直接组装法制备氧化铈基金属支撑固体氧化物燃料电池

doi:10.15541/jim20240498

无机材料学报 ›› 2025, Vol. 40 ›› Issue (7): 765-771.DOI: 10.15541/jim20240498

直接组装法制备氧化铈基金属支撑固体氧化物燃料电池

柴润宇¹^,²(), 张镇³(), 王孟龙¹^,², 夏长荣²^,³^,⁴()

1.中国科学技术大学纳米科学与技术学院, 苏州 215123
2.安徽壹石通材料科技股份有限公司能源材料中心, 合肥230088
3.中国科学技术大学先进技术研究院, 合肥 230031
4.中国科学技术大学材料科学与工程学院, 中国科学院能量转换材料重点实验室, 合肥 230026

收稿日期:2024-11-29 修回日期:2025-01-26 出版日期:2025-07-20 网络出版日期:2025-02-25
通讯作者: 张镇, 博士. E-mail: zhenge@ustc.edu.cn;
夏长荣, 教授. E-mail: xiacr@ustc.edu.cn
作者简介:柴润宇(2000-), 男, 硕士研究生. E-mail: sa22226007@mail.ustc.edu.cn
基金资助:
中国科学技术大学先进技术研究院-安徽壹石通材料科技股份有限公司固体氧化物燃料电池联合实验室项目(JL07223001H)

Preparation of Ceria Based Metal-supported Solid Oxide Fuel Cells by Direct Assembly Method

CHAI Runyu¹^,²(), ZHANG Zhen³(), WANG Menglong¹^,², XIA Changrong²^,³^,⁴()

1. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China
2. Energy Materials Center, Anhui Estone Materials Technology Co., Ltd., Hefei 230088, China
3. Institute of Advanced Technology, University of Science and Technology of China, Hefei 230031, China
4. CAS Key Laboratory of Materials for Energy Conversion, School of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China

Received:2024-11-29 Revised:2025-01-26 Published:2025-07-20 Online:2025-02-25
Contact: ZHANG Zhen, PhD. E-mail: zhenge@ustc.edu.cn;
XIA Changrong, professor. E-mail: xiacr@ustc.edu.cn
About author:CHAI Runyu (2000-), male, Master candidate. E-mail: sa22226007@mail.ustc.edu.cn
Supported by:
Research Program of the Joint Laboratory of the Institute of Advanced Technology, University of Science and Technology of China and the Anhui Estone Materials Technology Co., Ltd.(JL07223001H)

摘要/Abstract

摘要：

传统的金属支撑固体氧化物燃料电池(Metal-supported solid oxide fuel cell, MS-SOFC)通常使用氧化钇稳定的氧化锆(Yttria stabilized zirconia, YSZ)作为电解质, 工作温度约为800 ℃。为了使MS-SOFC能够在中低温下工作, 本研究选择在低温下导电性较高的钆掺杂氧化铈(Gadolinium doped ceria, GDC)作为电解质, 以促进MS-SOFC的实际应用。本研究采用流延法制备了薄膜阳极(NiO-GDC)和薄膜电解质(GDC), 采用超声喷涂法制备了阴极材料La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ(LSCF)-GDC。将所得电池组装在金属支撑体上, 制备了带有GDC薄膜电解质的MS-SOFC, 并评价其电化学性能。在650 ℃时, 电池的总阻抗为0.50 Ω·cm², 其中欧姆阻抗为0.23 Ω·cm², 极化阻抗为0.27 Ω·cm², 最大功率密度为336 mW/cm²。此外, 电池在550 ℃、0.5 V恒定电压条件下运行100 h, 电流密度没有明显衰减。温等静压与共烧结制备的电解质与阳极结合十分紧密, 电池在长期运行后各层之间并未发生分层现象, 这种结构稳定性为MS-SOFC的长期运行提供了保障。本研究通过流延-温等静压-直接组装法的工艺路线制备了具有优异电化学性能和长期稳定性的MS-SOFC, 为中低温SOFC的工业化生产提供了新方案。

关键词: 金属支撑固体氧化物燃料电池, 流延法, 钆掺杂氧化铈

Abstract:

