固体氧化物燃料电池复合阴极的多孔结构对气体扩散阻抗的影响规律

doi:10.15541/jim20250485

无机材料学报 ›› 2026, Vol. 41 ›› Issue (9): 1201-1210.DOI: 10.15541/jim20250485

固体氧化物燃料电池复合阴极的多孔结构对气体扩散阻抗的影响规律

杨艺文¹(), 潘宁¹, 蒋玉楠², 蒋学鑫², 夏长荣¹^,²()

¹ 中国科学技术大学化学与材料科学学院, 合肥 230026
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

收稿日期:2025-12-09 修回日期:2026-01-26 出版日期:2026-09-20 网络出版日期:2026-02-28
通讯作者: 夏长荣, 教授. E-mail: xiacr@ustc.edu.cn
作者简介:杨艺文(2001-), 男, 硕士研究生. E-mail: sa23014040@mail.ustc.edu.cn
基金资助:
国家自然科学基金(52572272)

Influence of Porous Structure of Composite Cathode on Gas Diffusion Impedance in Solid Oxide Fuel Cells

YANG Yiwen¹(), PAN Ning¹, JIANG Yunan², JIANG Xuexin², XIA Changrong¹^,²()

¹ School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China
² Energy Materials Center, Anhui Estone Materials Technology Co., Ltd., Hefei 230088, China

Received:2025-12-09 Revised:2026-01-26 Published:2026-09-20 Online:2026-02-28
Contact: XIA Changrong, professor. E-mail: xiacr@ustc.edu.cn
About author:YANG Yiwen (2001-), male, Master candidate. E-mail: sa23014040@mail.ustc.edu.cn
Supported by:
National Natural Science Foundation of China(52572272)

摘要/Abstract

摘要：

固体氧化物燃料电池(Solid Oxide Fuel Cell, SOFC)阴极通常是多孔结构的复合材料, 以满足气体扩散要求。然而, 电极结构与气体扩散阻抗的关系有待进一步揭示。本工作以典型复合阴极镧锶钴铁-掺杂氧化铈(La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ-Sm_0.2Ce_0.8O_1.9, LSCF-SDC)为对象, 结合交流阻抗谱(Electrochemical Impedance Spectroscopy, EIS)技术、弛豫时间分布(Distribution of Relaxation Time, DRT)分析与三维(Three-dimensional, 3D)重构方法, 揭示阴极结构与气体扩散阻抗的关系。结果显示: 在恒电流放电下, 扩散阻抗随阴极厚度呈近线性增加; 在1.0 A·cm^-2的大电流密度下, 受集流体及外部滞流层对传质的限制作用, 阻抗-厚度拟合出现了0.11288 Ω·cm²的非零截距。微观结构分析表明, 随着孔径主峰从~0.3 μm移至~1 μm, 气体传输机制从Knudsen扩散向分子扩散根本性转变, 导致扩散阻抗大幅降低。孔隙率增加虽有利于传质, 却导致三相界面(Triple Phase Boundary, TPB)密度从233.5 μm·μm^-3降至196.7 μm·μm^-3, 引起表面交换阻抗升高。综合权衡, 添加15%(质量分数)草酸铵可以实现传质能力与反应活性之间的最佳平衡。本研究建立了包含孔隙率、曲折因子及孔径的定量扩散阻抗模型, 为SOFC阴极微观结构设计提供了可验证的实验依据和理论支持。

关键词: 气体扩散阻抗, 扩散阻抗模型, 氧还原反应, LSCF-SDC复合阴极, 固体氧化物燃料电池

Abstract:

Solid oxide fuel cell (SOFC) cathodes are typically composite materials with porous structure to meet gas diffusion requirements. However, the relationship between electrode structure and gas diffusion impedance remains to be further elucidated. Taking the typical composite cathode lanthanum strontium cobalt ferrite-doped ceria (La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ-Sm_0.2Ce_0.8O_1.9, LSCF-SDC) as the research object, this study reveals the relationship between cathode structure and gas diffusion impedance by combining electrochemical impedance spectroscopy (EIS), distribution of relaxation time (DRT) analysis, and three-dimensional (3D) reconstruction methods. The results indicate that under galvanostatic discharge, the diffusion impedance increases nearly linearly with cathode thickness. Specifically, at a high current density of 1.0 A·cm^-2, a non-zero intercept of 0.11288 Ω·cm² appears in the impedance-thickness fitting, attributed to the mass transfer limitations imposed by the current collector and the external stagnant layer. Microstructural analysis demonstrates that as the dominant pore size increases from ~0.3 to ~1 μm, a fundamental transition in the gas transport mechanism from Knudsen diffusion to molecular diffusion occurs, resulting in a substantial reduction in diffusion impedance. However, while the increased porosity facilitates mass transfer, it leads to a decrease in triple-phase boundary (TPB) density from 233.5 to 196.7 μm·μm^-3, thereby inducing an increase in surface exchange impedance. Comprehensive analysis demonstrates that addition of 15% (in mass) ammonium oxalate achieves an optimal balance between mass transport capability and reaction activity. In this work, a quantitative diffusion impedance model incorporating porosity, tortuosity, and pore size factor is established, providing verifiable experimental evidence and theoretical support for the microstructural design of SOFC cathodes.

