碱性离子膜内强化离子传递策略及研究进展

doi:10.11949/0438-1157.20240445

摘要/Abstract

摘要：

碱性离子膜（阴离子交换膜）作为电解水制氢、二氧化碳还原等电化学过程的关键材料，在传递离子、分隔阴阳两极和阻隔气体渗透方面，具有重要应用价值。现有碱性离子膜起源于电渗析过程，其离子传导率偏低，无法满足电化学过程对高电流密度、高稳定性需求。针对电解水制氢过程对高通量、低电阻、低能耗的需求，本文从膜内离子传递过程出发，结合氢氧根传递特点，分析满足综合性能需求的碱性离子膜结构特征，重点阐述膜内强化离子传递策略。归纳分析最新研究成果，分类讨论交联、定向排列、微相分离以及构筑微孔等具体策略，指明高性能碱性离子膜研究路径，促进以电解水制氢为代表的电化学反应器技术发展。

关键词: 碱性离子膜, 自由体积理论, 离子传递, 离子传导率, 电解水

Abstract:

As key materials in electrochemical processes such as water electrolysis and CO₂ electroreduction, anion exchange membranes have important application value in ions transport, separating anode and cathode, and blocking gas penetration. Originating from electrodialysis process, most commercial anion exchange membranes have low conductivity, which can't meet the demand of high current density and high stability in electrochemical process. For demands of high flux, low resistance and low energy consumption in water electrolysis, this work investigates ions transport in membranes, combined with features of hydroxide ions, analyzes the structural characteristics of anion exchange membranes that meet the comprehensive performance requirements, and focuses on the strategies of enhanced ion transport. The latest research are summarized, and specific strategies such as cross-linking, directional alignment, microphase separations and micropore construction are discussed, indicating the direction of high-performance anion exchange membranes, and promoting the development of electrochemical progresses such as water electrolysis.

Key words: anion exchange membrane, free volume theory, ion transport, ion conductivity, water electrolysis

中图分类号:

TQ021.4

庞茂斌, 徐子昂, 甄翊含, 许琴, 林董澄, 刘京, 王保国. 碱性离子膜内强化离子传递策略及研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20240445.

Maobin PANG, Zi'ang XU, Yihan ZHEN, Qin XU, Dongcheng LIN, Jing LIU, Baoguo WANG. Recent progress of strategies for enhanced ion transport in anion exchange membranes[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240445.

图/表 15

图1 阴离子交换膜内氢氧根的输运机制[29]

Fig.1 Transport mechanisms proposed for hydroxide ions in anion-exchange membranes[29]

图2 氢氧根传递机制研究进展[32-35]注:(a)氢氧根Grotthuss机制;(b)AEM内氢氧根传递;(c)水通道"瓶颈"处氢氧根传递(d)QENS测试结果;(e~g)膜内氢氧根传递行为解耦

Fig.2 Progress of hydroxide ion transfer mechanism[32-35](a) Grotthuss mechanism of hydroxide; (b) Hydroxide transfers in AEM; (c) Hydroxide transfers at "bottleneck" of water channel; (d)QENS test results; (e~g) Decoupling of hydroxyl transfer behavior in membranes

图3 膜内氢氧根传递机制电路类比[29]

Fig.3 Electric circuit analogy of the transport mechanisms for hydroxide ions in anion exchange membranes[29]

图4 交联策略常见结构示意图[45,54-55]注:(a) PBP-ASU-PPO结构; (b) PPO-EO/BEO/TEO结构; (c)PEP80结构及合成路径

Fig.4 Schematic illustration of common structures of cross-linking strategies[45,54-55](a) PBP-ASU-PPO structure; (b) PO-EO/BEO/TEO structure; (c)PEP80 structure and synthesis pathway

图5 QAPS结构微相分离策略示意图[59-60]注:(a~b) aQAPS-Sx结构; (c~f) TEM图像;(g)SAXS图像;(h) 离子传导率与温度关系;(i) 溶胀率与温度关系;(j) PBTP及PBnPip结构

