固体氧化物电解池材料和结构优化的研究进展

doi:10.19799/j.cnki.2095-4239.2025.0680

摘要/Abstract

摘要：

固体氧化物电解池（SOEC）作为新一代高温电化学能量转换装置，通过固体氧化物电解质的氧离子传导特性，实现了电能向化学能的高效转化，在分布式储能和可再生能源领域展现出巨大的价值。其核心优势在于：SOEC可与光伏或光热系统高效耦合，实现间歇性电能向可储运氢能的灵活转化。此外，SOEC具备CO₂/H₂O共电解功能，能够通过化学链转化过程，将温室气体高效转化为甲醇、甲烷等清洁燃料，进而构建“电-氢-化学品”的级联式资源利用体系。本文系统讲述了SOEC的热力学基础与构造特征，重点分析了燃料电极、氧电极及电解质的研究进展，并分析了目前SOEC所面临的问题，总结归纳电极材料、电池结构以及流场和热管理等改进策略。同时，本文基于目前研究进展，对SOEC在高温共电解等方向的发展路径及其在构建低碳能源体系所能发挥的作用进行了展望。

关键词: 固体氧化物电解池, CO₂/H₂O共电解, 电极材料, 电池结构

Abstract:

Solid oxide electrolysis cells (SOECs), as a new generation of high-temperature electrochemical energy conversion devices, have been demonstrated to great advantages in the fields of distributed energy storage and renewable energyutilization due to the efficient conversion of electrical energy to chemical energy. Also, SOEC can be effectively integrated with photovoltaic or solar thermal systems, facilitating the flexible transformation of intermittent electrical energy into storable and transportable hydrogen energy. Furthermore, SOECs possess the capability to co-electrolyze CO₂ and H₂O, enabling the efficient conversion of greenhouse gases into clean fuels such as methanol and methane through chemical chain conversion processes, thereby establishing a cascading resource utilization system referred to as the "electricity-hydrogen-chemicals" framework. This paper provides a systematic overview of the thermodynamic foundations and structural characteristics of SOECs, with particular emphasis on recent advances in fuel electrodes, oxygen electrodes, and electrolyte materials. It also examines the current challenges confronting SOEC technologies and summarizes improvement strategies related to electrode material development, cell architecture, flow field optimization, and thermal management. The potential development pathways for SOECs in the areas of co-electrolysis and the developing of low-carbon energy system.

Key words: solid oxide electrolysis cells, co-electrolysis of CO₂/H₂O, electrode materials, cell architecture

中图分类号:

O646

姚昊天, 董珊芝, 郝杨, 邵勤思, 刘杨, 赵玉峰, 张久俊. 固体氧化物电解池材料和结构优化的研究进展[J]. 储能科学与技术, doi: 10.19799/j.cnki.2095-4239.2025.0680.

Haotian YAO, Shanzhi DONG, Yang HAO, Qinsi SHAO, Yang LIU, Yufeng ZHAO, Jiujun ZHANG. Research progress on material and structural optimization of solid oxide electrolyzer cells[J]. Energy Storage Science and Technology, doi: 10.19799/j.cnki.2095-4239.2025.0680.

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项目	碱性电解水（ALK）	质子交换膜（PEM）	阴离子交换膜（AEM）	固体氧化物电解池（SOEC）
电解质	20%~30% KOH/NaOH	固体聚合物电解质（SPE）	含1mol·L^-1 KOH/NaOH二乙烯基苯（DVB）聚合物	氧化钇稳定的氧化锆（YSZ）
电流密度/A·cm^-2	0.2-0.5	1.0-3.0	0.8-2.5	0.3-2.0
电压/V	1.4-3.0	1.4-2.5	1.4-2.0	1.0-1.5
工作温度/℃	70~90	50~90	50~90	700~850
阴极催化剂	Ni	Pt/C	Ni	Ni/YSZ
阳极催化剂	Ni	IrO₂	Ni/NiFeCo	LSM/LSCF
电解效率	59~70%	65~82%	60~75%	85~100%
能耗率（标准条件，kW·h·m^-3）	4.2-5.9	4.2-4.6	4.2-4.6	＞3
环保性	碱液、石棉隔膜污染	无污染	无污染	无污染
启停速度	启动时间长	秒级相应	分钟级相应	启动时间长
优势	技术成熟，成本低，适合大规模制氢项目	效率高，氢气纯度高（>99.99%），适合车规级氢能及加氢站场景	成本低（非贵金属催化剂），潜在效率高，结合ALK的经济性和PEM的灵活性	理论效率最高，余热利用可提升系统效率至85%以上，可逆运行（氢储能）
不足	效率较低，废液处理成本，不适合波动性电源	贵金属依赖导致成本高，膜电极寿命需提升	膜和电极材料耐久性不足，技术未成熟，商业化进程缓慢	商业化程度低