Key words: gas diffusion impedance, diffusion impedance model, oxygen reduction reaction, LSCF-SDC composite cathode, solid oxide fuel cell

中图分类号:

TM911

杨艺文, 潘宁, 蒋玉楠, 蒋学鑫, 夏长荣. 固体氧化物燃料电池复合阴极的多孔结构对气体扩散阻抗的影响规律[J]. 无机材料学报, 2026, 41(9): 1201-1210.

YANG Yiwen, PAN Ning, JIANG Yunan, JIANG Xuexin, XIA Changrong. Influence of Porous Structure of Composite Cathode on Gas Diffusion Impedance in Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2026, 41(9): 1201-1210.

图/表 11

表1 各实验组阴极编号

Table 1 Sample codes of cathodes in each experimental group

Sample	L/μm	LSCF : SDC : Terpineol : AO (in mass)
T-5	5.2	60 : 40 : 150 : 0
T-9	9.6	60 : 40 : 150 : 0
T-14	14.0	60 : 40 : 150 : 0
T-18	18.2	60 : 40 : 150 : 0
P-5	~30	60 : 40 : 150 : 5
P-15	~30	60 : 40 : 150 : 15
P-35	~30	60 : 40 : 150 : 35
P-55	~30	60 : 40 : 150 : 55

图1 LSCF-SDC复合阴极的物相和P-15的微观形貌及单电池性能

Fig. 1 Phase composition of LSCF-SDC composite cathode and microstructure and single cell performance of P-15 (a) XRD patterns of powders and sintered cathode; (b) Low-magnification cross-sectional SEM image of single cell; (c) High-magnification SEM image of electrolyte/anode interface; (d) I-V-P curves at 700-800 ℃; (e) Cross-sectional SEM image of the cathode/electrolyte interface after I-V and EIS measurements at 700-800 ℃

图2 750 ℃下T-5单电池的阻抗解析

Fig. 2 Impedance analysis of T-5 single cell at 750 ℃ (a) Nyquist spectra under different oxygen partial pressures at OCV; (b) DRT curves under different oxygen partial pressures at OCV; (c) Variation of ${{\text{P}}_{\text{M}1}}$ and ${{\text{P}}_{\text{M}2}}$ peak areas with oxygen partial pressure; (d) Nyquist spectra under different discharge currents; (e) DRT curves under different discharge currents; (f) Variation of ${{\text{P}}_{\text{L}}}$ and ${{\text{P}}_{\text{M}3}}$ peak areas with current density. Colorful figures are available on website

图3 T-5~T-18阴极微观结构的三维重构

Fig. 3 3D microstructural reconstruction of T-5-T-18 cathodes (a) 2D backscattered electron (BSE) mode images after phase segmentation; (b) 3D microstructures reconstructed by DCFs algorithm; (c) Spatial distribution of active TPB within the cathodes. Colorful figures are available on website

表2 T-5~T-18、P-5~P-55的部分微结构特征

Table 2 Selected microstructural characteristics of T-5-T-18 and P-5-P-55

Sample	$\varepsilon $/%	$\tau $	TPB density/(μm·μm^-3)
Sample	$\varepsilon $/%	$\tau $	Active	Isolated
T-5	42.94	1.53	257.7	11.2
T-9	44.99	1.49	249.5	9.7
T-14	42.17	1.54	265.0	13.7
T-18	43.66	1.51	254.7	10.7
P-5	52.65	1.36	233.5	14.7
P-15	55.16	1.32	220.0	18.2
P-35	62.66	1.25	204.9	25.3
P-55	68.66	1.19	196.7	30.7

