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

doi:10.15541/jim20190576

摘要/Abstract

摘要：

本研究采用高温固相反应法合成了BaCe_0.7Zr_0.1Y_0.2O_3-_d (BCZY7)质子导体氧化物, 对材料的物相结构和微观形貌进行表征和分析, 并将BCZY7作为固体氧化物燃料电池(SOFC)的电解质, 通过浸渍法和共烧结法成功制备了阳极支撑的NiO-BCZY7/BCZY7/La_0.6Sr_0.4Co_0.2Fe_0.8O_3-_δ(LSCF)-BCZY7钮扣式电池。以氢气(含3vol% H₂O)为燃料, 空气为氧化剂, 对电池的电化学性能进行测试。结果表明, 在600、550、500 ℃时, 电池的最高功率密度分别为203, 123, 92 mW×cm^-2, 而传统(ZrO₂)_0.92(Y₂O₃)_0.08基SOFC在600 ℃时通常只有几十毫瓦的单位面积输出, 质子导体电解质可以极大改善SOFC的中低温性能, 缓解SOFC工作温度高的问题。

关键词: 质子导体, 固体氧化物燃料电池, 中低温固体电解质, 活化能

Abstract:

Proton conducting oxide BaCe_0.7Zr_0.1Y_0.2O_3-_d (BCZY7) was synthesized by high temperature solid-state reaction method, which crystal structure and microstructure morphology were characterized. The anode-supported button solid oxide fuel cell (SOFC), NiO-BCZY7/BCZY7/La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(LSCF)-BCZY7, was fabricated by combining the dip-coating and co-sintering processes. It operated by using H₂ (containing 3vol% H₂O) as fuel and ambient air as oxidant. The maximum power density of the cell reaches 203, 123 and 92 mW×cm^-2 at 600, 550 and 500 ℃, respectively. However, traditional SOFCs based on (ZrO₂)_0.92(Y₂O₃)_0.08 electrolyte usually display only tens of milliwatts output per unit area at 600 ℃. Proton conducting electrolyte greatly improves the low and medium temperature performance of SOFCs and provides a promising solution to reduce SOFCs’ operating temperature.

Key words: proton conductor, solid oxide fuel cell, reduced temperature electrolyte, activation energy

中图分类号:

TM911

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.

CAO Dan,ZHOU Mingyang,LIU Zhijun,YAN Xiaomin,LIU Jiang. Fabrication and Characterization of Anode-supported Solid Oxide Fuel Cell Based on Proton Conductor Electrolyte[J]. Journal of Inorganic Materials, 2020, 35(9): 1047-1052.

图/表 7

表1 0.5NiO-BCZY7电解质浆料成分

Table 1 Composition of 0.5NiO-BCZY7 electrolyte slurry

Component	BCZY7	NiO	DOP	PEG-600	TEA	Ethanol
Weight/g	5	0.025	0.30	0.30	0.36	15

图1 NiO-BCZY7/BCZY7/LSCF-BCZY7电池的实物照片

Fig. 1 Photograph of cell NiO-BCZY7/BCZY7/LSCF-BCZY7

图2 高温固相反应法合成的BCZY7粉体的(a) SEM微观形貌和(b) XRD图谱

Fig. 2 (a)SEM morphology and (b)XRD pattern of BZCY7 powder synthesized by high temperature solid-state reaction method

图3 NiO-BCZY7/BCZY7/LSCF-BCZY7单电池在不同温度下的(a)输出性能, (b)实际开路电压与理论开路电压的对比

Fig. 3 (a) Output performance and (b) comparision between theoretical and practical OCV of NiO-BCZY7/BCZY7/LSCF- BCZY7 single cell operated at different temperatures

图4 单电池(a)在不同温度、开路下的电池交流阻抗图谱, (b)欧姆电阻和极化电阻随温度的变化曲线, (c) 0.5NiO-BCZY7的Arrhenius曲线

Fig. 4 (a) Impedance plots of single cell under OCV at different temperature, (b) variation of Ohmic resistance and polarization resistance as the function of temperature, and (c) Arrhenius plot for 0.5NiO-BCZY7

图5 (a)测试后电池截面, 以及(b)测试前和(c)测试后阳极截面的SEM微观形貌

Fig. 5 Cross-sectional SEM images of (a) the tested cell, the anodes (b) before and (c) after testing

图6 测试后电池阳极表面析出颗粒的SEM照片和EDX元素分布图

Fig. 6 SEM image and EDX mappings of the particle observed in the anode surface of tested cell

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