硅酸盐学报

金属支撑固体氧化物燃料电池阳极造孔及电化学性能

PDF下载

林凯生 ¹ , 朱志刚 ¹^,² , 宋琛 ¹ , 刘太楷 ¹ , 文魁 ¹ , 毛杰 ¹ , 张小锋 ¹ , 邓畅光 ¹ , 邓春明 ¹ , 刘敏 ¹

硅酸盐学报 | 研究论文 2025,54(4): 1359-1369

收起

硅酸盐学报 | 研究论文 2025, 54(4): 1359-1369

金属支撑固体氧化物燃料电池阳极造孔及电化学性能

全屏

林凯生¹, 朱志刚¹^,², 宋琛¹, 刘太楷¹, 文魁¹, 毛杰¹, 张小锋¹, 邓畅光¹, 邓春明¹, 刘敏¹

作者信息

^1．广东省科学院新材料研究所，现代材料表面工程技术国家工程实验室，广东省现代表面工程技术重点实验室，粤港现代表面工程技术联合实验室，广州 510650

^2．华南理工大学材料科学与工程学院，发光材料与器件国家重点实验室，广州 510641

林凯生（1979—），男，工程师。

LIN Kaisheng (1979-), male, Engineer. E-mail: links168@163.com

通讯作者:

宋琛（1990—），男，高级工程师。

Pore-Forming and Electrochemical Performance of Anodes for Metal-Supported Solid Oxide Fuel Cells

Kaisheng LIN¹, Zhigang ZHU¹^,², Chen SONG¹, Taikai LIU¹, Kui WEN¹, Jie MAO¹, Xiaofeng ZHANG¹, Changguang DENG¹, Chunming DENG¹, Min LIU¹

Affiliations

^1.Institute of New Materials, Guangdong Academy of Sciences; National Engineering Laboratory of Modern Materials Surface Engineering Technology; Guangdong Provincial Key Laboratory of Modern Surface Engineering Technology; Guangdong-Hong Kong Joint Laboratory of Modern Surface Engineering Technology, Guangzhou 510650, China

^2.School of Materials Science and Engineering, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510641, China

出版时间: 2025-12-29 doi: 10.14062/j.issn.0454-5648.20250682

文章导航

摘要

收起

金属支撑固体氧化物燃料电池（MS-SOFC）的阳极微观结构如孔隙率、三相界面（TPB）及催化活性位点的分布显著影响其电化学性能。为系统研究并调控其微观结构，本工作采用喷雾造粒和机械混合工艺，在NiO-Gd_0.2Ce_0.8O_1.9（GDC）粉末中引入石墨造孔剂，探究其添加形式对大气等离子喷涂（APS）制备阳极的微观结构及电化学性能的影响。结果表明：未添加石墨的阳极呈现典型的喷涂态层状堆叠结构，其特征主要为亚微米级裂纹和细小孔洞；而通过复合团聚引入石墨的阳极涂层内部孔隙结构尺度适中、分布均匀，并伴随少量微裂纹，为燃料传输与产物排出提供了有效通道；机械混合添加的石墨因聚集成约5 μm的颗粒，喷涂后形成大尺寸孤立孔洞，破坏了Ni导电网络的连续性，并减少了TPB有效活性位点。电化学阻抗谱分析表明，石墨可调控喷涂过程中粉末的热响应行为，促进粉末熔融而形成更均匀的微观结构，从而增强电荷转移并降低高频极化电阻。石墨的添加形式对孔隙结构及反应活性位点具有关键调控作用，机械混合添加形成的大尺寸孔隙阻碍了燃料吸附／解离过程，导致其低频极化电阻最大。尽管添加石墨有助于调控孔隙，但其在喷涂过程中的热分解会提高阳极表面粗糙度，影响电解质沉积质量，导致含石墨电池的开路电压降低，欧姆电阻升高，整体输出性能下降。后续工作可通过阳极表面改性，协同孔隙结构均匀性优化，构建更多有效的反应活性位点，以提升MS-SOFC的综合输出性能。