Fig.5 Schematic illustration of microphase separation for QAPS structure[59-60](a~b) Structure of aQAPS-Sx; (c~f) TEM images; (g) SAXS image; (h) Relation between Ionic conductivity and temperature; (i) Relation between Swelling degree and temperature; (j) Structure of PBTP and PCTP-n

图6 PBnPip结构微相分离策略示意图[46]注:(a~d) TEM图像;(a'~d') AFM图像;(e)溶胀率与温度关系;(f)离子传导率与温度关系;(g)分子结构

Fig.5 Schematic illustration of microphase separation for PBnPip structure[46](a~d) TEM images; (a '~d') AFM image; (e) Relationship between swelling rate and temperature;(f) Relation between conductivity and temperature; (g) Molecular structure

图7 多重交联结构PXm-Tn用于高效传递氢氧根[62]注:(a)分子结构及合成路径; (b)有序/无序通道下氢氧根传递能垒对比

Fig.6 Multiple cross-linked PXm-Tn for OH- transportation highway[62](a) Molecular structure and synthetic pathways; (b) Hydroxyl transfer barrier comparison in ordered/disordered channels

图8 磁场定向构筑稳定二茂铁基离子交换膜[63]注:(a)分子结构;(b)筑膜液及膜材料图像;(c)磁场对膜材料TEM图像的影响;(d)筑膜条件对膜材料离子传导率的影响

Fig.7 Magnetic-field-oriented mixed-valence-stabilized ferrocenium AEM[63](a) Molecular structure; (b) Images of film building fluid and membranes; (c) Influence of magnetic field on TEM images;(d) The influence of different conditions on the conductivity of membranes

图9 PIM类碱性离子膜合成路径[64]注:(a)Troger's Base类AEM合成路线;(b) 基于PIM-1结构的AEM改性路线

Fig.9 Synthetic route of AEM from positively charged PIMs[64](a)Troger's Base AEM synthesis route; (b) AEM modification route based on PIM-1 structure

图10 COFs材料合成路径[78-79]注:(a) 醛单体调节COF-QAs结构;(b) 侧链长度调节COF-QAs结构

Fig.10 Synthetic route of COFs[78-79](a) Structures of COF-QAs regulated by aldehyde monomers; (b) COF-QAs structure regulated by length side chains

图11 COFs结构强化离子传递策略[80]

Fig.11 Schematic illustration of enhanced ion transport of COFs[80]

图12 Cu2+交联壳聚糖AEM强化离子传递[81]

Fig.12 Cu2+ crosslinked chitosan AEM enhances ion transport[81]

图13 “可移动快车”策略路径[64]

Fig.13 Synthesis route of Mobile Ion Shuttles strategy[64]

表1 不同离子传递强化策略的代表AEMs

Table 1 Representative AEMs of reinforcement strategies for promoting ion transfer

传递强化策略	AEMs名称	IEC/ (mmol·g^-1)	水含量（%，80℃）	溶胀率（%，80℃）	OH型离子传导率/ （mS·cm^-1，80℃）	机械强度/ MPa	文献
高IEC情况交联抑制溶胀	10% PBP-ASU-PPO	2.61	140	25	128	32	^[41]
	PEP80-20PS	4.05	256	50.2	354	1.1	^[54]
	x-BEO-PPO	2.23	101.8	18.18	132	27	^[55]
微相分离构建局部传递通道	PCTP-2	2.83	54.2	19.8	135	42	^[60]
	aQAPS-S₈	1		21	105	12.1	^[59]
	PB2Pip-5C8F	2.53	101.4（30℃）	48.3	168.5	37	^[46]
定向排列提升通道利用率	PX75-T50	0.91	7.9	2.6	111.6	172	^[62]
定向排列提升通道利用率	MM-LPF-OH	1.654	37	7（TP） 28（IP）	160（95℃，TP） 18（95℃，IP）	22	^[63]
微孔构筑刚性传递通道	BPPO-MPC₆₀	0.62	3.65	2＜	182		^[66]
	DMBP-QTB	0.82	36（30℃）	5＜	164.4		^[68]
	COF-QA-2	2.38	81	20	212	50	^[79]
	COF-SDQA	2.70	77.7	11.71	329.4	27	^[80]
其他策略	Chitosan-Cu	1.6	56		67（rt）	112	^[81]
其他策略	AAEM_3d-e·2OH-	0.68	18.4（60℃）	7.5（60℃）	189		^[82]

