基于Y0.08Zr0.92O2-δ/Er0.4Bi1.6O3复合电解质的Ca3Co4O9+δ氧电极电化学性能

丁利利; 张旭; 吴学英; 李媛; 田彦婷

doi:10.13801/j.cnki.fhclxb.20221129.002

基于Y_0.08Zr_0.92O_2-δ/Er_0.4Bi_1.6O₃复合电解质的Ca₃Co₄O_9+δ氧电极电化学性能

doi: 10.13801/j.cnki.fhclxb.20221129.002

太原理工大学　物理学院，太原 030024

基金项目: 山西省应用基础研究计划项目(20210302123111；20210302123151)

详细信息

通讯作者:
田彦婷，博士，副教授，硕士生导师，研究方向为固体氧化物燃料电池　E-mail：yanting_005@163.com

中图分类号: TB383.1；TM911.4；TB331
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出版历程
- 收稿日期: 2022-08-15
- 修回日期: 2022-11-03
- 录用日期: 2022-11-18
- 网络出版日期: 2022-11-30
- 刊出日期: 2023-08-15

Electrochemical performance of Ca₃Co₄O_9+δ oxygen electrode based on Y_0.08Zr_0.92O_2-δ/Er_0.4Bi_1.6O₃composite electrolyte

School of Optoelectronic Engineering, Taiyuan University of Technology, Taiyuan 030024, China

Funds: Fundamental Research Program of Shanxi Province (20210302123111; 20210302123151)

摘要

摘要: 可逆固体氧化物电池(RSOCs)是一种清洁高效的能量转换和电化学存储装置，由于目前使用的钙钛矿氧电极存在Sr偏析现象，对氧电极的耐久性提出了新的要求。采用溶液浸渍法在多孔Y_0.08Zr_0.92O_2-δ(YSZ)骨架上制备了YSZ/Er_0.4Bi_1.6O₃(ESB)复合电解质和Ca₃Co₄O_9+δ(CCO)氧电极，800℃时的极化电阻为0.45 Ω·cm²。氧电极在100 h的阴、阳极交替极化过程中表现出良好的稳定性，阳极和阴极极化对电极性能具有相反的影响机制，电解模式下氧电极性能的损耗可以通过电池模式得以恢复。Ni-YSZ/YSZ/ESB/CCO单电池在800℃时的最大输出功率为722 mW·cm⁻²，电解电压为1.5 V时的电解电流密度为−1204 mA·cm⁻²，对应的产氢率为503.3 mL·cm⁻²·h⁻¹，实现了较高的能量转化。
- 可逆固体氧化物电池 /
- 固体氧化物燃料电池 /
- 固体氧化物电解池 /
- Ca₃Co₄O_9+δ氧电极 /
- 极化稳定性
Abstract: Reversible solid oxide cell (RSOC) is a clean and efficient electrochemical conversion and storage devices. Due to the Sr segregation in the now available perovskite oxygen electrodes, new requirements are put forward for the durability of oxygen electrodes. Y_0.08Zr_0.92O_2-δ/Er_0.4Bi_1.6O₃ (YSZ/ESB) composite electrolyte and Ca₃Co₄O_9+δ (CCO) oxygen electrode were prepared by solution impregnation method in this paper. The polarization resistance of CCO oxygen electrode at 800°C was 0.45 Ω·cm². The oxygen electrode showed superior durability in the process of alternating anodic and cathodic polarization for 100 h. Anodic and cathodic polarization displayed opposite influence mechanisms on the electrode performance. The degradation induced in the electrolysis mode can be eliminated by reversibly cycling between electrolysis and fuel-cell modes. The Ni-YSZ/YSZ/ESB/CCO single cell obtained a maximum power density of 722 mW·cm⁻² at 800℃. The electrolysis current density at 1.5 V was 1204 mA·cm⁻², which corresponded to the hydrogen production rate of 503.3 mL·cm⁻²·h⁻¹. Results showed that CCO with good reversible polarization performance and long-term stability achieved a high energy conversion rate.
- reversible solid oxide cell /
- solid oxide fuel cell /
- solid oxide electrolysis cell /
- Ca₃Co₄O_9+δ oxygen electrode /
- polarization stability

