固体氧化物电解池阳极材料研究进展

doi:10.13208/j.electrochem.2215006

摘要/Abstract

摘要：

近年来，固体氧化物电解池（SOEC）作为一种高效的电化学能量转换装置，由于其大电流密度、高法拉第效率和高能量效率受到广泛的关注。阳极析氧反应（OER）是SOEC中重要的电极反应，涉及四电子转移过程，反应动力学缓慢，在电解过程中阳极极化电阻较大且能耗高。因此，设计高效稳定的阳极材料对提高SOEC性能及推动SOEC实际应用至关重要。近年来，高性能阳极研究取得了一系列进展。在本综述中，重点介绍了CO₂和H₂O电解的反应机理，总结了不同类型阳极材料的物理化学和电化学性能，讨论了各种有效的阳极优化策略。此外，还对SOEC的未来研究进行了展望。这对阳极材料的发展和SOEC的实际应用有一定的指导意义。

关键词: 固体氧化物电解池, 阳极材料, CO₂ 和/或H₂O电解, 钙钛矿氧化物

Abstract:

Solid oxide electrolysis cell (SOEC) as an electrochemical energy conversion device has attracted increasing attention due to its large current density, high Faradaic efficiency and energy efficiency. Oxygen evolution reaction at the anode, a four-electron transfer process, is an important half-reaction for SOEC, which contributes to the main polarization resistance and consumes most electric energy during the electrolysis process. Hence, designing anode materials with high activity and stability is crucial for the performance improvement and practical application of SOEC. Recently, some advances have been made in the development of high-performance anode. In the current review, the mechanisms for CO₂ and/or H₂O electrolysis are highlighted. The physicochemical and electrochemical properties of different types of anodes are summarized. Various efficient strategies for anode optimization are introduced. Furthermore, the outlook for the future research of SOEC is included. This review might be helpful for the development of anode materials and the practical application of SOEC.

Key words: Solid oxide electrolysis cell, Anode materials, CO₂ and/or H₂O electrolysis, Perovskite oxide

邹庚, 冯炜程, 宋月锋, 汪国雄. 固体氧化物电解池阳极材料研究进展[J]. 电化学（中英文）, 2023, 29(2): 2215006.

Geng Zou, Wei-Cheng Feng, Yue-Feng Song, Guo-Xiong Wang. Recent Advances in Anode Materials of Solid Oxide Electrolysis Cells[J]. Journal of Electrochemistry, 2023, 29(2): 2215006.

图/表 11

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Material	Electrical conductivity (S·cm⁻¹)	Ionic conductivity (S·cm⁻¹)	D* (cm²·s⁻¹)	k* (cm·s⁻¹)	TEC (K⁻¹)
LSM[5, 6, 10]	1.0×10² (800 °C)	1.0×10⁻⁷-1.0×10⁻⁸ (800 °C)	3.2×10⁻¹⁶ (700 °C)	2.0×10⁻⁹ (700 °C)	ca. 10.0×10⁻⁶
LSC[14, 15]	1.6×10³ (800 °C)	2.2×10⁻¹ (800 °C)	9.5×10⁻⁷ (800 °C)	7.0×10⁻⁶ (800 °C)	20.5×10⁻⁶
LSF[24-26]	213.0 (650 °C)	0.2×10⁻²-4.7×10⁻² (800 °C)	———	———	11.7×10⁻⁶
LSCF[39, 40, 42, 43]	57.0 (600 °C)	2.6×10⁻⁴ (800 °C)	5.0×10⁻⁷ (900 °C)	4.0×10⁻⁵ (900 °C)	17.5×10⁻⁶
BSCF[47-49, 51]	———	1.9 (900 °C)	8.0×10⁻⁷ (800 °C)	5.0×10⁻⁵ (750 °C)	19.7×10⁻⁶
SFM[55, 56, 58]	20.9 (600 °C)	2.1×10⁻⁴ (800 °C)	9.0×10⁻⁶ (800 °C)	8.0×10⁻⁵ (800 °C)	ca. 16.0×10⁻⁶
PBC[76, 77]	645.0 (600 °C)	———	ca. 1.0×10⁻⁵ (350 °C)	ca. 1.0×10⁻³ (350 °C)	21.8×10⁻⁶
GBC[76, 77]	318.0 (600 °C)	———	3.0×10⁻⁷ (350 °C)	2.0×10⁻⁶ (350 °C)	19.3×10⁻⁶
NBC[76, 78]	308.0 (600 °C)	———	3.5×10⁻⁵ (700 °C)	ca. 3.0×10⁻⁴ (700 °C)	20.0×10⁻⁶
SBC[77, 79]	815.0-434.0 (500-800 °C)	———	2.8 × 10⁻⁶ (700 °C)	1.9 × 10⁻³ (700 °C)	———

