双钙钛矿Sr2CoFeO5+δ阴极材料的制备及其中温固体氧化物燃料电池性能研究

doi:10.15541/jim20230428

无机材料学报 ›› 2024, Vol. 39 ›› Issue (3): 337-344.DOI: 10.15541/jim20230428 CSTR: 32189.14.10.15541/jim20230428

所属专题：【能源环境】燃料电池(202409)

• 研究快报 • 上一篇

双钙钛矿Sr₂CoFeO₅₊_δ阴极材料的制备及其中温固体氧化物燃料电池性能研究

陈正鹏¹(), 金芳军²^,³(), 李明飞¹, 董江波¹, 许仁辞¹, 徐韩昭⁴, 熊凯⁵, 饶睦敏¹, 陈创庭¹, 李晓伟², 凌意瀚²()

1.广东能源集团科技研究院有限公司, 广州510000
2.中国矿业大学材料科学与物理学院, 徐州 221116
3.长春理工大学, 长春 130022
4.广东省能源集团有限公司, 广州510000
5.广东惠州天然气发电有限公司, 惠州 516000

收稿日期:2023-09-20 修回日期:2023-11-16 出版日期:2024-03-20 网络出版日期:2023-11-28
通讯作者: 凌意瀚, 教授. E-mail: lyhyy@cumt.edu.cn;
金芳军, 副教授. E-mail: jinfj@cumt.edu.cn
作者简介:陈正鹏(1991-)，男，硕士. E-mail: chenzhengpeng@geg.com.cn

Double Perovskite Sr₂CoFeO₅₊_δ: Preparation and Performance as Cathode Material for Intermediate-temperature Solid Oxide Fuel Cells

CHEN Zhengpeng¹(), JIN Fangjun²^,³(), LI Mingfei¹, DONG Jiangbo¹, XU Renci¹, XU Hanzhao⁴, XIONG Kai⁵, RAO Muming¹, CHEN Chuangting¹, LI Xiaowei², LING Yihan²()

1. Guangdong Energy Group Science and Technology Research Institute Co., Ltd, Guangzhou 510000, China
2. School of Materials Science and Physics, China University of Mining and Technology, Xuzhou 221116, China
3. School of Physics, Changchun University of Science and Technology, Changchun 130022, China
4. Guangdong Energy Group Co., Ltd., Guangzhou 510000, China
5. Guangdong Huizhou LNG Power Co., Ltd., Huizhou 516000, China

Received:2023-09-20 Revised:2023-11-16 Published:2024-03-20 Online:2023-11-28
Contact: LING Yihan, professor. E-mail: lyhyy@cumt.edu.cn;
JIN Fangjun, associate professor. E-mail: jinfj@cumt.edu.cn
About author:CHEN Zhengpeng (1991-), male, Master. E-mail: chenzhengpeng@geg.com.cn
Supported by:
The Key-Area Research and Development Program of Guangdong Province(2022B0111130004);National Natural Science Foundation of China(52272257);Innovation Team of Jiangsu Province(JSSCTD202241)

摘要/Abstract

摘要：

随着操作温度降低, 中温固体氧化物燃料电池(IT-SOFCs)需要更高催化活性的阴极材料来提升电池性能。为此, 本研究采用溶胶-凝胶法合成了双钙钛矿Sr₂CoFeO₅₊_δ (SCF)阴极材料, 并探讨了SCF阴极与摩尔分数20% Sm₂O₃掺杂的CeO₂(SDC)进行不同比例的复合对电极性能的影响, 优化了电极的化学膨胀和面积比电阻(ASR)，进而提升了SOFC单电池的电化学性能。结果表明, SCF作为SOFC阴极, 经950 ℃退火10 h后与普通电解质具有良好的化学相容性; 其中, SCF与SDC按照质量比1 : 1复合的样品可以将纯SCF样品的平均热膨胀系数(TEC)从2.44×10⁻⁵ K⁻¹显著降到15.4×10⁻⁵ K⁻¹。此外, SCF-xSDC(x=20, 30, 40, 50, x为SDC的质量分数)复合阴极的ASR在800 ℃下分别低至0.036、0.034、0.028和0.092 Ω·cm², SCF-40SDC在所有温度范围内都表现出更小的ASR。复合SDC可以优化SCF的三相界面且进一步提高SCF阴极的催化活性, 以0.3mm厚La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-_δ(LSGM)为电解质的SCF-40SDC单电池(757 mW·cm⁻²)比SCF单电池(684 mW·cm⁻²)的最大功率密度更优, 且超过目前大部分的文献报道。本研究制备的SCF−40SDC是一种性能优异的复合阴极材料, 有望应用于中温固体氧化物燃料电池。

