碱性膜电解水制氢技术现状与展望

doi:10.11949/0438-1157.20211264

摘要/Abstract

摘要：

开发清洁高效的可再生能源是未来能源转型的必然趋势。氢能作为一种绿色无污染的能源载体，可通过电解水技术实现氢能与电能的高效转化，有望作为风力、光伏发电的重要调节手段。碱性膜电解水制氢能够提高电流密度，增加能量转化效率，优于碱性水溶液电解水制氢；与此同时，可采用铁、镍等非贵金属制备催化剂，克服质子交换膜电解水制氢使用贵金属催化剂带来的设备昂贵、资源受限问题。本文综述了碱性膜电解制氢技术发展现状，重点围绕自支撑催化电极、耐碱腐蚀离子膜、有序结构膜电极开展讨论，包括催化剂制备策略，耐碱离子膜发展现状，以及有序化膜电极的应用优势，阐释电化学工程中的传质与反应耦合原理。本文为进一步研究开发高性能电化学关键材料提供了指导思路，推动电解水制氢技术的发展。

关键词: 制氢, 催化剂, 膜, 电解, 膜电极

Abstract:

The development of clean and efficient renewable energy is an inevitable trend in the future energy transition. Hydrogen, as a green and pollution-free energy carrier can achieve efficient conversion of hydrogen energy and electric energy via water electrolysis technology, which is expected to be an important regulating means of wind and photovoltaic power generation. Water electrolysis produces hydrogen without pollutant emission, which is expected to be used as an efficient tool to storage and regulate the intermittent power of wind and photovoltaic generation. Comparing with the conventional water electrolysis using alkaline aqueous solution, water electrolysis based-on alkaline membrane can increase current density and improve energy conversion efficiency. Moreover, non-precious metals such as iron and nickel can be used to prepare catalysts for both hydrogen emission reaction (HER) and oxygen emission reaction (OER), no suffering from the drawbacks of expensive resources caused by the use of precious metal catalysts in proton exchange membrane electrolysis of water (PEMWE). In this study, we review the present status of alkaline membrane electrolysis technology for hydrogen production, focusing on self-supported catalytic electrode, alkali corrosion resistant anion exchange membranes (AEMs) and ordered membrane electrode assembles (MEA), including the preparation strategy of self-supported catalysts, the development trend of alkali corrosion resistant ion membrane and advantages of ordered MEA, explaining the coupling principle of mass transfer and reaction in electrochemical engineering. Therefore, this paper will provide guidance for further research of high-performance electrochemical key materials, and promote the development of hydrogen production technology from water electrolysis.

Key words: hydrogen production, catalysts, membrane, electrolysis, membrane electrode assemble

中图分类号:

TQ 151

王培灿, 万磊, 徐子昂, 许琴, 王保国. 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.

Peican WANG, Lei WAN, Zi'ang XU, Qin XU, Baoguo WANG. Hydrogen production based-on anion exchange membrane water electrolysis: a critical review and perspective[J]. CIESC Journal, 2021, 72(12): 6161-6175.

图/表 9

参考文献 51

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项目	碱性水溶液 (AWE)	质子交换膜 (PEMWE)	碱性离子膜 (AEM)
温度/℃	70~90	65~85	65~85
压强/10⁵ Pa	1~32	1~35	1~32
电流密度/（A·cm^-2）	0.2~0.5	1.5~2.5	0.8~2.1
标准工况下能耗/(kWh·m^-3 H₂)	4.3~5.1	4.3~4.6	4.2~4.6
电解液	5~7 mol·L^-1 KOH	纯水	1 mol·L^-1 KOH/纯水
隔膜	石棉布、PPS布	全氟磺酸膜	阴离子膜
阳极(析氧电极)	不锈钢镀镍	氧化铱	镍网
阴极(析氢电极)	不锈钢镀镍	贵金属铂碳	NiFeCo合金
双极板	不锈钢镀镍	不锈钢镀镍	不锈钢镀镍
技术成熟度	9	7	4

项目	碱性水溶液 (AWE)	质子交换膜 (PEMWE)	碱性离子膜 (AEM)
温度/℃	70~90	65~85	65~85
压强/10⁵ Pa	1~32	1~35	1~32
电流密度/（A·cm^-2）	0.2~0.5	1.5~2.5	0.8~2.1
标准工况下能耗/(kWh·m^-3 H₂)	4.3~5.1	4.3~4.6	4.2~4.6
电解液	5~7 mol·L^-1 KOH	纯水	1 mol·L^-1 KOH/纯水
隔膜	石棉布、PPS布	全氟磺酸膜	阴离子膜
阳极(析氧电极)	不锈钢镀镍	氧化铱	镍网
阴极(析氢电极)	不锈钢镀镍	贵金属铂碳	NiFeCo合金
双极板	不锈钢镀镍	不锈钢镀镍	不锈钢镀镍
技术成熟度	9	7	4

制备方法	优点	缺点	适用情况
水热法/溶剂热法	高效，通用，制备催化剂稳定，自支撑与粉末催化剂均可制备	需要在高压反应釜中进行具有一定安全风险，且不适用于大面积工业化制备	通常用于制备金属氧化物、氢氧化物、羟基氧化物等催化材料
电化学沉积法	简单，高效，反应时间短，催化剂负载量、形貌可调控	大面积制备催化剂时会面临电沉积不均匀的问题	需要外加电场
化学气相沉积法	制备金属磷/硫/硒化物的有效手段	通常需要与其他制备方法耦合	可用于制备过渡金属磷/硫/硒化物
化学溶液法	操作简单，反应条件温和，制备成本低，易于放大	反应时间较长，金属离子负载量很低	大规模制备有独特优势

制备方法	优点	缺点	适用情况
水热法/溶剂热法	高效，通用，制备催化剂稳定，自支撑与粉末催化剂均可制备	需要在高压反应釜中进行具有一定安全风险，且不适用于大面积工业化制备	通常用于制备金属氧化物、氢氧化物、羟基氧化物等催化材料
电化学沉积法	简单，高效，反应时间短，催化剂负载量、形貌可调控	大面积制备催化剂时会面临电沉积不均匀的问题	需要外加电场
化学气相沉积法	制备金属磷/硫/硒化物的有效手段	通常需要与其他制备方法耦合	可用于制备过渡金属磷/硫/硒化物
化学溶液法	操作简单，反应条件温和，制备成本低，易于放大	反应时间较长，金属离子负载量很低	大规模制备有独特优势

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