图4 T-5~T-18阴极阻抗演变规律与扩散模型验证

Fig. 4 Impedance evolution and diffusion model verification for T-5-T-18 cathodes (a) Variation of gas diffusion impedance$({{R}_{\text{PL}}})$with cathode thickness under different current densities; (b) Correlation between surface exchange impedance$\text{(}{{R}_{\text{PM12}}})$and ${{R}_{\text{PL}}}$; Model fittings of${{R}_{\text{PL}}}$at (c) 0.5 and (d) 1.0 A·cm–2

图5 不同孔隙结构的阴极微观形貌及孔径分布

Fig. 5 Microstructures and pore size distributions of cathodes with different pore structures Cross-sectional SEM images of (a) T-18 (0 AO), (b) P-5 (5% AO), and (c) P-55 (55% AO); (d) Pore size distribution curves of P-5-P-55 cathodes (colorful figure is available on website)

图6 P-5~P-55微观结构参数对阴极气体扩散过程的调控机制与理论验证

Fig. 6 Regulatory mechanism of microstructural parameters on cathode gas diffusion and theoretical verification for P-5-P-55 (a) Variation of gas diffusion impedance ${{R}_{\text{PL}}}$ with porosity ε at 0.5 A·cm–2; (b) Correlation between surface exchange impedance ${{R}_{\text{PM12}}}$ and ${{R}_{\text{PL}}}$; (c) Fitting of ${{R}_{\text{PL}}}$ with geometric resistance factor $\frac{\tau }{\varepsilon }$ at 0.5 A·cm–2; (d) Fitting of ${{R}_{\text{PL}}}$ with pore size resistance factor $\frac{1}{r}$ at 0.5 A·cm–2

表S1 本研究的试剂信息

Table S1 Information of reagents used in this study

Reagent	Purity/Specification	Manufacturer
LSCF
La(NO₃)₃·6H₂O	AR	Sinopharm
Sr(NO₃)₂	AR	Sinopharm
Co(NO₃)₂·6H₂O	99.9%	Sinopharm
Fe(NO₃)₃·9H₂O	AR	Sinopharm
Citric acid monohydrate	AR	Sinopharm
Ethylenediaminetetraacetic Acid, EDTA	AR	Sinopharm
SDC
Ce(NO₃)₃·6H₂O	AR	Sinopharm
Sm(NO₃)₃·6H₂O	AR	Sinopharm
Glycine	AR	Sinopharm
(NH₄)₂CO₃	AR	Sinopharm
NiO
Ni₂CO₃(OH)₂	AR	Aladdin
8YSZ
Zr_0.92Y_0.16O_2-_δ	Commercial powder	Fuelcell
Anode Support Additives
Polyethersulfone, PESF (Mw=5800)	AR	Macklin
Polyvinylpyrrolidone, PVP(K-30)	AR	Aladdin
1-Methyl-2-pyrrolidone, NMP	AR	Sinopharm
Dispersant
Terpineol	AR	Sinopharm
Pore Former
(NH₄)₂C₂O₄	AR	Sinopharm
Ethanol	AR	Sinopharm

表S2 阳极支撑体浆料的配方(含电解质和阻隔层的浸涂浆料)

Table S2 Detailed composition of anode support slurry (including dip-coating slurries for electrolyte and barrier layers)

Component	Amount/Remarks
Anode Support Slurry	Planetary ball milled with zirconia balls
PESF	60 g
PVP	15 g
NMP	300 g
NiO	84.5 g
8YSZ	45.5 g
Electrolyte Slurry	Rolling ball milled with zirconia balls
Ethanol	50 g
8YSZ	5 g
Dispersant	5 g
Barrier Layer Slurry	Rolling ball milled with zirconia balls
Ethanol	50 g
SDC	5 g
Dispersant	5 g

图S1 T系列与P系列单电池的电化学性能汇总

Fig. S1 Summary of electrochemical performance of T-series and P-series single cells (a) I-V-P curves of T-5-T-18 single cells at 750 ℃; (b) I-V-P curves of T-5 single cell at 700, 750 and 800 ℃; (c) Peak power densities of T-5-T-18 single cells at 700, 750 and 800 ℃; (d) I-V-P curves of P-5-P-55 single cells at 750 ℃; (e) Peak power densities of P-5-P-55 single cells at 700, 750 and 800 ℃

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固体氧化物燃料电池复合阴极的多孔结构对气体扩散阻抗的影响规律

Influence of Porous Structure of Composite Cathode on Gas Diffusion Impedance in Solid Oxide Fuel Cells

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