质子传导型固体氧化物燃料电池BaZr0.1Ce0.7Y0.1Yb0.1O3电解质的氟化研究

doi:10.15541/jim20240535

无机材料学报 ›› 2025, Vol. 40 ›› Issue (12): 1356-1364.DOI: 10.15541/jim20240535

• 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

质子传导型固体氧化物燃料电池BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃电解质的氟化研究

姜玥宏(), 宋云峰(), 张磊磊(), 马季, 宋昭远, 龙文

辽宁石油化工大学理学院, 抚顺 113001

收稿日期:2024-12-24 修回日期:2025-03-18 出版日期:2025-12-20 网络出版日期:2025-04-09
通讯作者: 宋云峰, 实验师. E-mail: yunfs@lnpu.edu.cn;
张磊磊, 教授. E-mail: petuzll@163.com
作者简介:姜玥宏(1994-), 女, 硕士研究生. E-mail: jyh_940315@163.com
基金资助:
国家自然科学基金(62105132);辽宁省教育厅基本科研项目(LJ212410148055);辽宁省教育厅基本科研项目(LJ212410148058)

Fluorination of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell

JIANG Yuehong(), SONG Yunfeng(), ZHANG Leilei(), MA Ji, SONG Zhaoyuan, LONG Wen

College of Science, Liaoning Petrochemical University, Fushun 113001, China

Received:2024-12-24 Revised:2025-03-18 Published:2025-12-20 Online:2025-04-09
Contact: SONG Yunfeng, lecturer. E-mail: yunfs@lnpu.edu.cn;
ZHANG Leilei, professor. E-mail: petuzll@163.com
About author:JIANG Yuehong (1994-), female, Master candidate. E-mail: jyh_940315@163.com
Supported by:
National Natural Science Foundation of China(62105132);Scientific Research Fund Project of Education Department of Liaoning Province(LJ212410148055);Scientific Research Fund Project of Education Department of Liaoning Province(LJ212410148058)

摘要/Abstract

摘要：

质子传导型固体氧化物燃料电池(H⁺-SOFC)因温度依赖性弱和能量转换效率高而备受关注。本工作通过氟化诱导提高了电解质BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃(BZCYYb)的质子传导性。在450~800 ℃温区, 氟化后的BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_2.9F_0.1 (BZCYYbF)钙钛矿在干氢气中的电导率(σ)为4.59×10^-3~2.14×10^-2 S/cm, 高于未氟化BZCYYb电解质的电导率(σ=3.99×10^-3~1.86×10^-2 S/cm)。电解质氟化可以明显降低阳极对氢氧化反应的极化阻抗, 700 ℃条件下从氟化前的2.50 Ω·cm²降低到1.94 Ω·cm², 300 μm厚电解质支撑单电池(BSCN|电解质|LSFMN)的总阻抗从氟化前的1.54 Ω·cm²降低到氟化后的1.47 Ω·cm²。因此, 电解质氟化的单电池输出功率明显高于电解质未氟化的单电池。700 ℃时, 氟化电解质支撑单电池的最大输出功率密度P_max为172 mW·cm^-2, 明显高于未氟化电解质支撑单电池(P_max=144 mW·cm^-2)。追本溯源, 这是由于电解质氟化不但提高了电解质质子传导能力, 而且强化了阳极侧三相界面对氢燃料的吸附/解离和扩散速率。综上, 氟化能明显改善BZCYYb电解质的质子传导能力, 有助于提升H⁺-SOFC的电化学性能。

关键词: 质子传导型固体氧化物燃料电池, 质子导电电解质, 氟化, 导电性, 电化学性能

Abstract:

Proton-conducting solid oxide fuel cells (H⁺-SOFC) have gained great attention due to weak temperature dependence and high energy conversion efficiency. However, how to improve their proton conductivity still remains an open problem. In this work, a fluorination strategy based on the BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ (BZCYYb) electrolyte was proposed to improve the proton conductivity. It is found that the conductivity (σ) of the fluorinated BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_2.9F_0.1 (BZCYYbF) is 4.59×10^-3-2.14×10^-2 S/cm at 450-800 ℃ in dry H₂, higher than that of the primitive BZCYYb electrolyte (σ=3.99×10^-3-1.86×10^-2 S/cm). The electrolyte fluorination significantly reduces anode polarization resistance for hydrogen oxidation reaction from 2.50 Ω·cm² to 1.94 Ω·cm², and total resistance of the single cell with 300-μm-thick electrolyte supporting from 1.54 Ω·cm² to 1.47 Ω·cm². Therefore, the BZCYYbF single cell shows much higher maximum power density (172 mW·cm^-2) than the BZCYYb single cell (144 mW·cm^-2) at 700 ℃. This result is attributed to the fact that the electrolyte fluorination not only improves the proton conduction capacity but also enhances the rates of H₂ diffusion and adsorption/dissociation on the anode sides. In conclusion, the fluorination of BZCYYb electrolyte can significantly improve its proton conductivity and thereby contribute to superior electrochemical performance of H⁺-SOFC.

Key words: proton-conducting solid oxide fuel cell, proton conducting electrolyte, fluorination, conductivity, electrochemical performance

中图分类号:

TQ15

姜玥宏, 宋云峰, 张磊磊, 马季, 宋昭远, 龙文. 质子传导型固体氧化物燃料电池BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃电解质的氟化研究[J]. 无机材料学报, 2025, 40(12): 1356-1364.

