固体氧化物燃料电池Pr1+xBa1-xFe2O5+δ阴极材料的制备及电化学性能研究

doi:10.15541/jim20240404

无机材料学报 ›› 2025, Vol. 40 ›› Issue (4): 363-371.DOI: 10.15541/jim20240404 CSTR: 32189.14.10.15541/jim20240404

固体氧化物燃料电池Pr₁₊_xBa_1-_xFe₂O₅₊_δ阴极材料的制备及电化学性能研究

薛柯¹^,²^,³(), 蔡长焜¹^,²^,³, 谢满意¹^,²^,³, 李舒婷¹^,²^,³, 安胜利¹^,²^,³()

1.内蒙古科技大学稀土产业学院(稀土工程技术学院), 包头 014010
2.内蒙古科技大学内蒙古自治区先进陶瓷材料与器件重点实验室, 包头 014010
3.内蒙古科技大学轻稀土资源绿色提取与高效利用教育部重点实验室, 包头 014010

收稿日期:2024-09-09 修回日期:2024-11-08 出版日期:2025-04-20 网络出版日期:2024-11-25
通讯作者: 安胜利, 教授. E-mail: shengli_an@126.com
作者简介:薛柯(1994-), 男, 博士研究生. E-mail: xue_ke0@126.com
基金资助:
国家自然科学基金(51974167);内蒙古自然科学基金(2023QN05038);内蒙古自治区高等教育碳达峰碳中和研究项目(STZX202210)

Pr₁₊_xBa_1-_xFe₂O₅₊_δ Cathode Materials for Solid Oxide Fuel Cells: Preparation and Electrochemical Performance

XUE Ke¹^,²^,³(), CAI Changkun¹^,²^,³, XIE Manyi¹^,²^,³, LI Shuting¹^,²^,³, AN Shengli¹^,²^,³()

1. School of Rare Earth Industry, Inner Mongolia University of Science and Technology, Baotou 014010, China
2. Inner Mongolia Key Laboratory of Advanced Ceramic Materials and Devices, Inner Mongolia University of Science and Technology, Baotou 014010, China
3. Key Laboratory of Green Extraction & Efficient Utilization of Light Rare-Earth Resources, Ministry of Education, Inner Mongolia University of Science and Technology, Baotou 014010, China

Received:2024-09-09 Revised:2024-11-08 Published:2025-04-20 Online:2024-11-25
Contact: AN Shengli, professor. E-mail: shengli_an@126.com
About author:XUE Ke (1994-), male, PhD candidate. E-mail: xue_ke0@126.com
Supported by:
National Natural Science Foundation of China(51974167);Natural Science Foundation of Inner Mongolia(2023QN05038);Higher Education Carbon Peak Carbon Neutral Research Project of Inner Mongolia Autonomous Region(STZX202210)

摘要/Abstract

摘要：

PrBaFe₂O₅₊_δ(PBF)是中温固体氧化物燃料电池(IT-SOFC)技术最有前途的阴极材料之一。虽然, PBF的极化面电阻(ASR)与Co基阴极材料相近, 但电子电导率低了一个数量级。针对此问题, 目前已报道了各种掺杂优化策略。本研究用过量Pr替换PBF中的Ba, 采用溶胶-凝胶法成功合成了PBF和Pr₁₊_xBa_1-_xFe₂O₅₊_δ(PBF_x, x=0.01、0.02、0.04)材料, 并评价了其作为IT-SOFC阴极的电化学性能。结果表明, x=0.01时, 过量Pr进入PBF的晶格间隙; x≥0.02时, 过量0.01(摩尔分数)的Pr进入间隙位置, 其余过量Pr置换PBF中的Ba。在650~800 ℃范围内, Pr过量提高了PBF的电导率, 其中, PBF_0.01的电导率最高, 达到109.21 S•cm^-1, 提高了76%, 这是由于Pr过量使电子传输路径缩短。而且, Pr过量使阴极产生的晶格应变和晶格位错密度降低了氧还原反应(ORR)活性, 导致ASR略微增加。最终, 本研究制备的Ni-SDC|SDC|PBF_0.01(SDC: Sm_0.2Ce_0.8O_2-_δ)单电池的峰值功率密度比PBF器件提高了49%, 表明Pr过量可以显著提升阴极材料的电化学性能。

关键词: 固体氧化物燃料电池, PrBaFe₂O₅₊_δ, 阴极, 电化学性能

Abstract:

PrBaFe₂O₅₊_δ (PBF) is one of the most promising cathode materials for intermediate-temperature solid oxide fuel cell (IT-SOFC). Although PBF possesses similar area specific resistance (ASR) to that of Co-based cathode materials, electronic conductivity of PBF is an order of magnitude lower. Up to now, various doping strategies have been reported to enhance the electrochemical performance of this material, but still leaving it an open issue. In this study, PBF and Pr₁₊_xBa₁₋_xFe₂O₅₊_δ (PBF_x, x=0.01, 0.02, and 0.04) materials were synthesized by replacing Ba in PBF with excessive Pr using a Sol-Gel method, and their electrochemical performances as IT-SOFC cathodes were evaluated. For x=0.01, excessive Pr enters the lattice interstitials of PBF. For x≥0.02, 0.01 (in molar) excessive Pr occupies interstitial sites, while the rest replaces Ba in PBF. Over the temperature range of 650-800 ℃, excessive Pr promotes the conductivity of PBF, and PBF_0.01 exhibits the highest conductivity of 109.21 S•cm^-1, improving by 76%, which is attributed to the reduction in electronic transport path length. Furthermore, the excessive Pr contributes to lattice stress and dislocation density, reducing oxygen reduction reaction (ORR) activity and slightly increasing ASR of the cathode. Compared to PBF device, the peak power density of the Ni-SDC|SDC|PBF_0.01 (SDC: Sm_0.2Ce_0.8O_2-_δ) single cell increased by approximately 49%, indicating that excessive Pr can significantly improve the electrochemical performance of cathode materials.

Key words: solid oxide fuel cell, PrBaFe₂O₅₊_δ, cathode, electrochemical performance

中图分类号:

TM911

薛柯, 蔡长焜, 谢满意, 李舒婷, 安胜利. 固体氧化物燃料电池Pr₁₊_xBa_1-_xFe₂O₅₊_δ阴极材料的制备及电化学性能研究[J]. 无机材料学报, 2025, 40(4): 363-371.

XUE Ke, CAI Changkun, XIE Manyi, LI Shuting, AN Shengli. Pr₁₊_xBa_1-_xFe₂O₅₊_δ Cathode Materials for Solid Oxide Fuel Cells: Preparation and Electrochemical Performance[J]. Journal of Inorganic Materials, 2025, 40(4): 363-371.