电池/电解池氧电极材料	燃料	温度/℃	电压/V	电流密度/(A·cm^-2）	稳定性	文献
LSCF-GDC@YSZ	90%CO₂-10%CO	800	1.5	1.26	220 h（800 ℃、-0.20 A·cm^-2）	[35]
PBCFN-SDC	3%H₂O-97% H₂	850	1.3	0.65	10 h（850℃、1.3V）	[36]
LSM/LSM-YSZ	60%H₂O-40%CO₂	750	1.0	2.0	256 h（750℃、1V）	[37]
BCCF	20%H₂O	650	1.3	2.73	100 h（650℃、 0.3 A·cm^-2）	[38]
LSGM/SSZ	50%H₂O-50%H₂	800	1.3	1.15	100 h（在1023 K和10%H₂O-90%H₂时，SOFC模式1.2 V和SOEC模式0.85 V之间循环运行	[39]
PBCO-1.5	CO₂	800	1.6	2.29	600 h	[40]
BLF-GDC	50%H₂-50% H₂O	800	1.5	2.42	200 h（2.30 A·cm^-2、800℃ 40%H₂O-10%CO₂-50%H₂）	[41]
	50%H₂-50%CO₂	800	1.5	1.53
	40%H₂O-10% CO₂-50% H₂	800	1.5	2.08
PNCO-LSC	90%空气-8%CO₂-2%H₂	800	1.5	0.917	100 h（800℃和0.4 A·cm^-2）	[42]
PBC	CO₂	800	2.0	3.40	200 h（1.2 V）	[43]
PBSCF@BZCYYb	20%H₂O-80%空气	650	1.3	0.7754	60 h	[44]
RP-LSCFNMC	60%H₂O	800	1.3	2.10	120 h（750℃、1.3V、60%H₂O）	[45]
LCFC	50%H₂O-50%H₂	800	1.5	2.89	140 h（SOFC和SOEC模式运行）	[46]
CCO-1.5	50%H₂O、H₂和Ar混合气	800	1.5	2.451	100 h	[47]
CCO-3	50%H₂O、H₂和Ar混合气	800	1.5	1.101	-	[47]

电池/电解池燃料电极材料	燃料	温度/℃	电压/V	电流密度/(A·cm^-2）	稳定性	文献
LSCFF	50%CO-50%CO₂	800	1.5	1.09	-	[54]
LSCFF95	50%CO-50%CO₂	800	1.5	1.28	6 h（800℃和 1.6 A·cm^-2）	[54]
Ni@SFTCMMN	CO₂	800	1.5	1.91	160 h（800℃和 1.2 V）	[55]
SFCM	50%CO₂-50%CO	850	1.4	2.12	20 h（800℃和 0.4 A·cm^-2）	[56]
SFCM	45%CO₂-45%H₂O-10%H₂	800	1.5	2.30	50 h（1 A·cm^-2）	[56]
Pr(Ca)Fe(Ni)O₃-Ca₂Fe₂O₅	CO₂	800	1.5	0.76	300 h（800℃和 0.3 A·cm^-2）	[57]
LSFMCa0.3	CO₂	800	1.5	1.891	-	[58]
MFCC20	55% H₂O/Ar	800	1.3	0.48	150 h（800℃、1.3 V、55% H₂O/Ar）	[59]
MFCC5	55% H₂O/Ar	800	1.3	0.60	150 h（800℃、1.3 V、55% H₂O/Ar）	[59]
LSFM_0.05	CO₂	800	1.5	1.06	30 h（800℃、 1.2 V ）	[60]
LCF64-GDC （6：4）	60% H₂O/H₂	850	1.3	0.702	60 h（750℃、60% H₂O-H₂、1.3V）	[61]
LSFW-GDC	CO₂	800	1.5	1.48	50 h（800℃和1.2 V）	[62]
LSFTi91	CO₂	800	1.5	1.11	10 h（800℃和1.2 V）	[63]
PCFN95	CO₂	800	1.5	1.76	100 h（800℃和 0.5 A·cm^-2）	[64]
LCTNi-Ce	50% CO₂-50% H₂	800	1.3	0.557	-	[65]
LCTNi-Ce	50% CO₂-50% CO	800	1.3	0.429	-	[65]
R-PB95FN	CO₂	800	1.5	1.093	100 h（800℃和1.5 V）	[66]