JIANG Yuehong, SONG Yunfeng, ZHANG Leilei, MA Ji, SONG Zhaoyuan, LONG Wen. Fluorination of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell[J]. Journal of Inorganic Materials, 2025, 40(12): 1356-1364.

图/表 12

图1 BZCYYb和BZCYYbF样品的XRD图谱及其Rietveld精修图谱

Fig. 1 XRD patterns and Rietveld refinements for BZCYYb and BZCYYbF samples (a) XRD patterns; Rietveld refinements for (b) BZCYYb and (c) BZCYYbF. Colorful figures are available on website

图2 BZCYYb和BZCYYbF在空气中的(a)热膨胀曲线以及(b)一阶微分曲线

Fig. 2 (a) Thermal expansion and (b) first order differential curves of BZCYYb and BZCYYbF in air

图3 (a) BZCYYb和(b) BZCYYbF电解质的Ce3d XPS谱图

Fig. 3 Ce3d XPS spectra for (a) BZCYYb and (b) BZCYYbF electrolytes

图4 (a)空气中BZCYYb和BZCYYbF的电导率; (b) BZCYYb和(c) BZCYYbF的表面SEM照片; (d)干氢气中BZCYYb和BZCYYbF的电导率

Fig. 4 (a) Electrical conductivities of BZCYYb and BZCYYbF in air; (b, c) Surface SEM images of (b) BZCYYb and (c) BZCYYbF; (d) Electrical conductivities of BZCYYb and BZCYYbF in dry H2

图5 BZCYYb和BZCYYbF对称电池在(a, b, e, f) 600和(c, d, g, h) 700 ℃, (a~d)空气和(e~h)湿氢气下的(a, c, e, g) EIS谱图以及(b, d, f, h) DRT曲线

Fig. 5 (a, c, e, g) EIS spectra and (b, d, f, h) DRT curves for BZCYYb and BZCYYbF symmetric cells in (a-d) air and (e-h) wet H2 at (a, b, e, f) 600 and (c, d, g, h) 700 ℃

图6 电解质支撑单电池在700 ℃的(a) I-V/I-P曲线以及(b) EIS谱图

Fig. 6 (a) I-V/I-P curves and (b) EIS spectra for electrolyte-supported single cells at 700 ℃

图7 单电池在0.55 V恒电位下电流密度随时间的变化曲线

Fig. 7 Time dependent current densities for single cells under a constant potential of 0.55 V

图8 (a)阳极支撑单电池在600 ℃的I-V/I-P曲线以及(b)以BZCYYbF作电解质的阳极支撑电池稳定性测试后的断面SEM照片

Fig. 8 (a) I-V/I-P curves for anode-supported single cell at 600 ℃ and (b) cross-sectional SEM image for anode-supported single cell with BZCYYbF electrolyte after cell stability test

表S1 基于Pbnm空间群的BZCYYb和BZCYYbF样品的Rietveld精修结果

Table S1 Rietveld refinement results for BZCYYb and BZCYYbF samples based on space group Pbnm

Sample	BZCYYb		BZCYYbF
Sample	Refined	Sigmas	Refined	Sigmas
a/Å	6.2146	0.000851	6.210605	0.000363
b/Å	6.2443	0.000511	6.197102	0.000486
c/Å	8.7578	0.00058	8.701261	0.00077
α/(°)	90	-	90	-
β/(°)	90	-	90	-
γ/(°)	90	-	90	-
V/Å³	339.858	0.054	334.892	0.04
χ²	1.711	-	2.346	-
R_wp/%	14.83	-	14.07	-
R_p/%	9.99	-	11.54	-

图S1 BZCYYbF电解质的F1s XPS谱图

Fig. S1 F1s XPS spectra for BZCYYbF electrolyte

图S2 (a, b)不同模式测得的(a) BZCYYb和(b) BZCYYbF在空气下的电导率曲线; (c)三种电导率测试模式的示意图; (d, e)按不同测试模式所测得(d) BZCYYb和(e) BZCYYbF的电导率柱状图; (f) BZCYYb与BZCYYbF的电导率柱状对比图

Fig. S2 (a, b) Electrical conductivity curves for (a) BZCYYb and (b) BZCYYbF in air measured by different models; (c) Schematic diagram for three different conductivity testing models; (d, e) Histograms of conductivities for (d) BZCYYb and (e) BZCYYbF measured by different models; (f) Comparison of conductivities for BZCYYb and BZCYYbF

图S3 (a) BZCYYb和(b) BZCYYbF在H2中的电导率曲线; (c)两种电导率测试模式的示意图; (d)按不同测试模式所测得BZCYYbF的电导率柱状图; (e) BZCYYb与BZCYYbF的电导率柱状对比图

Fig. S3 (a, b) Electrical conductivity curves for (a) BZCYYb and (b) BZCYYbF in H2 measured by different models; (c) Schematic diagram for two different conductivity testing models; (d) Histogram for BZCYYbF measured by different models; (e) Comparison of conductivities of BZCYYb and BZCYYbF

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质子传导型固体氧化物燃料电池BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃电解质的氟化研究

Fluorination of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O₃ as Electrolyte Material for Proton-conducting Solid Oxide Fuel Cell

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