关键词

阳极 / 石墨造孔剂 / 大气等离子喷涂 / 金属支撑型固体氧化物燃料电池 / 电化学性能

Abstract

收起

Introduction

Solid oxide fuel cells (SOFCs) are high-efficient solid-state energy conversion devices. However, all-ceramic self-supported SOFCs face several challenges such as high brittleness, difficulty in mechanical processing, poor thermal shock resistance, and limited weldability, which result in high manufacturing costs and restrict the applications in mobile power systems. In contrast, metal-supported SOFCs (MS-SOFCs) with metal materials as the external structural support, exhibit remarkable mechanical strength, low cost, and rapid start-up capability, making it highly promising for mobile applications. The anode is a critical component of MS-SOFCs, serving as the site where fuel oxidation occurs to generate electrons. Its microstructure significantly influences the density and effectiveness of the triple-phase boundaries (TPB), where the gas phase, the ionic phase, and the electronic phase intersect. The TPB density largely determines the polarization resistance, with its low-frequency component being inversely related to anode gas diffusion. A common strategy to enhance gas transport is the incorporation of pore-formers, such as graphite, into the anode raw materials. Most studies focus on the type, particle size, and content of pore-formers, which directly affect the pores number, size, and distribution. In this work, atmospheric plasma spraying (APS) was employed to fabricate three types of anodes and corresponding cells. APS reduces thermal input to the metal substrate, effectively preventing oxidation, deformation, and elemental interdiffusion between the metal support and the anode at high temperatures. This study systematically investigates the influence of graphite incorporation methods on the microstructural evolution of the anode and the resulting cell performance, providing important theoretical insights into the operational mechanisms of SOFC anodes.

Methods

Porous 430L stainless steel substrates were used as supports. Three different NiO-GDC (Gd_0.2Ce_0.8O_1.9) anode powders were prepared. C1 is the baseline without a pore-former. C2 contains 40% (in volume fraction) graphite, which is mixed by spray granulation process to produce composite particles. C3 is made by mechanically mixing 40% of the same graphite with C1 powder. All powders are spherical with good fluidity. Anode layers were deposited via APS. Subsequently, the C2 and C3 anodes were heat-treated in air to remove the graphite pore-former at 750 ℃ for 2 h. A ScSZ (Sc₂O₃-ZrO₂) electrolyte and an LSCF (La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ) cathode were subsequently deposited by APS to build single cells. The microstructure and porosity of the anodes were characterized using scanning electron microscopy (SEM) and image analysis software. The surface roughness was measured by profilometer. The electrochemical performance, including the open-circuit voltage (OCV), current-voltage-power (I-V-P) and electrochemical impedance spectroscopy (EIS), were evaluated in the range of 600-750 ℃ using humidified H₂ as fuel and air as oxidant. The equivalent circuit fitting of EIS data is carried out to quantitatively analyze the contribution of charge transfer, surface adsorption/dissociation and gas diffusion in polarization impedance.