Traditional metal-supported solid oxide fuel cells (MS-SOFCs) typically utilize yttria stabilized zirconia (YSZ) as the electrolyte with operating temperature of about 800 ℃. In order to enable MS-SOFC to serve at low temperature, this study used gadolinium doped ceria (GDC), which exhibits higher conductivity at lower temperature, as the electrolyte to facilitate the practical application of MS-SOFC. Tape casting was employed to fabricate thin-film anodes (NiO-GDC) and electrolytes (GDC), while ultrasonic spraying was used to prepare the cathode material La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ(LSCF)-GDC. The resulting components were assembled onto a metal support to construct an MS-SOFC with a thin-film GDC electrolyte, and its electrochemical performance was evaluated. At 650 ℃, the total impedance of the cell was 0.50 Ω·cm², with Ohmic impedance of 0.23 Ω·cm² and polarization impedance of 0.27 Ω·cm², and the maximum power density was 336 mW/cm². The cell was operated at 550 ℃ under a constant voltage of 0.5 V for 100 h without significant degradation. Its electrolyte and anode, which were prepared by warm isostatic pressing and co-sintering, were tightly bonded. After long-term operation, no delamination between layers of the cell was observed, indicating that structural stability ensured the long-term stability of the MS-SOFC. MS-SOFCs in this study prepared via a process route combining tape casting, warm isostatic pressing, and direct assembly, displayed excellent electrochemical performance and long-term stability, providing a new approach for industrial production of low-temperature SOFCs.

Key words: metal-supported solid oxide fuel cell, tape casting, gadolinium doped ceria

中图分类号:

TQ174

柴润宇, 张镇, 王孟龙, 夏长荣. 直接组装法制备氧化铈基金属支撑固体氧化物燃料电池[J]. 无机材料学报, 2025, 40(7): 765-771.

CHAI Runyu, ZHANG Zhen, WANG Menglong, XIA Changrong. Preparation of Ceria Based Metal-supported Solid Oxide Fuel Cells by Direct Assembly Method[J]. Journal of Inorganic Materials, 2025, 40(7): 765-771.

图/表 6

表1 流延浆料的成分组成(质量分数, %)

Table 1 Composition of casting slurries (in mass, %)

Slurry		Electrolyte	Anode
Powder	GDC	45	12
Powder	NiO	0	28
Solvent	Ethanol	25.5	28.5
Solvent	2-Butanone	14	16
Dispersant	Triethanolamine	1.5	1.5
Plasticizer	PEG-400	4	4
Plasticizer	Dibutyl phthalate	5	5
Binder	PVA	5	5

图1 阳极-电解质复合生坯的照片(淡黄色为电解质侧, 绿色为阳极侧)

Fig. 1 Picture of anode-electrolyte composite green tape (yellow showing electrolyte side and green showing anode side)

图2 阳极与电解质材料在烧结过程中的线膨胀曲线

Fig. 2 Linear expansion curves of anode and electrolyte

图3 电堆级MS-SOFC

Fig. 3 MS-SOFC for stack level

图4 MS-SOFC的SEM照片

Fig. 4 SEM images of MS-SOFC (a) Cross-section; (b) Cross-sectional junction between anode and electrolyte; (c) Surface of electrolyte; (d) Bond between the nickel mesh and the cell; (e) Bond between the nickel mesh and the cell after operation at 550 ℃ for 100 h

图5 MS-SOFC的电化学性能

Fig. 5 Electrochemical performance of MS-SOFC (a) I-V-P curves of the cell at 500-650 ℃; (b) Performance of MS-SOFC in this study and other literature[24-29] at 650 ℃, and corresponding electrolyte materials used and their thickness; (c) Nyquist plots of a single cell at 500-650 ℃; (d) DRT curves of a single cell at 500-650 ℃; (e) Stability performance of the cell running at 550 ℃ and 0.5 V for 100 h. Colorful figures are available on website

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直接组装法制备氧化铈基金属支撑固体氧化物燃料电池

Preparation of Ceria Based Metal-supported Solid Oxide Fuel Cells by Direct Assembly Method

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