表2 主要离子传递强化策略对比

Table 2 Comparison of reinforcement strategies for promoting ion transfer

传递强化策略	优点	缺点
交联	提升IEC及抑制溶胀率	交联程度有限（5%＜） IEC利用程度下降成本提升（工序增加）
微相分离	局部传递通道阻力降低	微相分离程度难以控制材料均一性问题亲水区域局部溶胀较高
定向排列	传递通道利用效率提升	适用范围较小（结构特殊性）成本提升（工序繁琐）
微孔构筑	水环境浓度提升刚性通道传递阻力下降	结构适配性不足（稳定性、功能基团种类）机械强度（高分子链非紧密堆积）
微孔构筑	水环境浓度提升刚性通道传递阻力下降	IEC过低限制离子传导率进一步提升

参考文献 83

1	Chu S, Majumdar A. Opportunities and challenges for a sustainable energy future[J]. Nature, 2012, 488(7411): 294-303.
2	Heide D, von Bremen L, Greiner M, et al. Seasonal optimal mix of wind and solar power in a future, highly renewable Europe[J]. Renewable Energy, 2010, 35(11): 2483-2489.
3	Li D G, Park E J, Zhu W L, et al. Highly quaternized polystyrene ionomers for high performance anion exchange membrane water electrolysers[J]. Nature Energy, 2020, 5: 378-385.
4	Ulleberg Ø, Nakken T, Eté A. The wind/hydrogen demonstration system at Utsira in Norway: Evaluation of system performance using operational data and updated hydrogen energy system modeling tools[J]. International Journal of Hydrogen Energy, 2010, 35(5): 1841-1852.
5	Bergen A, Pitt L, Rowe A, et al. Transient electrolyser response in a renewable-regenerative energy system[J]. International Journal of Hydrogen Energy, 2009, 34(1): 64-70.
6	Zeng K, Zhang D K. Recent progress in alkaline water electrolysis for hydrogen production and applications[J]. Progress in Energy and Combustion Science, 2010, 36(3): 307-326.
7	Carmo M, Fritz D L, Mergel J, et al. A comprehensive review on PEM water electrolysis[J]. International Journal of Hydrogen Energy, 2013, 38(12): 4901-4934.
8	Diaz L A, Coppola R E, Abuin G C, et al. Alkali-doped polyvinyl alcohol–Polybenzimidazole membranes for alkaline water electrolysis[J]. Journal of Membrane Science, 2017, 535: 45-55.
9	Pavel C C, Cecconi F, Emiliani C, et al. Highly efficient platinum group metal free based membrane-electrode assembly for anion exchange membrane water electrolysis[J]. Angewandte Chemie International Edition, 2014, 53(5): 1378-1381.
10	Xu T W. Ion exchange membranes: State of their development and perspective[J]. Journal of Membrane Science, 2005, 263(1-2): 1-29.
11	Xiong P, Zhang L Y, Chen Y Y, et al. A chemistry and microstructure perspective on ion-conducting membranes for redox flow batteries[J]. Angewandte Chemie International Edition, 2021, 60(47): 24770-24798.
12	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.
13	Nawn G, Vezzù K, Cavinato G, et al. Opening doors to future electrochemical energy devices: the anion-conducting polyketone polyelectrolytes[J]. Advanced Functional Materials, 2018, 28(29): 1706522.
14	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.
15	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.
16	尹卓毓, 吴洪, 姜忠义. 阴离子交换膜离子传导率与耐碱稳定性研究进展[J].膜科学与技术, 2023, 43(6): 112-127.
	Yin Z Y, Wu H, Jiang Z Y. Progress in the research of ionic conductivity and alkaline stability of anion exchange membranes[J].Membrane Science and Technology(Chinese), 2023, 43(6): 112-127.
17	Ziv N, Dekel D R. A practical method for measuring the true hydroxide conductivity of anion exchange membranes[J]. Electrochemistry Communications, 2018, 88: 109-113.
18	葛倩倩, 葛亮, 汪耀明, 等. 离子交换膜的发展态势与应用展望[J].化工进展, 2016, 35(6): 1774-1785.
	Ge Q Q, Ge L, Wang Y M, et al. Perspective in ion exchange membranes[J].Chemical Industry and Engineering Progress, 2016, 35(6): 1774-1785.
19	Abbasi R, Setzler B P, Lin S S, et al. A roadmap to low-cost hydrogen with hydroxide exchange membrane electrolyzers[J]. Advanced Materials, 2019, 31(31): 1805876.
20	Vincent I, Bessarabov D. Low cost hydrogen production by anion exchange membrane electrolysis: A review[J]. Renewable and Sustainable Energy Reviews, 2018, 81: 1690-1704.
21	王培灿, 万磊, 徐子昂, 等. 碱性膜电解水制氢技术现状与展望[J].化工学报, 2021, 72(12): 6161-6175.