关键词: 固体氧化物燃料电池, 双钙钛矿, 阴极, Sr₂CoFeO₅₊_δ, 复合电极, 电化学性能

Abstract:

Intermediate-temperature solid oxide fuel cells (IT-SOFCs), as the operating temperature decreases, require cathode materials with high catalytic activity. In this study, double perovskite Sr₂CoFeO₅₊_δ (SCF) was synthesized by Sol-Gel method, and effect of SCF cathode compounded with 20% (molar fraction) Sm₂O₃ doped CeO₂ (SDC) at different ratios on the electrode performance was elucidated. The SOFC single-cell performance was improved by optimized chemical expansion and area-specific resistance (ASR) from composite electrodes. Results show that, SCF cathode after annealing at 950 ℃ for 10 h exhibits good chemical compatibility with common electrolytes. For the composite of SCF and SDC at a mass ratio of 1 : 1, the average thermal expansion coefficient (TEC) can be significantly reduced from 2.44×10⁻⁵K^-1of pure SCF to 1.54×10⁻⁵ K^-1. ASR of SCF−xSDC (x=20, 30, 40, 50, x: mass percentage) composite cathodes are as low as 0.036, 0.034, 0.028 and 0.092 Ω·cm² at 800 ℃, respectively. The SCF−40SDC composite cathode displays the lowest ASR value among SCF−xSDC in the whole temperature range. Based on the 0.3 mm-thick La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-_δ (LSGM) electrolyte, the maximum power density of SOFC using SCF−40SDC (757 mW·cm⁻²) as a cathode is higher than that of pure SCF (684 mW·cm⁻²). These results demonstrate that the SCF−40SDC composite cathode is a promising candidate for application in IT-SOFCs.

Key words: solid oxide fuel cell, double perovskite, cathode, Sr₂CoFeO₅₊_δ, composite electrode, electrochemical performance

中图分类号:

陈正鹏, 金芳军, 李明飞, 董江波, 许仁辞, 徐韩昭, 熊凯, 饶睦敏, 陈创庭, 李晓伟, 凌意瀚. 双钙钛矿Sr₂CoFeO₅₊_δ阴极材料的制备及其中温固体氧化物燃料电池性能研究[J]. 无机材料学报, 2024, 39(3): 337-344.

CHEN Zhengpeng, JIN Fangjun, LI Mingfei, DONG Jiangbo, XU Renci, XU Hanzhao, XIONG Kai, RAO Muming, CHEN Chuangting, LI Xiaowei, LING Yihan. Double Perovskite Sr₂CoFeO₅₊_δ: Preparation and Performance as Cathode Material for Intermediate-temperature Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2024, 39(3): 337-344.

图/表 15

Fig. 1 XRD patterns of (a) Rietveld refined SCF and (b) mixture of SCF with different electrolyte materials

Fig. 2 O2-TPD curves of SCF and SCF−40SDC

Fig. 3 Core-level XPS spectra of SCF at room temperature (a) O1s; (b) Sr3d; (c) Co2p; (d) Fe2p

Fig. 4 (a) Thermal expansion behaviors and (b) thermal expansion coefficient curves of SCF-xSDC composite cathodes in the temperature range of 30-950 ℃ Colorful figures are available on website

Table 1 TEC of SCF-xSDC composite cathodes

Sample	Average TEC/(×10⁻⁶, K⁻¹)
SCF	17.4 (30−400 ℃)	28.8 (400−1000 ℃)
SCF−20SDC	15.6 (30−300 ℃)	26.3 (300−950 ℃)
SCF−30SDC	15.0 (30−300 ℃)	24.3 (300−950 ℃)
SCF−40SDC	14.5 (30−300 ℃)	19.8 (300−950 ℃)
SCF−50SDC	12.5 (30−300 ℃)	16.3 (300−950 ℃)

