铁基钙钛矿La0.25M0.75FeO3-δ (M=Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究

doi:10.15541/jim20240500

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1365-1372.DOI: 10.15541/jim20240500

• 专栏：高温燃料电池关键材料(客座编辑：凌意瀚) • 上一篇下一篇

铁基钙钛矿La_0.25M_0.75FeO_3-_δ (M=Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究

杨恒强(), 张馨月, 马义初, 周青军()

上海理工大学理学院, 上海 200093

收稿日期:2024-12-02 修回日期:2025-01-27 出版日期:2025-12-20 网络出版日期:2025-02-25
通讯作者: 周青军, 教授. E-mail: qjzhou@usst.edu.cn
作者简介:杨恒强(1998-), 男, 硕士研究生. E-mail: 719645404@qq.com
基金资助:
国家自然科学基金(U2233206)

Iron-based Perovskite Material La_0.25M_0.75FeO_3-_δ (M=Ca, Sr, Ba): Preparation and Performance as Cathode for Solid Oxide Fuel Cells

YANG Hengqiang(), ZHANG Xinyue, MA Yichu, ZHOU Qingjun()

College of Science, University of Shanghai for Science and Technology, Shanghai 200093, China

Received:2024-12-02 Revised:2025-01-27 Published:2025-12-20 Online:2025-02-25
Contact: ZHOU Qingjun, professor. E-mail: qjzhou@usst.edu.cn
About author:YANG Hengqiang (1998-), male, Master candidate. E-mail: 719645404@qq.com
Supported by:
National Natural Science Foundation of China(U2233206)

摘要/Abstract

摘要：

固体氧化物燃料电池(SOFC)的性能受阴极氧还原反应(ORR)的制约, 其对整个电池性能至关重要。本研究通过容限因子和结构特征设计合成了La_0.25M_0.75FeO_3-_δ (M=Ba, Sr, Ca, 标记为LBF、LSF、LCF)钙钛矿阴极, 研究了Ba、Sr、Ca元素取代的特性及其对阴极电化学性能的影响。不同碱土元素对晶体结构有显著影响, LBF为Pm-3m立方相, LSF为R-3c菱方相, 而LCF为P21ma正交和Pcmn菱方的复合相。晶体结构的差异也导致了材料不同的热膨胀系数(TEC)和电导率, LCF具有最小的TEC(1.38×10^-5 K^-1), LSF具有最高的电导率, 其电导率在550 ℃达到404.4 S·cm^-1。三种Fe基阴极在空气和CO₂气氛下都呈现出优异的稳定性, 以及与电解质的化学兼容性。此外, 不同的碱土元素也影响着材料的催化活性, LSF和LBF具有低的面比电阻(ASR), 在800 ℃时ASR仅为0.022和0.027 Ω·cm², 优于LCF的0.351 Ω·cm²。较高的氧还原活性归因于其晶体结构, 以及氧的吸附和解离能力。鉴于Ba²⁺、Sr²⁺、Ca²⁺在阴极性能上各有优缺点, 未来可以在A位有效引入中高熵设计, 充分发挥各自的优势以获得综合性能优异的SOFC阴极。

关键词: 固体氧化物燃料电池, 钙钛矿, 无钴阴极, 电化学性能

Abstract:

The performance of solid oxide fuel cell (SOFC) is mainly constrained by the cathode's oxygen reduction reaction (ORR), which is crucial for overall cell efficiency. In this study, La_0.25M_0.75FeO_3-_δ (M=Ca, Sr, Ba, abbreviated as LCF, LSF, LBF) perovskite cathodes were synthesized based on tolerance factors and structural design, and effects of Ba, Sr, and Ca doping on electrochemical performance was examined. Different alkaline earth elements have a significant effect on the crystal structure. LBF is Pm-3m cubic phase, LSF is R-3c rhombohedral phase, and LCF is a composite phase of P21ma orthogonal and Pcmn rhombohedral. Difference of crystal structure also leads to various thermal expansion coefficient (TEC) and electrical conductivity. LCF possesses the smallest TEC (1.38×10^-5 K^-1), while LSF possesses the highest conductivity, which reaches 404.4 S·cm^-1 at 550 ℃. All three Fe-based cathodes exhibit excellent stability in air and CO₂ atmospheres, as well as chemical compatibility with electrolytes. In addition, different alkaline earth elements also affect catalytic activity of the material. LSF and LBF have low area specific resistance (ASR). At 800 ℃, their ASR are only 0.022 and 0.027 Ω·cm², which are better than the 0.351 Ω·cm² of LCF. The higher oxygen reduction activity is attributed to its crystal structure, oxygen adsorption and dissociation ability. In view of the advantages and disadvantages of Ba²⁺, Sr²⁺ and Ca²⁺ in cathode performance, medium/high-entropy design can be effectively introduced in A-site in the future to give full play to their respective advantages to obtain SOFC cathode with excellent comprehensive performance.