	Wang P C, Wan L, Xu Z A, et al. Hydrogen production based-on anion exchange membrane water electrolysis: a critical review and perspective[J].CIESC Journal, 2021, 72(12): 6161-6175.
22	Xu Z A, Wan L, Liao Y W, et al. Anisotropic anion exchange membranes with extremely high water uptake for water electrolysis and fuel cells[J]. Journal of Materials Chemistry A, 2021, 9(41): 23485-23496.
23	Wan L, Xu Z A, Xu Q, et al. Key components and design strategy of the membrane electrode assembly for alkaline water electrolysis[J]. Energy & Environmental Science, 2023, 16(4): 1384-1430.
24	Song W J, Peng K, Xu W, et al. Upscaled production of an ultramicroporous anion-exchange membrane enables long-term operation in electrochemical energy devices[J]. Nature Communications, 2023, 14: 2732.
25	Zeng M Y, He X Y, Wen J, et al. N-methylquinuclidinium-based anion exchange membrane with ultrahigh alkaline stability[J]. Advanced Materials, 2023, 35(51): 2306675.
26	Cohen M H, Turnbull D. Molecular transport in liquids and glasses[J]. The Journal of Chemical Physics, 1959, 31(5): 1164-1169.
27	Zielinski J M, Duda J L. Predicting polymer/solvent diffusion coefficients using free-volume theory[J]. AIChE Journal, 1992, 38(3): 405-415.
28	徐晖, 王绍宁, 郑俊民. 用自由体积理论描述扩散现象[J].中国药剂学杂志(网络版), 2004, 2(1): 7-13.
	Xu H, Wang S N, Zheng J M. Description of the diffusion phenomenon using free volume theory[J].Chinese Journal of Pharmaceutics(Online Edition), 2004, 2(1): 7-13.
29	Ramírez S C, Paz R R. New Trends in Ion Exchange Studies[M]. Turkey: Selcan Karakuş, 2018: 51-70.
30	Thampan T, Malhotra S, Tang H, et al. Modeling of conductive transport in proton-exchange membranes for fuel cells[J]. Journal of the Electrochemical Society, 2000, 147(9): 3242.
31	Wang Z X, Chen K, Han J H, et al. Anion exchange membranes for fuel cells: equilibrium water content and conductivity characterization[J]. Advanced Functional Materials, 2023, 33(40): 2303857.
32	Tuckerman M E, Marx D, Parrinello M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution[J]. Nature, 2002, 417: 925-929.
33	Chen C, Tse Y L S, Lindberg G E, et al. Hydroxide solvation and transport in anion exchange membranes[J]. Journal of the American Chemical Society, 2016, 138(3): 991-1000.
34	Dong D P, Zhang W W, van Duin A C T, et al. Grotthuss versus vehicular transport of hydroxide in anion-exchange membranes: insight from combined reactive and nonreactive molecular simulations[J]. The Journal of Physical Chemistry Letters, 2018, 9(4): 825-829.
35	Foglia F, Berrod Q, Clancy A J, et al. Disentangling water, ion and polymer dynamics in an anion exchange membrane[J]. Nature Materials, 2022, 21: 555-563.
36	Perrin J C, Lyonnard S, Volino F. Quasielastic neutron scattering study of water dynamics in hydrated nafion membranes[J]. The Journal of Physical Chemistry C, 2007, 111(8): 3393-3404.
37	Lyonnard S, Berrod Q, Brüning B A, et al. Perfluorinated surfactants as model charged systems for understanding the effect of confinement on proton transport and water mobility in fuel cell membranes. A study by QENS[J]. The European Physical Journal Special Topics, 2010, 189(1): 205-216.
38	Berrod Q, Hanot S, Guillermo A, et al. Water sub-diffusion in membranes for fuel cells[J]. Scientific Reports, 2017, 7(1): 8326.
39	Park J S, Park S H, Yim S D, et al. Performance of solid alkaline fuel cells employing anion-exchange membranes[J]. Journal of Power Sources, 2008, 178(2): 620-626.
40	Yang Y X, Li P, Zheng X B, et al. Anion-exchange membrane water electrolyzers and fuel cells[J]. Chemical Society Reviews, 2022, 51(23): 9620-9693.
41	Du N Y, Roy C, Peach R, et al. Anion-exchange membrane water electrolyzers[J]. Chemical Reviews, 2022, 122(13): 11830-11895.
42	Chen N J, Long C, Li Y X, et al. High-performance layered double hydroxide/poly(2,6-dimethyl-1,4-phenylene oxide) membrane with porous sandwich structure for anion exchange membrane fuel cell applications[J]. Journal of Membrane Science, 2018, 552: 51-60.
