2013, 25(9): 1858-1867.
64	Wang J H, Gu S, Kaspar R B, et al. Stabilizing the imidazolium cation in hydroxide-exchange membranes for fuel cells[J]. ChemSusChem, 2013, 6(11): 2079-2082.
65	Zhu Y, He Y, Ge X, et al. A benzyltetramethylimidazolium-based membrane with exceptional alkaline stability in fuel cells: role of its structure in alkaline stability[J]. Journal of Materials Chemistry A, 2018, 6(2):527-534
66	Hugar K M, Kostalik H A, Coates G W. Imidazolium cations with exceptional alkaline stability: a systematic study of structure-stability relationships[J]. Journal of the American Chemical Society, 2015, 137(27): 8730-8737.
67	Kim Y, Wang Y, France-Lanord A, et al. Ionic highways from covalent assembly in highly conducting and stable anion exchange membrane fuel cells[J]. Journal of the American Chemical Society, 2019, 141(45): 18152-18159.
68	Ye Y S, 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.
69	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.
70	Barnes A, Du Y F, Zhang W X, et al. Phosphonium-containing block copolymer anion exchange membranes: effect of quaternization level on bulk and surface morphologies at hydrated and dehydrated states[J]. Macromolecules, 2019, 52(16): 6097-6106.
71	Tang H Y, Li D F, Li N W, et al. Anion conductive poly(2, 6-dimethyl phenylene oxide)s with clicked bulky quaternary phosphonium groups[J]. Journal of Membrane Science, 2018, 558: 9-16.
72	Zhang B Z, Kaspar R B, Gu S, et al. A new alkali-stable phosphonium cation based on fundamental understanding of degradation mechanisms[J]. ChemSusChem, 2016, 9(17): 2374-2379.
73	Kwasny M T, Zhu L, Hickner M A, et al. Thermodynamics of counterion release is critical for anion exchange membrane conductivity[J]. Journal of the American Chemical Society, 2018, 140(25): 7961-7969.
74	Zhu T, Sha Y, Firouzjaie H A, et al. Rational synthesis of metallo-cations toward redox-and alkaline-stable metallo-polyelectrolytes[J]. Journal of the American Chemical Society, 2020, 142(2): 1083-1089.
75	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.

[1]	黄琮琪, 吴一梅, 陈建业, 邵双全. 碱性电解水制氢装置热管理系统仿真研究[J]. 化工学报, 2023, 74(S1): 320-328.
[2]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[3]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[4]	罗来明, 张劲, 郭志斌, 王海宁, 卢善富, 相艳. 1~5 kW高温聚合物电解质膜燃料电池堆的理论模拟与组装测试[J]. 化工学报, 2023, 74(4): 1724-1734.
[5]	钱志广, 樊越, 王世学, 岳利可, 王金山, 朱禹. 吹扫条件对PEMFC阻抗弛豫现象和低温启动的影响[J]. 化工学报, 2023, 74(3): 1286-1293.
[6]	郭祥, 乔金硕, 王振华, 孙旺, 孙克宁. 碳燃料固体氧化物燃料电池结构研究进展[J]. 化工学报, 2023, 74(1): 290-302.
[7]	张童, 杨扬, 叶丁丁, 陈蓉, 朱恂, 廖强. 催化剂分布对可渗透阳极微流体燃料电池性能特性影响的研究[J]. 化工学报, 2022, 73(9): 4156-4162.
[8]	方辉煌, 程金星, 罗宇, 陈崇启, 周晨, 江莉龙. 氨电氧化催化剂及其低温直接氨碱性膜燃料电池性能的研究进展[J]. 化工学报, 2022, 73(9): 3802-3814.
[9]	雍加望, 赵倩倩, 冯能莲. 基于非线性动态模型的质子交换膜燃料电池故障诊断[J]. 化工学报, 2022, 73(9): 3983-3993.
[10]	张婉晨, 陈晓阳, 吕秋秋, 钟秦, 朱腾龙. Co掺杂SrTi_0.3Fe_0.7O_3-_δ 阳极SOFC在化工副产气燃料下的性能及稳定性[J]. 化工学报, 2022, 73(9): 4079-4086.
[11]	邵健, 冯军宗, 柳凤琦, 姜勇刚, 李良军, 冯坚. 酚醛树脂基炭微球结构调控与功能化制备研究进展[J]. 化工学报, 2022, 73(9): 3787-3801.
[12]	艾承燚, 乔金硕, 王振华, 孙旺, 孙克宁. 原位析出纳米合金的PrBaFe₂O_6-_δ 基阳极构筑及其在固体碳燃料电池中的应用研究[J]. 化工学报, 2022, 73(8): 3708-3719.
[13]	魏琳, 郭剑, 廖梓豪, Dafalla Ahmed Mohmed, 蒋方明. 空气流量对空冷燃料电池电堆性能的影响研究[J]. 化工学报, 2022, 73(7): 3222-3231.
[14]	张红锐, 张田, 隆曦孜, 李先宁. 光催化与微生物燃料电池耦合对Cu-EDTA的降解特性[J]. 化工学报, 2022, 73(5): 2149-2157.
[15]	李文怀, 周嵬. 高氧离子电导钙钛矿的影响因素分析和设计策略[J]. 化工学报, 2022, 73(4): 1455-1471.