Fig. 5 (a) Temperature dependence of electrical conductivity and (b) Arrhenius plot of SCF

Fig. 6 Typical impedance spectra of SCF−xSDC composite cathodes

Fig. 7 (a) ASR and (b) Arrhenius plots of the polarization resistance for SCF-xSDC composite cathodes

Table S1 Atomic occupancy information (atomic parameters) of XRD refinement

Atom	Wyck.	S.O.F.	x/a	y/b	z/c	U/Å²
Sr1	8c	1	0.25	0.25	0.25	0.01083(1)
Co1	4b	1	0.5	0.5	0.5	0.01311(1)
Fe1	4a	1	0	0	0	0.0115(2)
O1	24e	1	0.2496(5)	0	0	0.00995(2)

Fig. S1 XRD patterns of SCF−LSGM mixtures calcined at 950 ℃ for 10 h

Fig. S2 XRD patterns of SCF−SDC mixtures calcined at 950 ℃ for 10 h

Fig. S3 XRD patterns of SCF−GDC mixtures calcined at 950 ℃ for 10 h

Fig. S4 SEM micrographs of (a) SCF cathode, (b) SCF−20SDC, (c) SCF−30SDC, (d) SCF−40SDC, and (e) SCF−50SDC composite cathodes

Table S2 Electrochemical performance for cathode materials using hydrogen fuels

Cathode	Electrolyte	T/℃	Power density/(mW·cm^-2)	Ref.
YBaCo_2/3Fe_2/3Cu_2/3O₅₊_δ	LSGM	800	543	[1]
SrCo_0.7Fe_0.2Ta_0.1O₃₋_δ	LSGM	800	652.9	[2]
PrBaCo_2/3Fe_2/3Cu_2/3O₅₊_δ	GDC	800	659	[3]
Pr_1.9Ca_0.1BaCoFeO₅₊_δ	LSGM	800	728	[4]
SCF−40SDC	LSGM	800	757	This work