43	Fan J T, Zhu H, Li R, et al. Layered double hydroxide–polyphosphazene-based ionomer hybrid membranes with electric field-aligned domains for hydroxide transport[J]. Journal of Materials Chemistry A, 2014, 2(22): 8376-8385.
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	Chen N J, Lu C R, Li Y X, et al. Robust poly(aryl piperidinium)/N-spirocyclic poly(2,6-dimethyl-1,4-phenyl) for hydroxide-exchange membranes[J]. Journal of Membrane Science, 2019, 572: 246-254.
46	Xu G D, Pan J, Zou X Y, et al. High-performance Poly(biphenyl piperidinium) type anion exchange membranes with interconnected ion transfer channels: cooperativity of dual cations and fluorinated side chains[J]. Advanced Functional Materials, 2023, 33(35): 2302364.
47	徐子昂, 万磊, 刘凯, 等. 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.
	Xu Z A, Wan L, Liu K, et al. Recent progress of molecular design for highly stable alkaline anion exchange membranes[J].CIESC Journal, 2021, 72(8): 3891-3906.
48	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.
49	Li D G, Matanovic I, Lee A S, et al. Phenyl oxidation impacts the durability of alkaline membrane water electrolyzer[J]. ACS Applied Materials & Interfaces, 2019, 11(10): 9696-9701.
50	Li D G, Chung H T, Maurya S, et al. Impact of ionomer adsorption on alkaline hydrogen oxidation activity and fuel cell performance[J]. Current Opinion in Electrochemistry, 2018, 12: 189-195.
51	Gilliam R J, Graydon J W, Kirk D W, et al. A review of specific conductivities of potassium hydroxide solutions for various concentrations and temperatures[J]. International Journal of Hydrogen Energy, 2007, 32(3): 359-364.
52	Pan J, Chen C, Zhuang L, et al. Designing advanced alkaline polymer electrolytes for fuel cell applications[J]. Accounts of Chemical Research, 2012, 45(3): 473-481.
53	Bai T T, Cong M Y, Jia Y X, et al. Preparation of self-crosslinking anion exchange membrane with acid block performance from side-chain type polysulfone[J]. Journal of Membrane Science, 2020, 599: 117831.
54	Chen H H, Bang K T, Tian Y, et al. Poly(ethylene piperidinium)s for anion exchange membranes[J]. Angewandte Chemie International Edition, 2023, 62(38): e202307690.
55	Sung S, Mayadevi T S, Min K, et al. Crosslinked PPO-based anion exchange membranes: The effect of crystallinity versus hydrophilicity by oxygen-containing crosslinker chain length[J]. Journal of Membrane Science, 2021, 619: 118774.
56	Wu L, Pan Q, Varcoe J R, et al. Thermal crosslinking of an alkaline anion exchange membrane bearing unsaturated side chains[J]. Journal of Membrane Science, 2015, 490: 1-8.
57	Wang L Z, Hickner M A. Low-temperature crosslinking of anion exchange membranes[J]. Polymer Chemistry, 2014, 5(8): 2928-2935.
58	Yang B W, Zhang C M. Progress in constructing high-performance anion exchange Membrane: Molecular design, microphase controllability and In-device property[J]. Chemical Engineering Journal, 2023, 457: 141094.
59	Pan J, Chen C, Li Y, et al. Constructing ionic highway in alkaline polymer electrolytes[J]. Energy & Environmental Science, 2014, 7(1): 354-360.
60	Cai Z H, Gao X L, Gao W T, et al. Effect of hydrophobic side chain length on Poly(carbazolyl terphenyl piperidinium) anion exchange membranes[J]. ACS Applied Energy Materials, 2022, 5(8): 10165-10176.
61	Zhang A R, Li L, Ma L L, et al. Soft template promoted microphase separation in anion exchange membrane of electrodialysis[J]. Journal of Membrane Science, 2022, 658: 120758.
62	Kim Y, Wang Y M, 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.
63	Liu X, Xie N, Xue J D, et al. Magnetic-field-oriented mixed-valence-stabilized ferrocenium anion-exchange membranes for fuel cells[J]. Nature Energy, 2022, 7: 329-339.
