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(202512)

• 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

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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

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