参考文献 37

[1]	GUO T M, DONG J B, CHEN Z P, et al. Enhanced compatibility and activity of high-entropy double perovskite cathode material for IT-SOFC. Journal of Inorganic Materials, 2023, 38(6): 693. DOI
[2]	HAN X, LING Y H, YANG Y, et al. Utilizing high entropy effects for developing chromium-tolerance cobalt-free cathode for solid oxide fuel cells. Advanced Functional Materials, 2023, 33(43): 202304728.
[3]	TAI L W, NASRALLAH M M, ANDERSON H U, et al. Structure and electrical properties of La_1-_xSr_xCo_1-_yFe_yO₃. Part 1. The system La_0.8Sr_0.2Co_1-_yFe_yO₃. Solid State Ionics, 1995, 76(3/4): 259. DOI URL
[4]	TAI L W, NASRALLAH M M, ANDERSON H U, et al. Structure and electrical properties of La_1-_xSr_xCo_1-_yFe_yO₃. Part 2. The system La_1-_xSr_xCo_0.2Fe_0.8O₃. Solid State Ionics, 1995, 76(3/4): 273. DOI URL
[5]	SHAO Z, HAILE S M. A high-performance cathode for the next generation of solid-oxide fuel cells. Nature, 2004, 431(7005): 170. DOI
[6]	WEI B, LU Z, LI S Y, et al. Thermal and electrical properties of new cathode material Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ for solid oxide fuel cells. Electrochemical and Solid State Letters, 2005, 8(8): A428. DOI URL
[7]	ZHANG K, GE L, RAN R, et al. Synthesis, characterization and evaluation of cation-ordered LnBaCo₂O₅₊_δ as materials of oxygen permeation membranes and cathodes of SOFCs. Acta Materialia, 2008, 56(17): 4876. DOI URL
[8]	JIN F J, SHEN Y, WANG R, et al. Double-perovskite PrBaCo_2/3Fe_2/3Cu_2/3O₅₊_δ as cathode material for intermediate-temperature solid-oxide fuel cells. Journal of Power Sources, 2013, 234: 244. DOI URL
[9]	LI J, SUN N, LIU X, et al. Investigation on Nd_1-_xCa_xBaCo₂O₅₊_δ double perovskite as new oxygen electrode materials for reversible solid oxide cells. Journal of Alloys and Compounds, 2022, 913: 165245. DOI URL
[10]	JIN F, XU H, LONG W, et al. Characterization and evaluation of double perovskites LnBaCoFeO₅₊_δ (Ln=Pr and Nd) as intermediate- temperature solid oxide fuel cell cathodes. Journal of Power Sources, 2013, 243: 10. DOI URL
[11]	LIU X, JIN F, SUN N, et al. Nd³⁺-deficiency double perovskite Nd_1-_xBaCo₂O₅₊_s and performance optimization as cathode materials for intermediate-temperature solid oxide fuel cells. Ceramics International, 2021, 47(23): 33886. DOI URL
[12]	BEZDICKA P, FOURNES L, WATTIAUX A, et al. Mössbauer characteristics of the Sr₂CoFeO₆ perovskite obtained by electrochemical oxidation. Solid State Communications, 1994, 91(7): 501. DOI URL
[13]	MARTÍNEZ-LOPE MARÍA J, ALONSO JOSÉ A, CASAIS MARÍA T, et al. Preparation, crystal and magnetic structure of the double perovskites Ba₂CoBO₆ (B=Mo, W). European Journal of Inorganic Chemistry, 2002, 2002(9): 2463. DOI URL
[14]	YOSHII K. Magnetic transition in the perovskite Ba₂CoNbO_6-_δ. Journal of Solid State Chemistry, 2000, 151(2): 294. DOI URL
[15]	COX D E, SHIRANE G, FRAZER B C. Neutron-diffraction study of antiferromagnetic Ba₂CoWO₆ and Ba₂NiWO₆. Journal of Applied Physics, 1967, 38(3): 1459. DOI URL
[16]	RAMMEH N, EHRENBERG H, FUESS H, et al. Structure and magnetic properties of the double-perovskites Ba₂(B,Re)₂O₆ (B=Fe, Mn, Co and Ni). Physica Status Solidi (c), 2006, 3(9): 3225.
[17]	XIAO G L, LIU Q A, ZHAO F, et al. Sr₂Fe_1.5Mo_0.5O₆ as cathodes for intermediate-temperature solid oxide fuel cells with La_0.8Sr_0.2Ga_0.87Mg_0.13O₃ electrolyte. Journal of Electrochem Society, 2011, 158: B455. DOI URL
[18]	MENG J L, LIU X J, HAN L, et al. Improved electrochemical performance by doping cathode materials Sr₂Fe_1.5Mo_0.5-_xTa_xO_6-_δ (0≤x≤0.15) for solid state fuel cell. Journal of Power Sources, 2014, 247: 845. DOI URL
[19]	DENG Z Q, SMIT J P, NIU H J, et al. B cation ordered double perovskite Ba₂CoMo_0.5Nb_0.5O_6-_δ as a potential SOFC cathode. Chemistry of Materials, 2009, 21(21): 5154. DOI URL