64	Zuo P P, Xu Z A, Zhu Q, et al. Ion exchange membranes: constructing and tuning ion transport channels[J]. Advanced Functional Materials, 2022, 32(52): 2207366.
65	Li Z Q, Guo J, Zheng J F, et al. A microporous polymer with suspended cations for anion exchange membrane fuel cells[J]. Macromolecules, 2020, 53(24): 10998-11008.
66	Yang Z J, Liu Y Z, Guo R, et al. Highly hydroxide conductive ionomers with fullerene functionalities[J]. Chemical Communications, 2016, 52(13): 2788-2791.
67	Zhang H Q, Zhang Y, Zhang F, et al. Enhancing side chain swing ability by novel all-carbon twisted backbone for high performance anion exchange membrane at relatively low IEC level[J]. Journal of Membrane Science Letters, 2021, 1(2): 100007.
68	Yang Z J, Guo R, Malpass-Evans R, et al. Highly conductive anion-exchange membranes from microporous tröger's base polymers[J]. Angewandte Chemie International Edition, 2016, 55(38): 11499-11502.
69	Inoue K, Ishiwari F, Fukushima T. Selective synthesis of diazacyclooctane-containing flexible ladder polymers with symmetrically or unsymmetrically substituted side chains[J]. Polymer Chemistry, 2020, 11(22): 3690-3694.
70	Ishiwari F, Takeuchi N, Sato T, et al. Rigid-to-flexible conformational transformation: an efficient route to ring-opening of a tröger's base-containing ladder polymer[J]. ACS Macro Letters, 2017, 6(7): 775-780.
71	Huang T, Zhang J F, Pei Y B, et al. Mechanically robust microporous anion exchange membranes with efficient anion conduction for fuel cells[J]. Chemical Engineering Journal, 2021, 418: 129311.
72	Ishiwari F, Sato T, Yamazaki H, et al. An anion-conductive microporous membrane composed of a rigid ladder polymer with a spirobiindane backbone[J]. Journal of Materials Chemistry A, 2016, 4(45): 17655-17659.
73	Yang Z Z, Guo W, Mahurin S M, et al. Surpassing Robeson upper limit for CO₂/N₂ separation with fluorinated carbon molecular sieve membranes[J]. Chem, 2020, 6(3): 631-645.
74	Xin L, Zhang D Z, Qu K, et al. Zr-MOF-enabled controllable ion sieving and proton conductivity in flow battery membrane[J]. Advanced Functional Materials, 2021, 31(42): 2104629.
75	Wu B, Ge L, Yu D B, et al. Cationic metal–organic framework porous membranes with high hydroxide conductivity and alkaline resistance for fuel cells[J]. Journal of Materials Chemistry A, 2016, 4(38): 14545-14549.
76	Khan N A, Zhang R N, Wu H, et al. Solid-vapor interface engineered covalent organic framework membranes for molecular separation[J]. Journal of the American Chemical Society, 2020, 142(31): 13450-13458.
77	Shen J L, Zhang R N, Su Y L, et al. Polydopamine-modulated covalent organic framework membranes for molecular separation[J]. Journal of Materials Chemistry A, 2019, 7(30): 18063-18071.
78	Kong Y, He X Y, Wu H, et al. Tight covalent organic framework membranes for efficient anion transport via molecular precursor engineering[J]. Angewandte Chemie International Edition, 2021, 60(32): 17638-17646.
79	He X Y, Yang Y, Wu H, et al. De novo design of covalent organic framework membranes toward ultrafast anion transport[J]. Advanced Materials, 2020, 32(36): 2001284.
80	Kong Y, Lyu B H, Fan C Y, et al. Manipulation of cationic group density in covalent organic framework membranes for efficient anion transport[J]. Journal of the American Chemical Society, 2023, 145(51): 27984-27992.
81	Wu M L, Zhang X, Zhao Y, et al. A high-performance hydroxide exchange membrane enabled by Cu2+-crosslinked chitosan[J]. Nature Nanotechnology, 2022, 17(6): 629-636.
82	Ge X L, He Y B, Guiver M D, et al. Alkaline anion-exchange membranes containing mobile ion shuttles[J]. Advanced Materials, 2016, 28(18): 3467-3472.
83	Ge X L, He Y B, Zhang K Y, et al. Fast bulky anion conduction enabled by free shuttling phosphonium cations[J]. Research, 2021, 2021: 9762709.