Results and discussion

The incorporation of graphite pore-former significantly modified the pore size distribution and total porosity within the anodes. The measured porosity of C1, C2, and C3 was 26%±2%, 37%±3.1%, and 42%±2.3%, respectively. The C1 anode featured a relatively dense structure with uniformly distributed pores, which primarily consisted of submicron cracks and fine pores originating from the thermal stress inherent to the APS process. In contrast, the C2 anode showed a notable increase in both the number and size of pores, which were homogeneously dispersed without significant agglomeration. The C3 anode, however, contained a substantial amount of large pores, mostly ~5 μm in diameter, attributed to the agglomeration of graphite particles during mechanical mixing, resulting in coarse and irregular pore structures after heat treatment. Furthermore, the addition of graphite modified the thermal response characteristics of the agglomerated powder during the spraying process, promoting the formation of a more uniformly melted microstructure in the anode layer. The average surface roughness (R_a) values for C1, C2, and C3 were 6.64, 7.06 nm, and 7.66 μm, respectively, indicating that graphite addition increased anode surface roughness. This phenomenon is due to the thermal decomposition of graphite during the plasma spraying process, where high temperatures cause partial oxidation of graphite in the open atmosphere, thereby generating CO₂ gas. The release of this gas from the incompletely solidified anode surface etches irregular pits and protrusions, ultimately leading to increased surface roughness. The cell without graphite pore-former (C1) consistently demonstrated the highest OCV and maximum power density, reaching 1.0 V and 957 mW·cm^-2 at 750 ℃, respectively. EIS analysis revealed that the anodes with graphite pore-former (C2 and C3) exhibited improved charge transfer capability, thereby reducing the high-frequency polarization resistance. Despite this, the overall output performance of C2 and C3 did not show effective enhancement, which is attributed to their increased ohmic resistance (R_o) and lower OCV. The elevated surface roughness and inherent porosity in the C2 and C3 anodes adversely affected the quality of the subsequently sprayed electrolyte layer, introducing microcracks and gas permeation pathways. This resulted in increased R_o and reduced OCV, ultimately weakening the benefits gained from the reduced polarization resistance.

Conclusions

The method of graphite pore-former addition significantly affects the anode microstructure and overall cell performance. Compared with mechanical mixing, spray granulation produces a superior and uniform pore structure. However, contrary to conventional expectation, the introduction of graphite pore-forming agent into the APS anode reduces overall cell performance due to induced electrolyte defects, which elevated R_o and lowered OCV. Future optimization should focus on strategies to reduce anode surface roughness and refine pore structure without affecting the quality of electrolyte deposition. It is anticipated that this will further enhance the output performance of MS-SOFCs.

Key words

anode / graphite pore-former / atmospheric plasma spraying / metal-supported solid oxide fuel cells / electrochemical performance

引用本文

林凯生, 朱志刚, 宋琛, 刘太楷, 文魁, 毛杰, 张小锋, 邓畅光, 邓春明, 刘敏. 金属支撑固体氧化物燃料电池阳极造孔及电化学性能. 硅酸盐学报, 2025 , 54 (4) : 1359 -1369 . DOI: 10.14062/j.issn.0454-5648.20250682

Kaisheng LIN, Zhigang ZHU, Chen SONG, Taikai LIU, Kui WEN, Jie MAO, Xiaofeng ZHANG, Changguang DENG, Chunming DENG, Min LIU. Pore-Forming and Electrochemical Performance of Anodes for Metal-Supported Solid Oxide Fuel Cells[J]. Journal of the Chinese Ceramic Society, 2025 , 54 (4) : 1359 -1369 . DOI: 10.14062/j.issn.0454-5648.20250682

基金

收起

国家重点研发计划(2023YFE0108000)
国家自然科学基金(52201069)
广东省科技计划项目(2023B1212060045; 2023B1212120008)
广东省科学院青年人才专项(2024GDASQNRC-0208)
广东省科学院发展专项资金项目(2024GDASZH-2024010102)
广东省科学院新材料研究所专项资金项目(2023GINMZX-202301020104)
广州市基础与应用基础研究项目(2025A04J5111)

参考文献

收起

2025年第54卷第4期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20250682

接收时间：2025-09-22
首发时间：2026-05-20
出版时间：2025-12-29

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2025-09-22
修回日期：2025-10-21

基金

国家重点研发计划(2023YFE0108000)

国家自然科学基金(52201069)

广东省科技计划项目(2023B1212060045; 2023B1212120008)

广东省科学院青年人才专项(2024GDASQNRC-0208)

广东省科学院发展专项资金项目(2024GDASZH-2024010102)

广东省科学院新材料研究所专项资金项目(2023GINMZX-202301020104)

广州市基础与应用基础研究项目(2025A04J5111)

作者信息

^2．华南理工大学材料科学与工程学院，发光材料与器件国家重点实验室，广州 510641

通讯作者:

宋琛（1990—），男，高级工程师。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250682

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT