电解水制高压氢气——技术挑战与研究进展

doi:10.19799/j.cnki.2095-4239.2023.0541

摘要/Abstract

摘要：

利用可再生能源电解水制氢替代化石燃料用于交通和工业领域是实现碳减排的重要技术路径，电解水制取高压氢气有利于简化氢能供应链工艺从而减少压缩机等设备投入，同时，利用电化学等温压缩减小综合能耗，对于降低可再生能源制氢综合成本具有重要意义。电解水制氢压力提高导致电解槽气密性和材料耐氢蚀要求提高，工作状态下更易发生氢氧互混导致氧中氢浓度增加以及电流效率下降，面临技术挑战。本文综述了质子交换膜电解水和碱性电解水两种技术路线在制取高压氢气方面的研究进展，开发高强度、低渗漏、高电导的隔膜材料以及适应隔膜溶胀形变的耐高压密封结构是差压式质子交换膜电解水实现高性能和高可靠性的关键，研发氢氧互混管理新工艺及过程控制技术是实现碱性电解水安全制取高压氢气的关键。

关键词: 电解, 制氢, 高压, 膜, 过程控制, 安全

Abstract:

Hydrogen produced through water electrolysis using renewable energy shows promise as a substitute for fossil fuels in transportation and industrial applications, offering a pathway to reduce carbon dioxide emissions. Pressurized water electrolyzers have the potential to generate high-pressure hydrogen and reduce the demand for subsequent hydrogen compressing, which is often necessary for high-density storage and transportation to end-users. This reduction in overall operating expenses and energy consumption results from the diminished reliance on state-of-the-art mechanical compressors and theoretically higher efficiency via isothermal compression in the electrolyzer. However, the increase in hydrogen pressure introduces challenges related to gas tightness, material durability caused by hydrogen embrittlement, safety concerns, and lowered current efficiency attributed to intensified hydrogen/oxygen crossover. These issues impact the large-scale application of pressurized electrolyzers. This study reviews the research progress in high-pressure proton exchange membrane water electrolysis and alkaline water electrolysis. For proton exchange membrane electrolysis, the critical elements for achieving high-performance and durable high-pressure electrolyzers include the development of gas-tight, reinforced, and ion-conductive membranes with an adopted sealing design. Conversely, alkaline water electrolysis requires process innovation and optimization of control strategies to manage hydrogen/oxygen crossover effectively, ensuring safe and efficient high-pressure operation.

Key words: electrolysis, hydrogen production, high pressure, membrane, process control, safety

中图分类号:

TK91

韩宁宁, 许壮, 何广利. 电解水制高压氢气——技术挑战与研究进展[J]. 储能科学与技术, 2024, 13(2): 626-633.

Ningning HAN, Zhuang XU, Guangli HE. Pressurized water electrolysis： Challenges and recent progress[J]. Energy Storage Science and Technology, 2024, 13(2): 626-633.

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序号	技术分类	氢气压力/ 氧气压力/MPa	制氢量/ (Nm³/h)	关键结论	参考文献
1	碱性电解水	10/10	~0.1	在氢气压力1～3 MPa范围内，压力增加时电解电压降低；在10 MPa下，氢气纯度损失1.5%以上，氢氧互混的安全性管控是挑战。	[24]
2	质子交换膜电解水	10/10 5/0.1	<0.01	差压式电解槽电压随氢气压力增大而增加，均压式电解槽电压随氢气压力升高基本不变；10 MPa均压模式下，由于阴极Pt催化氧还原，氢中氧浓度极低，氧中氢浓度达到3%。	[19]
3	质子交换膜电解水	10/10	<0.01	操作压力增大后可能导致水在催化层的穿透能力增强，阴阳极反应动力学加快，传质阻力下降，电解槽电压增加不显著。	[15]
4	质子交换膜电解水	70/0.1	0.7	为达到差压耐受力，隔膜厚度需要优化；隔膜水含量差异导致局部厚度差异，影响密封气密性；采用电化学压缩至70 MPa比往复式压缩实测综合能耗降低30%以上。	[25]
5	碱性电解水	13.8/13.8	~0.5	氧中氢浓度过高时导致氢氧反应放热，产生安全隐患。	[6]
6	质子交换膜电解水	13/13	1	在高压氢气下，即使采用厚的隔膜也发生显著的氢氧互混；大面积电极易发生水分布不均导致隔膜润湿不均，局部反应受阻，发生氢气聚集，成为安全隐患。	[35]

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