[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]	余后川, 任腾, 张宁, 姜晓滨, 代岩, 张晓鹏, 鲍军江, 贺高红. 二维氧化石墨烯膜离子选择性传递调控的研究进展[J]. 化工学报, 2023, 74(1): 303-312.
[3]	黄盼, 练成, 刘洪来. 基于模拟退火算法的真实多孔电极中热-质传递的研究[J]. 化工学报, 2022, 73(6): 2529-2542.
[4]	朱嫣然, 葛亮, 李兴亚, 徐铜文. 三相结构离子交换膜的构筑及应用研究[J]. 化工学报, 2022, 73(6): 2397-2414.
[5]	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.
[6]	祝海涛, 杨波, 吴雅琴, 高从堦. 电渗析脱盐过程离子传递现象的数值模拟[J]. 化工学报, 2020, 71(8): 3518-3526.
[7]	常明，陈爱平，何洪波，马磊，李春忠. 层层组装修饰Ni片阳极的光催化辅助电解水制氢[J]. 化工学报, 2012, 63(7): 2195-2201.
[8]	朱玉婵, 任占冬, 刘晔, 张智勇. 氧化电解水杀菌特性及其对肉品杀菌作用 [J]. 化工学报, 2009, 60(10): 2583-2589.
[9]	吕宏凌;王保国 . 高分子聚合物中溶剂扩散系数的预测 [J]. CIESC Journal, 2006, 57(1): 6-12.
[10]	王保国; 山口猛央; 中尾真一. 均相玻璃态高分子中溶剂扩散系数的数学模型 [J]. CIESC Journal, 2002, 53(4): 338-343.
[11]	蒋文华; 韩世钧. 3种芳香烃在聚乙烯膜中的无限稀释扩散系数 [J]. CIESC Journal, 2002, 53(3): 285-289.