Anode	Cathode	Fed gas	Current Density (A·cm⁻²)
LSM-YSZ[84]	Ni-YSZ	80% H₂O-20% H₂	0.85@1.3 V
RuO₂+LSM-YSZ[85]	Ni-YSZ	95% CO₂-5% N₂	0.74@1.2 V
Au+LSM-YSZ[3]	Ni-YSZ	95% CO₂-5% N₂	0.94@1.4 V
STFC+LSM-YSZ[86]	Ni-YSZ	50% H₂O-50% H₂	2.00@1.3 V
LSCN+LSM-GDC[19]	Ni-YSZ	42.8% H₂O-14.4% H₂-42.8% CO₂	1.16@1.3 V
LSM-DYSB[87]	Ni-YSZ	50% H₂O-50% H₂	1.32@1.3 V
LSC-GDC[16]	Ni-YSZ	90% H₂O-10% H₂	0.60@1.1 V
LNC-GDC[21]	LNC-GDC	Pure CO₂	2.32@2.0 V
LNC-GDC[22]	Ni-YSZ	50% H₂O-50% H₂	2.00@1.2 V
LSF-YSZ[27]	Ni-YSZ	50% H₂O-25% H₂-25% N₂	0.66@1.3 V
LSF-GDC[88]	Ni-YSZ	50% CO₂-50% H₂%	2.50@1.9 V
Pt-LSF-GDC[88]	Ni-YSZ	50% CO₂-50% H₂%	3.50@1.9 V
LSFNb[28]	Ni-YSZ	50% H₂O-50% H₂	0.89@1.3 V
LSFN-GDC[30]	LSFN-GDC	Pure CO₂	1.09@1.3 V
LSFM-GDC[32]	LSFM-GDC	Pure CO₂	1.11@2.0 V
BSFTa[34]	Ni-YSZ	70% CO₂-30% CO	0.81@1.5 V
BSF[34]	Ni-YSZ	70% CO₂-30% CO	0.45@1.5 V
LCFN-GDC[36]	LCFN-GDC	Pure CO₂	1.41@2.0 V
LSCF-GDC[16]	Ni-YSZ	90% H₂O-10% H₂	0.60@1.3 V
BSCFTa[53]	Ni-YSZ	70% H₂O-30% H₂	1.06@1.5 V
RuO₂-LBSCF[52]	Ni-YSZ	70% CO₂-30% CO	1.40@1.3 V
BCFNb[54]	Ni-GDC	40% H₂O-60% H₂	3.24@1.5 V
SFM[57]	SFM	40% H₂O-60% H₂	0.88@1.3 V
Ni-SFM-SDC[89]	SFM-SDC	74% H₂-26% H₂O	1.02@0.5 V
SFM-SDC[89]	SFM-SDC	74% H₂-26% H₂O	0.34@0.5 V
Ru-SFM-SDC[90]	SFM-SDC	74% H₂-26% H₂O	1.06@0.6 V
LNO[70]	Ni-YSZ	50% H₂-50% H₂O	1.42@1.5 V
LNCO[70]	Ni-YSZ	50% H₂-50% H₂O	1.60@1.5 V

Material	Advantage	Disadvantage
ABO₃_−δ-type perovskite oxides	High electronic conductivity	Sr segregation, low ionic conductivity
Double perovskites	Large D* and k*	Poor stability
RP phase oxides	Large D, k, matched TEC with electrolytes, and high OER activities	Poor stability
Spinel oxides	Suppressed Sr segregation	Poor stability and low ionic conductivity