[20]	PRADHEESH R, NAIR H S, KUMAR C M N, et al. Observation of spin glass state in weakly ferromagnetic Sr₂FeCoO₆ double perovskite. Journal of Applied Physics, 2012, 111(5): 053905. DOI URL
[21]	PRADHEESH R, NAIR HS, SANKARANARAYANAN V, et al. Large magnetoresistance and Jahn-Teller effect in Sr₂FeCoO₆. The European Physical Journal B, 2012, 85: 260. DOI URL
[22]	PRADHEESH R, NAIR HS, SANKARANARAYANAN V, et al. Exchange bias and memory effect in double perovskite Sr₂FeCoO₆. Applied Physics Letters, 2012, 101(14): 142401. DOI URL
[23]	CONG LG, HE TM, JI YA, et al. Synthesis and characterization of IT-electrolyte with perovskite structure La_0.8Sr_0.2Ga_0.85Mg_0.15O_3-_δ by glycine-nitrate combustion method. Journal of Alloys and Compounds. 2003, 348(1/2): 325. DOI URL
[24]	WANG Y, JIN F, HAO X, et al. B-site-ordered Co-based double perovskites Sr₂Co_1-_xNb_xFeO₅₊_δ as active and stable cathodes for intermediate-temperature solid oxide fuel cells. Journal of Alloys and Compounds, 2020, 829: 154470. DOI URL
[25]	WU H, QIAN Y, TAN W, et al. The theoretical search for half- metallic material: the non-stoichiometric perovskite oxide Sr₂FeCoO_6-_δ. Applied Physics Letters, 2011, 99(12): 123116. DOI URL
[26]	SHAO Z, XIONG G, TONG J, et al. Ba effect in doped Sr(Co_0.8Fe_0.2)O_3-_δ on the phase structure and oxygen permeation properties of the dense ceramic membranes. Separation and Purification Technology, 2001, 25(1/2/3): 419. DOI URL
[27]	SHAO Z, YANG W, CONG Y, et al. Investigation of the permeation behavior and stability of a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-_δ oxygen membrane. Journal of Membrane Science, 2000, 172(1/2): 177. DOI URL
[28]	LIU X, JIN F, LIU X, et al. Effect of calcium doping on Sm_1-_xCa_xBaCo₂O₅₊_δ cathode materials for intermediate-temperature solid oxide fuel cells. Electrochim Acta, 2021, 390: 138830. DOI URL
[29]	LING Y H, GUO T M, GUO Y Y, et al. New two-layer Ruddlesden-Popper cathode materials for protonic ceramics fuel cells. Journal of Advanced Ceramics, 2021, 10: 1052. DOI
[30]	JIN F, LIU J, NIU B, et al. Evaluation and performance optimization of double-perovskite LaSrCoTiO₅₊_δ cathode for intermediate-temperature solid-oxide fuel cells. International Journal of Hydrogen Energy, 2016, 41(46): 21439. DOI URL
[31]	GHAFFARI M, SHANNON M, HUI H, et al. Preparation, surface state and band structure studies of SrTi_(1-_x₎Fe₍_x₎O_(3-_δ₎ (x=0-1) perovskite-type nano structure by X-ray and ultraviolet photoelectron spectroscopy. Surface Science, 2012, 606(5/6): 670. DOI URL
[32]	PIKALOVA EY, MARAGOU VI, DEMINA AN, et al. The effect of co-dopant addition on the properties of Ln_0.2Ce_0.8O_2-_δ (Ln=Gd, Sm, La) solid-state electrolyte. Journal of Power Sources, 2008, 181(2): 199 DOI URL
[33]	JIN F, LIU J, SHEN Y, et al. Improved electrochemical performance and thermal expansion compatibility of LnBaCoFeO₅₊_δ- Sm_0.2Ce_0.8O_1.9 (LnPr and Nd) composite cathodes for IT-SOFCs. Journal of Alloys and Compounds, 2016, 685: 483. DOI URL
[34]	LIU B, SUNARSO J, ZHANG Y, et al. Highly oxygen non- stoichiometric BaSc_0.25Co_0.75O_3-_δ as a high-performance cathode for intermediate-temperature solid oxide fuel cells. ChemElectroChem, 2018, 5(5): 785. DOI URL
[35]	BU Y F, DING D, LAI S Y, et al. Evaluation of La_0.4Ba_0.6Fe_0.8Zn_0.2O_3-_δ+Sm_0.2Ce_0.8O_1.9 as a potential cobalt-free composite cathode for intermediate temperature solid oxide fuel cells. Journal of Power Sources, 2015, 275: 808. DOI URL
[36]	LI S L, ZHANG L K, XIA T, et al. Synergistic effect study of EuBa_0.98Co₂O₅₊_δ-Ce_0.8Sm_0.2O_1.9 composite cathodes for intermediate- temperature solid oxide fuel cells. Journal of Alloys and Compounds, 2019, 771: 513. DOI URL
[37]	STEELE BCH. Survey of materials selection for ceramic fuel cells II. cathodes and anodes. Solid State Ionics, 1996, 86: 1223.