Key words: solid oxide fuel cell, perovskite, cobalt-free cathode, electrochemical performance

中图分类号:

TM911

杨恒强, 张馨月, 马义初, 周青军. 铁基钙钛矿La_0.25M_0.75FeO_3-_δ (M=Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究[J]. 无机材料学报, 2025, 40(12): 1365-1372.

YANG Hengqiang, ZHANG Xinyue, MA Yichu, ZHOU Qingjun. Iron-based Perovskite Material La_0.25M_0.75FeO_3-_δ (M=Ca, Sr, Ba): Preparation and Performance as Cathode for Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2025, 40(12): 1365-1372.

图/表 8

图1 LBF、LSF、LCF样品的(a) XRD图谱及(b~d) XRD Rietveld精修图谱

Fig. 1 (a) XRD patterns and (b-d) Rietveld refined XRD patterns of LBF, LSF and LCF samples

表1 LBF、LSF和LCF粉末的晶胞参数

Table 1 Lattice parameters of LBF, LSF and LCF powders

Sample	Space group	a/Å	b/Å	c/Å	Volume/Å³	R_wp/%	GOF
LBF	Pm-3m	3.964	3.964	3.964	62.264	8.59	1.28
LSF	R-3c	5.480	5.480	13.428	349.249	8.12	1.62
LCF-1	P21ma	5.450	11.265	5.560	341.347	14.33	2.12
LCF-2	Pcmn	5.425	14.775	5.593	448.293	14.33	2.12

图2 LBF、LSF、LCF样品的稳定性及其与GDC的兼容性

Fig. 2 Stability of LBF, LSF and LCF samples and their compatibility with GDC (a-c) XRD patterns of (a) LBF, (b) LSF and (c) LCF calcined in 5% CO2-air at 800 ℃ for 10 h, and calcined in air at 800 ℃ for 72 h; (d) Thermal expansion curves of LBF, LSF and LCF; (e) XRD patterns of LBF-GDC, LSF-GDC and LCF-GDC calcined at 1100 ℃ for 5 h

图3 LBF、LSF、LCF的XPS谱图

Fig. 3 XPS spectra of LBF, LSF and LCF (a-c) O1s and (d-f) Fe2p of (a, d) LBF, (b, e) LSF and (c, f) LCF

表2 LBF、LSF和LCF样品中O1s和Fe2p的结合能及离子面积含量百分比

Table 2 Binding energies of O1s and Fe2p and the ionic area content percentages in LBF, LSF and LCF samples

Sample	O_ad/eV	O_lat/eV	Fe³⁺/eV	Fe⁴⁺/eV
LBF	531.77(70.40%)	529.13(29.60%)	710.25; 723.25(55.85%)	712.69; 725.57(44.15%)
LSF	531.87(71.67%)	529.03(28.33%)	710.29; 723.59(62.71%)	712.12; 724.95(37.29%)
LCF	531.50(66.93%)	529.15(33.07%)	710.18; 723.17(45.36%)	712.15; 725.40(54.64%)

图4 LBF、LSF、LCF的电导率和Arrhenius曲线

Fig. 4 Conductivities and Arrhenius curves of LBF, LSF and LCF (a) Temperature dependence of electrical conductivity; (b) Arrhenius curves

图5 LBF、LSF、LCF的对称电池阻抗

Fig. 5 Impedance of symmetric cells for LBF, LSF and LCF (a-c) EIS results of LBF, LSF and LCF cathodes at different temperatures; (d) Equivalent circuit; (e) Corresponding Arrhenius plots of the ASR; (f, g) DRT curves of EIS at 600 and 700 ℃

图6 LSF为阴极的单电池性能

Fig. 6 Performance of the single cell using LSF cathode (a) I-V and I-P curves at 600-800 ℃; (b) Cross-sectional SEM image of the LSF and GDC after performance test

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铁基钙钛矿La_0.25M_0.75FeO_3-_δ (M=Ba, Sr, Ca)的制备及其作为固体氧化物燃料电池阴极材料的性能研究

Iron-based Perovskite Material La_0.25M_0.75FeO_3-_δ (M=Ca, Sr, Ba): Preparation and Performance as Cathode for Solid Oxide Fuel Cells

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