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图 1 850℃煅烧10 h后的Ca₃Co₄O_9+δ(CCO)及CCO和Er_0.4Bi_1.6O₃(ESB)混合粉体的XRD图谱

Figure 1. XRD patterns of Ca₃Co₄O_9+δ (CCO) and CCO & Er_0.4Bi_1.6O₃ (ESB) mixture after calcination at 850℃ for 10 h

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图 2 Y_0.08Zr_0.92O_2-δ(YSZ)骨架、ESB隔离层和CCO氧电极的SEM图像

Figure 2. SEM images of Y_0.08Zr_0.92O_2-δ (YSZ) scaffold, ESB isolating layer and CCO oxygen electrode

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图 3 CCO2、CCO4和CCO6氧电极在不同温度下的极化阻抗图谱

Ca₃Co₄O_9+δ oxygen electrode impregnated with 2, 4, and 6 times were labeled as CCO2, CCO4 and CCO6, respectively

Figure 3. Impedance spectra of CCO2, CCO4 and CCO6 oxygen electrodes at different temperatures

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图 4 CCO2、CCO4和CCO6氧电极在800°C下的极化过电位曲线

Figure 4. Overpotential curves of CCO2, CCO4 and CCO6 oxygen electrodes at 800°C

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图 5 CCO氧电极在±500 mA·cm⁻²电流密度下的极化稳定性

Figure 5. Durability of CCO oxygen electrode at current density of ±500 mA·cm⁻²

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图 6 CCO氧电极在不同阴极极化次数后的阻抗图谱 (a) 和极化过电位曲线 (b)

Figure 6. Impedance spectra (a) and overpotential curves (b) of CCO oxygen electrode after different cathodic polarization times

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图 7 CCO氧电极在不同阳极极化次数后的阻抗图谱 (a) 和极化过电位曲线 (b)

Figure 7. Impedance spectra (a) and overpotential curves (b) of CCO oxygen electrode after different anodic polarization times

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图 8 单电池 (a) 和阴极 (b) 的截面SEM图像

Figure 8. SEM images for the cross-section of the single cell (a) and the electrode (b)

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图 9 单电池在800°C下的固体氧化物燃料电池(SOFC) (a)和固体氧化物电解池(SOEC) (b)输出性能

Figure 9. Solid oxide fuel cells (SOFC) (a) and solid oxide electrolytic cells (SOEC) (b) performances of the single cell at 800°C

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表 1 基于不同制备方法的CCO电极性能

Table 1. Electrode performances of CCO electrode based on different preparation methods

Synthesis condition	Electrode details	Electrolyte	T/℃	R_p/(Ω·cm²)	Ref.
Sol-gel proteic synthesis 900℃/2 h	Screen-printing 950℃/2 h+900℃/12 h CCO, 2 μm	GDC	700	2.74	[6]
Solid-state reaction 800℃/10 h	Hand painting 850℃/5 h CCO, 20-30 μm	SDC	700 800	3.44 0.58	[15]
Electrostatic spray deposition (ESD)	ESD-coat ing CCO, 25-33 μm	GDC	700	3.32	[16]
Solid state reaction 880℃/2 h	Screen-printing 900℃/1 h CCO, 30 μm	GDC	700	4.58	[16]
Electrostatic spray deposition (ESD)	ESD-coating CCO, 20 μm	GDC	700	3.40	[17]
Solution impregnation method 850℃/5 h	Solution impregnation method 850℃/5 h CCO, 30 μm	YSZ/ESB	700 800	1.15 0.45	This work
Notes: GDC—Ce_0.9Gd_0.1O_2-δ; SDC—Sm_0.2Ce_0.8O_1.9; T—Temperature; R_p—Resistance.

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