双钙钛矿Sr₂CoFeO₅₊_δ阴极材料的制备及其中温固体氧化物燃料电池性能研究

Double Perovskite Sr₂CoFeO₅₊_δ: Preparation and Performance as Cathode Material for Intermediate-temperature Solid Oxide Fuel Cells

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	潘建隆, 马官军, 宋乐美, 郇宇, 魏涛. 燃料还原法原位制备高稳定性/催化活性SOFC钴基钙钛矿阳极[J]. 无机材料学报, 2024, 39(8): 911-919.
[2]	叶梓滨, 邹高昌, 吴琪雯, 颜晓敏, 周明扬, 刘江. 阳极支撑型锥管串接式直接碳固体氧化物燃料电池组的制备及性能[J]. 无机材料学报, 2024, 39(7): 819-827.
[3]	张琨, 王宇, 朱腾龙, 孙凯华, 韩敏芳, 钟秦. LaNi_0.6Fe_0.4O₃阴极接触材料导电特性调控及其对SOFC电化学性能的影响[J]. 无机材料学报, 2024, 39(4): 367-373.
[4]	薛顶喜, 伊炳尧, 李国君, 马帅, 刘克勤. 功能梯度阳极固体氧化物燃料电池热应力数值模拟研究[J]. 无机材料学报, 2024, 39(11): 1189-1196.
[5]	王马超, 唐扬敏, 邓明雪, 周真真, 刘小峰, 王家成, 刘茜. 共沉淀法制备Cs₂Ag_0.1Na_0.9BiCl₆:Tm³⁺双钙钛矿及其近红外发光性能[J]. 无机材料学报, 2023, 38(9): 1083-1088.
[6]	张伦, 吕梅, 朱俊. Cs₂AgBiBr₆钙钛矿太阳能电池研究进展[J]. 无机材料学报, 2023, 38(9): 1044-1054.
[7]	郭天民, 董江波, 陈正鹏, 饶睦敏, 李明飞, 李田, 凌意瀚. 中温固体氧化物燃料电池的高熵双钙钛矿阴极材料: 兼容性与活性研究[J]. 无机材料学报, 2023, 38(6): 693-700.
[8]	杨颖康, 邵怡晴, 李柏良, 吕志伟, 王路路, 王亮君, 曹逊, 吴宇宁, 黄荣, 杨长. Cl掺杂对CuI薄膜发光性能增强研究[J]. 无机材料学报, 2023, 38(6): 687-692.
[9]	樊帅, 金天, 张山林, 雒晓涛, 李成新, 李长久. Li₂O烧结助剂对固体氧化物燃料电池LSGM电解质烧结特性及离子电导率的影响[J]. 无机材料学报, 2022, 37(10): 1087-1092.
[10]	刘芳芳, 传秀云, 杨扬, 李爱军. 氮/硫共掺杂对纤水镁石模板碳纳米管电化学性能的影响[J]. 无机材料学报, 2021, 36(7): 711-717.
[11]	张亚萍,雷宇轩,丁文明,于濂清,朱帅霏. 双铁电复合材料的制备及其光电化学性能研究[J]. 无机材料学报, 2020, 35(9): 987-992.
[12]	曹丹,周明扬,刘志军,颜晓敏,刘江. 阳极支撑质子导体电解质固体氧化物燃料电池的制备及其性能研究[J]. 无机材料学报, 2020, 35(9): 1047-1052.
[13]	湛菁,徐昌藩,龙怡宇,李启厚. 聚丙烯酰胺凝胶法制备Bi₂Mn₄O₁₀及其电化学性能[J]. 无机材料学报, 2020, 35(7): 827-833.
[14]	夏天, 孟燮, 骆婷, 占忠亮. 固体氧化物燃料电池La_xSr_2-3_x_/2Fe_1.5Ni_0.1Mo_0.4O_6-_δ阳极性能研究[J]. 无机材料学报, 2020, 35(5): 617-622.
[15]	郑坤, 罗永春, 邓安强, 杨洋, 张海民. A₂B₇型La_0.3Y_0.7Ni_3.4-_xMn_xAl_0.1储氢合金微观结构和电化学性能研究[J]. 无机材料学报, 2020, 35(5): 549-555.