质子导体固体电解池电解水制氢研究进展

doi:10.3969/j.issn.2097-0706.2022.08.008

摘要/Abstract

摘要：

鉴于天然气、煤炭、石油等传统燃料燃烧面临的能源危机和环境挑战,发展新型可持续能源是我国实现“双碳”目标的必经之路。氢能因能量密度高、高效、清洁而备受瞩目。电解水制氢具有工艺简单、氢气纯度高等优点。在H₂制备技术中,利用可再生能源供能的固体氧化物电解槽（SOEC）因具有高效和环保的特点而备受关注。传统氧离子导体固体氧化物电解池（O-SOEC）的发展受到工作温度过高等问题的限制,质子传导型固体氧化物电解池（H-SOEC）具有明显优势。总结H-SOEC电解质、氢电极与空气电极的材料,分析了不同水电解制氢技术的效率及影响电解效率的因素。在已有研究的基础上,指出了H-SOEC发展中存在的问题,并展望了今后的研发方向。

关键词: 固体电解池, 电解制氢, 质子传导, 储能, 法拉第效率, 新能源, 碳中和, 钙钛矿

Abstract:

Since traditional fossil fuels,such as nature gas,coal and petrol oil,have brought energy crisis and environment pollutant to our society, renewable energy becomes the solution to realization "dual carbon" goals. Hydrogen energy attracts much attention because of its high energy density, high efficiency and environmental protection. Hydrogen production from water electrolysis is of simple operation process and high purity product. Hydrogen production technology in solid oxide electrolytic cells（SOECs） powered by new energy attract much attention because of its high efficiency and low environment impact. Compared to the traditional oxygen-ion solid oxide electrolysis cells（O-SOECs）whose development is hampered by narrow operation temperature range,proton-conducting solid oxide electrolysis cells（H-SOECs）are of better performances. Based on the summary on the materials applied to the electrolyte, hydrogen electrodes and air electrodes of H-SOECs, the efficiency of different hydrogen production by water electrolysis technologies and the factors affecting their electrolysis are analyzed. Based on the research progress made on H-SOECs, the existing problems and challenges of the technologies are proposed.

Key words: solid oxide electrolytic cell, hydrogen production by water electrolysis, proton conduction, energy storage, Faradaic efficiency, new energy, carbon neutrality, perovskite

中图分类号:

TK91:TM911

陈晗钰, 周晓亮, 刘立敏, 钱欣源, 王宙, 何非凡, 绳阳. 质子导体固体电解池电解水制氢研究进展[J]. 综合智慧能源, 2022, 44(8): 75-85.

CHEN Hanyu, ZHOU Xiaoliang, LIU Limin, QIAN Xinyuan, WANG Zhou, HE Feifan, SHENG Yang. Research progress of hydrogen production from water electrolysis in proton-conducting solid electrolytic cells[J]. Integrated Intelligent Energy, 2022, 44(8): 75-85.

图/表 5

图1

表1

不同电解技术的主要特征[37]

项目	碱性电解		质子交换电解		氧离子传导电解
项目	液体	聚合物电解质膜		固体氧化物电解（SOE）
电荷载体	OH^-	OH^-	H⁺	H⁺	O^2-	O^2-
工作温度/℃	20~80	20~200	20~200	500~1 000	500~1 000	750~900
电解质	液体	固体	固体	固体	固体	固体
OER	4OH^-→2H₂O+ O₂+4e^-	4OH^-→2H₂O+O₂+4e^-	2H₂O→4H⁺+O₂+4e^-	2H₂O→4H⁺+O₂+4e^-	O^2-→ $12$ O₂+2e^-	O^2-→ $12$ O₂+2e^-
阳极材料	Ni>Co>Fe （氧化物）	镍基	IrO₂,RuO₂,Ir_xRu_1-_xO₂,	具有质子电子导电性的钙钛矿	La_xSr_1-_xMnO₃+Y-ZrO₂(LSM-YSZ)	La_xSr_1-_xMnO₃+Y-ZrO₂(LSM-YSZ)
HER	2H₂O+4e^-→4OH^_+2H₂	2H₂O+4e^-→ 4OH^-+2H₂	4H⁺+4e^-→2H₂	4H⁺+4e^-→2H₂	H₂O+2e^-→H₂+O^2-	H₂O+2e^-→H₂+O^2-
阴极材料	镍合金	Ni,Ni-Fe,NiFe₂O₄	Pt/C MoS₂	镍金属陶瓷	Ni-YSZ	Ni-YSZ钙钛矿
效率/%	59~70	—	65~82	100	100	—
适用性	商业化	实验室规模	近商业化	实验室规模	实验室规模	实验室规模
优势	成本低,相对稳定,技术成熟	碱性和H⁺-PEM电解的组合	紧凑设计、启动快速、高纯度H₂	增强反应动力学、热力学;更低的能源需求,更低的资本成本		合成气直接生产
劣势	腐蚀电解液、气体渗透、慢动力学	聚合物膜中的OH^-电导率低	高成本聚合物膜	安全问题,电极机械性能不稳定（开裂）;密封问题
挑战	提高可靠性和氧分解	改善电解液	减少贵金属利用	电极的微观结构变化;分层、TPB堵塞、钝化		碳沉积、电极的微结构变化

表1

图2

图3

图4

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