参考文献 31

[1]	ZHOU L F, MASON J H, LI W Y, et al. Comprehensive review of chromium deposition and poisoning of solid oxide fuel cells (SOFCs) cathode materials. Renewable and Sustainable Energy Reviews, 2020, 134: 110320.
[2]	ZHANG W, HU Y H. Recent progress in design and fabrication of SOFC cathodes for efficient catalytic oxygen reduction. Catalysis Today, 2023, 409: 71.
[3]	AHMAD M Z, AHMAD S H, CHEN R S, et al. Review on recent advancement in cathode material for lower and intermediate temperature solid oxide fuel cells application. International Journal of Hydrogen Energy, 2022, 47(2):1103.
[4]	TAHIR N N M, BAHARUDDIN N A, SAMAT A A, et al. A review on cathode materials for conventional and proton-conducting solid oxide fuel cells. Journal of Alloys and Compounds, 2022, 894: 162458.
[5]	WANG F F, KISHIMOTO H, ISHIYAMA T, et al. A review of sulfur poisoning of solid oxide fuel cell cathode materials for solid oxide fuel cells. Journal of Power Sources, 2020, 478: 228763.
[6]	CHEN S G, ZHANG H X, YAO C G, et al. Review of SOFC cathode performance enhancement by surface modifications: recent advances and future directions. Energy & Fuels, 2023, 37(5):3470.
[7]	CHEN D J, WANG F C, SHI H G, et al. Systematic evaluation of Co-free LnBaFe₂O₅₊_δ (Ln=lanthanides or Y) oxides towards the application as cathodes for intermediate-temperature solid oxide fuel cells. Electrochimica Acta, 2012, 78: 466.
[8]	LEE D, KIM D, SON S J, et al. Simultaneous A- and B-site substituted double perovskite (AA’B₂O₅₊_δ) as a new high- performance and redox-stable anode material for solid oxide fuel cells. Journal of Power Sources, 2019, 434: 226743.
[9]	WEN C Y, CHEN K, GUO D, et al. High performance and stability of PrBa_0.5Sr_0.5Fe₂O₅₊_δ symmetrical electrode for intermediate temperature solid oxide fuel cells. Solid State Ionics, 2022, 386: 116048.
[10]	IVANOV A I, KOLOTYGIN V A, TSIPIS E V, et al. Electrical conductivity, thermal expansion and electrochemical properties of perovskites PrBaFe_2-_xNi_xO₅₊_δ. Russian Journal of Electrochemistry, 2018, 54: 533.
[11]	LU C L, NIU B B, YI W D, et al. Efficient symmetrical electrodes of PrBaFe_2-_xCo_xO₅₊_δ (x = 0, 0.2, 0.4) for solid oxide fuel cells and solid oxide electrolysis cells. Electrochimica Acta, 2020, 358: 136916.
[12]	REN R Z, WANG Z H, MENG X G, et al. Boosting the electrochemical performance of Fe-based layered double perovskite cathodes by Zn²⁺ doping for solid oxide fuel cells. ACS Applied Materials & Interfaces, 2020, 12(21):23959.
[13]	ZHU C J, YI C S, CHAO L M. Preparation and performance of Pr-doped Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ cathode for IT-SOFCs. Journal of Rare Earths, 2011, 29(11):1070.
[14]	TOBY B H. EXPGUI, a graphical user interface for GSAS. Journal of Applied Crystallography, 2001, 34(2):210.
[15]	LARSON A C, VON DREELE R B. General structure analysis system (GSAS). Los Alamos National Laboratory Report LAUR 86-748, 2004.
[16]	梁敬魁. 粉末衍射法测定晶体结构. 北京: 科学出版社, 2003: 798.
[17]	COX-GALHOTRA R A, MCINTOSH S. Unreliability of simultaneously determining K_chem and D_chem via conductivity relaxation for surface-modified La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ. Solid State Ionics, 2010, 181(31/32):1429.
[18]	PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18):3865. DOI PMID
[19]	VANDERBILT D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Physical Review B, 1990, 41(11):7892. PMID
[20]	LIU Y, QIN H B, LI M L, et al. Direct synthesis of Ce_0.8Sm_0.2-_xZn_xO_2-_δ electrolyte by Sol-Gel for IT-SOFC. Ionics, 2022, 28(10):4675.
[21]	HAJIABADI M G, ZAMANIAN M, SOURI D. Williamson-Hall analysis in evaluation of lattice strain and the density of lattice dislocation for nanometer scaled ZnSe and ZnSe: Cu particles. Ceramics International, 2019, 45(11):14084.
[22]	CAI C K, XIE M Y, XUE K, et al. Enhanced electrochemical performance of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ cathode via Ba-doping for intermediate-temperature solid oxide fuel cells. Nano Research, 2022, 15: 3264.
[23]	YAO C G, YANG J X, ZHANG H X, et al. Ca-doped PrBa_1-_xCa_xCoCuO₅₊_δ (x=0-0.2) as cathode materials for solid oxide fuel cells. Ceramics International, 2022, 48(6):7652.
[24]	廖家轩, 潘笑风, 王洪全, 等. Ce掺杂Ba_0.6Sr_0.4TiO₃薄膜表面结构XPS研究. 稀有金属材料与工程, 2009, 38(11): 1987.
[25]	ZHANG Y, NIU B B, HAO X H, et al. Layered oxygen-deficient double perovskite GdBaFe₂O₅₊_δ as electrode material for symmetrical solid-oxide fuel cells. Electrochimica Acta, 2021, 370: 137807.
[26]	LIU J C, JIN F J, YANG X, et al. YBaCo₂O₅₊_δ-based double- perovskite cathodes for intermediate-temperature solid oxide fuel cells with simultaneously improved structural stability and thermal expansion properties. Electrochimica Acta, 2019, 297: 344.
[27]	CALLISTER JR W D, RETHWISCH D G. Materials Science and Engineering: an Introduction. 10th edition. Hoboken: Wiley, 2018: 653-656.
[28]	LIU Y H, WANG F Z, CHI B, et al. A stability study of impregnated LSCF-GDC composite cathodes of solid oxide fuel cells. Journal of Alloys and Compounds, 2013, 578: 37.
[29]	WANG J L, YANG Z B, YANG K C, et al. Chromium deposition and poisoning on Ba_0.9Co_0.7Fe_0.2Nb_0.1O_3-_δ cathode of solid oxide fuel cells. Electrochimica Acta, 2018, 289: 503.
[30]	LIU X, ZHANG L, ZHENG Y, et al. Uncovering the effect of lattice strain and oxygen deficiency on electrocatalytic activity of perovskite cobaltite thin films. Advanced Science, 2019, 6(6):1801898.
[31]	LIN T N, LEE M C, YANG R J, et al. Chemical state identification of Ce³⁺/Ce⁴⁺ in the Sm_0.2Ce_0.8O_2-_δ electrolyte for an anode-supported solid oxide fuel cell after long-term operation. Materials Letters, 2012, 81: 185.

固体氧化物燃料电池Pr₁₊_xBa_1-_xFe₂O₅₊_δ阴极材料的制备及电化学性能研究

Pr₁₊_xBa_1-_xFe₂O₅₊_δ Cathode Materials for Solid Oxide Fuel Cells: Preparation and Electrochemical Performance

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