电解水制氢用阴离子交换膜研究进展

doi:10.19799/j.cnki.2095-4239.2024.0553

摘要/Abstract

摘要：

阴离子交换膜电解水制氢融合了碱性电解水和质子交换膜电解水制氢技术的优点，具有电解效率高、响应速度快、成本低等特点，被认为是目前最有前景的可再生绿色能源制氢技术之一。阴离子交换膜(AEM)是提供OH^-离子传导和阻隔气体交叉的关键部件，其直接影响了阴离子交换膜电解水系统的性能和使用寿命。然而，目前的AEM隔膜面临着离子电导率低和稳定性差的问题。本文首先介绍了AEM在电解槽中的作用，高性能AEM应满足的性能要求和评价参数，并重点讨论了OH^-在AEM中的传输机制与影响因素。接着，本文进一步概述了AEM的结构组成，以及常见的阳离子基团和聚合物主链类型；阐述了不同阳离子基团的降解机理和聚合物主链的特点，重点阐释了阳离子官能团稳定性设计的策略，聚合物主链改性制备的方法，以及AEM性能表现。最后，展望了AEM隔膜未来面临的挑战和潜在研究方向，指出应在设计耐碱稳定性AEM的基础上，通过交联、嵌段共聚、侧链接枝和复合膜技术等策略构建和制备满足实际应用需求的高性能AEM隔膜，为AEM进一步发展提供借鉴和参考。

关键词: 绿电制氢, 阴离子交换膜电解水, 离子传导机理, 离子电导率, 耐碱稳定性

Abstract:

Anion exchange membrane water electrolysis (AEMWE), which integrates the advantages of alkaline water electrolysis and proton exchange membrane water electrolysis, features high electrolysis efficiency, rapid response, and low cost. It is currently regarded as one of the most promising technologies for renewable and sustainable hydrogen production. The anion exchange membrane (AEM) is a critical component responsible for OH^– conduction and gas crossover prevention, directly influencing the performance and longevity of AEMWE systems. However, existing AEMs face challenges such as low ionic conductivity and poor stability. This review first introduces the role of AEMs in electrolysis cells, outlines the requirements and evaluation parameters for high-performance AEMs, and emphasizes the OH^- transport mechanism and influencing factors in AEMs. The structural composition of AEMs, including common types of cationic groups and polymer backbones, is then detailed. The degradation mechanisms of various cationic groups and the characteristics of different polymer backbones are also discussed. We primarily focus on the design strategies for enhancing the stability of cationic functional groups, modification and preparation methods for polymer backbones, and the overall performance of AEMs. Finally, we address the challenges faced by AEM membranes and explore potential future research directions. This review suggests that high-performance AEMs suitable for practical applications should be developed through strategies such as crosslinking, block copolymerization, side-chain grafting, and composite membrane technology, based on the design of alkali-stable AEMs. These approaches provide valuable references and guidance for the advancement of AEMs in hydrogen production technologies.

Key words: hydrogen production by green electricity, anion exchange membrane water electrolysis, ionic conduction mechanism, ion conductivity, alkaline stability

中图分类号:

TQ 116.2

邢学奇, 宋鹏翔, 申爱景, 鲁仰辉, 陈俊, 刘伟. 电解水制氢用阴离子交换膜研究进展[J]. 储能科学与技术, 2024, 13(11): 3856-3870.

Xueqi XING, Pengxiang SONG, Aijing SHEN, Yanghui LU, Jun CHEN, Wei LIU. Recent progress of anion exchange membrane for hydrogen production via water electrolysis[J]. Energy Storage Science and Technology, 2024, 13(11): 3856-3870.

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项目	碱性电解水制氢	质子交换膜电解水制氢	阴离子交换膜电解水制氢
隔膜	多孔隔膜(如PPS织布)	质子交换膜(如Nafion)	阴离子交换膜
阴极	NiMo合金	铂族金属	过渡金属
阳极	NiCo合金	RuO _x 、IrO _x	过渡金属
双极板	不锈钢镀镍	石墨板或钛板	镍板或不锈钢板
电解液	KOH 溶液	纯水	碱溶液或纯水
电流密度/(A/cm²)	<0.5	1～2	1～2
操作温度/℃	60～90	50～90	40～80
气体纯度	>99.5%	>99.99%	>99.99%
寿命/h	约100000	<10000	<2000
成本	低	高	—
技术成熟度	成熟	小规模商业化	研发中
优点	技术成熟度高；使用非贵金属催化剂，成本低	能量效率高；气体纯度高；电流密度高；响应迅速	能量效率高；响应迅速；使用非贵金属催化剂，成本低；气体纯度高
缺点	能量效率低；电流密度低；气体纯度低；响应能力差	使用贵金属催化剂和Nafion膜，成本高；稳定性差	技术成熟度低；寿命短

隔膜	电导率		耐碱稳定性		参考文献
隔膜	OH^-电导率/(mS/cm)	温度/℃	测试条件^①	电导率保持率	参考文献
C6D40	28	室温	1 mol/L NaOH, 80 ℃, 2000 h	67%	[17]
PE-NH2-2.06	108.2	80	4 mol/L KOH, 80 ℃, 400 h	>80%	[19]
DQPPO-17-OH	63.9	80	2 mol/L NaOH, 80 ℃, 480 h	92.6%	[20]
PSU-P-PG	30.6	60	1 mol/L NaOH, 60 ℃, 30天	—	[28]
PPO-BG4-75	50.0	80	1 mol/L NaOH, 60 ℃, 30天	~93.0%	[57]
AAEM-17	22.0	22	1 mol/L KOH, 80 ℃, 19天	81.8%	[31]
MTPP-(2,4,6-Me)	27.0	室温	1 mol/L KOD/(CD₃OD+D₂O), 80 ℃, 5000 h	82.0%	[32]
PDB155P-HAH60	78.6	90	4 mol/L NaOH, 60 ℃, 10天	97.5%	[38]
PECryp13-Ba	81.0	60	15 mol/L NaOH, 60 ℃, 1500 h	>70%	[39]
TMImPPO	60.0	80	1 mol/L NaOD/D₂O/CD₃OD, 60 ℃, 7天	91.1%	[40]
AEM-1.95	~57.0	60	5 mol/L KOH, 50 ℃, 48 h	~89.0%	[41]
xBEO-PPO	132.0	80	1 mol/L KOH, 80 ℃, 620 h	68.0%	[43]
QPPEEK-PEG 20	102.0	80	1 mol/L KOH, 80 ℃, 400 h	85.0%	[44]
x-TriPPO-50SEBS	77.4	80	1 mol/L KOH, 80 ℃, 960 h	99.6%	[45]
bPES-Pip-10-5	105.4	80	1 mol/L KOH, 60 ℃, 336 h	88.0%	[46]
PyPBI-BuI	128.6	80	5 mol/L KOH, 60 ℃, 21天	~99.0%	[50]
PFTP-13	~175.0	80	5 mol/L KOH, 80 ℃, 2000 h	~80.0%	[51]
PTP-90	128.9	80	1 mol/L KOH, 80 ℃, 934 h	60.0%	[52]
PSAN69-[MVBPip][OH]25	49.4	80	1 mol/L KOH, 80 ℃, 480 h	85.4%	[53]
F20C9N	70	80	1 mol/L NaOH, 80 ℃, 500 h	91.0%	[55]
PEP80-30PS	204.7	80	1 mol/L KOH, 80 ℃, 35天	84.7%	[56]

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