电池/电解池	燃料	温度/℃	电压/V	电流密度/(A·cm^-2）	孔隙率	文献
NiO-YSZ//YSZ//GDC/BSCF-GDC	50%H₂O	800	1.5	4.30	60.53%/燃料电极	[70]
Ni-YSZ//YSZ//YSZ-LSC	-	800	-	3.40	27%/氧电极	[72]
Ni-YSZ/Ni-YSZ//YSZ//GDC/LSCF-GDC	90%H₂O- 10%H₂	750	1.3	1.86	48%/燃料电极	[73]
Ni-YSZ//YSZ//YSZ-LSM	50%H₂O-50%H₂	750	1.3	1.42	57.5%/燃料电极	[74]
Ni-YSZ//GDC/YSZ//LSF-GDC	50%CO₂/ H₂	800	1.7	1.91	52.3%/氧电极	[75]
GDC10/GDC10//ScSZ//GDC10/LSM20	81% CO₂-10% CO-9%N₂	850	1.5	0.72	-	[76]
LSCrF-YSZ//YSZ//LSM-YSZ	CO₂	800	1.5	1.02	-	[77]
NiO-YSZ /NiO-YSZ//YSZ/GDC//LSCF-GDC	30%CO₂-70%CO	750	1.5	1.12	51%/燃料电极	[78]
NiO-YSZ/CFL//YSZ/GDC//LSCF-HP	10%CO₂/H₂	800	1.7	1.78	34.6%/CFL	[79]
NiO-YSZ//YSZ//GDC/SFM-GDC	3% H₂O-air	800	1070 mW·cm^-2		59.5%/负极	[80]
Ni-YSZ//YSZ//LSM-YSZ	50%H₂	800	253 mW·cm^-2		46.9%/负极	[81]

电解池	燃料	温度/℃	电压/V	电流密度/(A·cm^-2）	稳定性	文献
LSM/LSM-YSZ//YSZ//LSCM	60%H₂O-40%CO₂	750	1.0	2.0	256 h（750℃、1V）	[37]
Ni-YSZ//YSZ/LSM-YSZ//LSM/LSCF	10%H₂-60% H₂O-30%CO₂	850	1.4	0.90	100 h（0.80 A·cm^-2、800℃）	[109]
Ni-YSZ//YSZ/GDC//LSGF-GDC	40%H₂O-40% CO₂-20% H₂	750	1.3	0.30	1000 h	[110]
Ni-YSZ//YSZ/GDC//LSGF-GDC	60%H₂O-25% CO₂-10% H₂	750	1.3	0.50	600 h（0.5 A·cm^-2）	[111]
Ni-YSZ/YSZ/CGO//LSCF-CGO	45%H₂O-45% CO₂-10% H₂	750	1.4	1.20	1400 h（前800 h为0.5 A·cm^-2 后0.75 A·cm^-2）	[112]
SFM//YbScSZ//SFM	75%H₂O-25%CO₂	900	1.3	1.10	42 h	[113]
SFMFe-LSGM//LSGM//SFM-LSGM	50%H₂O-50%CO₂	850	1.3	0.60	100 h（850℃、1.1 V）	[114]
SFM-SDC//LSGM//SFM-SDC	16% CO₂-16%H₂O-20%H₂-48%N₂	850	1.3	0.73	103 h（800℃、0.12 A·cm^-2）	[115]
LSFNi-GDC//LSGM//PBCC-GDC	20% H₂O- 80% CO₂	850	1.5	2.42	150 h（20% H₂O/CO₂、 800℃和0.5 A·cm^-2）	[116]
SFM-YSZ//YSZ//LSM-YSZ	20% H₂O- 80% CO₂	800	1.5	1.46	26 h（CO₂-20 vol% H₂O、1.3 V、800℃）	[117]
LSFNb//LSGM//LSFNb	20% H₂O- 80% CO₂	850	1.3	1.46	130 h（800℃、CO₂-20 vol% H₂O、0.48 A·cm^-2）	[118]
LSFNb//LSGM//LSFNb	20% H₂O- 80% CO₂	800	1.3	0.97	130 h（800℃、CO₂-20 vol% H₂O、0.48 A·cm^-2）	[118]
LSCM//YSZ//LSCM	50%CO₂-50% H₂O	850	1.5	0.30	-	[119]
Ni-YSZ//YSZ/CGO//LSCF-CGO	65% H₂O- 25% CO₂- 10% H₂	750	1.3	1.30	1000 h（750℃、0.5 A·cm^-2）	[120]
Ni-YSZ/YSZ/LSM-YSZ	45% H₂O-10%H₂-45%CO₂	850	1.3	1.00	700 h（1.5 A·cm²）	[121]