中温固体氧化物燃料电池Nd2NiO4+δ-Ce0.8Gd0.2O2-δ复合阴极性能研究

doi:10.15541/jim20160444

摘要/Abstract

摘要：

研究了Nd₂NiO₄₊_δ (NNO)-Ce_0.8Gd_0.2O_2-_δ (CGO)复合化合物在中温固体氧化物燃料电池的性能, 包括NNO-CGO复合阴极的烧结温度以及复合比例。采用流延法、丝网印刷法和高温烧结法相结合制备了尺寸为50 mm × 50 mm的平板式NiO-YSZ阳极支撑SOFC。单电池是由NiO-YSZ阳极支撑层、NiO-YSZ阳极功能层、YSZ电解质层, CGO阻挡层, NNO-CGO复合阴极层以及La_0.6Sr_0.4CoO_3-_δ (LSC)集流层共同组成。研究结果表明, 当70NNO-30CGO复合阴极烧结温度为1000℃, 单电池在800℃展现出最大功率密度385 mW/cm² (0.7 V), 欧姆阻抗、极化阻抗和面积比电阻分别为0.31、0.266和0.576 Ω·cm²。电化学阻抗分析结果表明, 电荷转移阻抗是电池极化阻抗的主要来源。测试后电池截面的SEM观察结果显示电池各层之间均展现出良好的烧结结合。同时, 与前期研究结果比较可以发现, 具有相同复合阴极层的电池增加CGO阻挡层后功率密度下降, 欧姆阻抗增加, 但极化阻抗却降低。

关键词: 中温固体氧化物燃料电池, 复合阴极, Nd₂NiO₄₊δ, 电化学性能

Abstract:

Nd₂NiO_4+δ (NNO)-Ce_0.8Gd_0.2O_2-δ (CGO) composites were further investigated as cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs). The effects of sintering temperature and the relative proportions of NNO and CGO on the cell performances were systematically investigated. Planar NiO-YSZ anode-supported cells in commercial size of 50 mm×50 mm were fabricated by tape casting, screen printing and co-sintering methods. A single cell consisted of a NiO-YSZ anode support, a NiO-YSZ anode interlayer, a YSZ electrolyte layer, a CGO interlayer, a NNO-CGO composite cathode layer, and a La_0.6Sr_0.4CoO_3-_δ (LSC) current collector from anode to cathode. The results show that the cell with 70NNO-30CGO composite cathode sintered at 1000℃ exhibits the highest power density of 385 mW/cm² at 0.7 V at 800℃. The ohmic resistance, polarization resistance and area specific resistance are 0.31, 0.266 and 0.576 Ω·cm², respectively. The analysis of electrochemical impedance spectra indicates that the polarization resistance mainly comes from charge transfer resistance. SEM image of the cross-section of the cell after testing reveals that each layer has a good adhesion. Meanwhile, compared with previous research, it can be concluded that adding a CGO interlayer in the single cells leads to an increase in the ohmic resistances and a decrease in the power densities, whereas the values of the polarization resistances decrease.

Key words: IT-SOFC, composite cathode, Nd₂NiO4₊δ, electrochemical performances

中图分类号:

TQ174

李斯琳, 屠恒勇, 于立军. 中温固体氧化物燃料电池Nd₂NiO₄₊_δ-Ce_0.8Gd_0.2O_2-_δ复合阴极性能研究[J]. 无机材料学报, 2017, 32(5): 469-475.

LI Si-Lin, TU Heng-Yong, YU Li-Jun. Performance of Nd₂NiO₄₊_δ-Ce_0.8Gd_0.2O_2-_δ Composite Cathodes for Intermediate Temperature Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2017, 32(5): 469-475.

图/表 7

表1 不同烧结温度和复合阴极比例的电池

Table 1 Cells with various composite cathodes sintered at different temperatures

Cell No.	1	2	3	4	5	6	7	8
Composite cathode	70NNO- 30CGO	70NNO- 30CGO	70NNO- 30CGO	50NNO- 50CGO	60NNO- 40CGO	80NNO- 20CGO	90NNO- 10CGO	NNO
T /℃	1000	1050	950	1000	1000	1000	1000	1000

图1 NNO前驱体的TGA-DSC曲线图

Fig. 1 TGA-DSC curves of the NNO precursor powder

图2 电池1, 2, 3的 (a)性能曲线和(b)交流阻抗谱图以及对应的等效电路图

Fig. 2 (a) Voltage and power density curves as a function of current density, and (b) electrochemical impedance spectra and fit results with the corresponding equivalent circuit Cell 1 (2, 3) were performed at 800℃ with 70NNO-30CGO composite cathode sintered at various temperatures

表2 不同电池的EIS等效电路(图3(b))拟合值

Table 2 EIS fitted values of the different cells associated to the equivalent circuit reported in Fig.3(b)

Cell No.	1	2	3	4	5	6	7	8	1	1
T /℃	800								750	700
L × 10^-7/ (Wb·A^-1)	7.7	7.8	7.6	7.1	7.3	7.6	7.7	7.7	7.7	7.7
R_s/ (Ω·cm²)	0.31	0.59	0.6	0.27	0.42	0.27	0.32	0.92	0.5	0.77
R₁/ (Ω·cm²)	0.15	0.23	0.25	0.31	0.25	0.25	0.28	0.28	0.30	0.50
R₂/ (Ω·cm²)	0.14	0.11	0.12	0.35	0.13	0.11	0.1	0.1	0.12	0.27
R_p/ (Ω·cm²)	0.29	0.34	0.37	0.66	0.38	0.36	0.38	0.38	0.42	0.77
ASR / (Ω·cm²)	0.6	0.93	0.97	0.93	0.80	0.63	0.70	1.30	0.92	1.51

图3 电池Cell 1, 4, 5, 6, 7, 8的(a)性能曲线和(b)交流阻抗图谱

Fig. 3 (a) Voltage and power density curves as a function of current density, and (b) electrochemical impedance spectra and fit results with the corresponding equivalent circuit Cell 1 (4, 5, 6, 7, 8) performed at 800℃ with various composite cathode sintered at 1000℃

图4 电池Cell 1在不同工作温度下的(a)性能曲线和(b)交流阻抗谱图

Fig. 4 (a) Voltage and power density curves as a function of current density, and (b) electrochemical impedance spectra and fit results with the corresponding equivalent circuit Cell 1 at different operating temperatures. Cell 1 has 70NNO-30CGO composite cathode sintered at 1000℃

图5 性能测试后单电池断面SEM照片

Fig. 5 SEM image of the cross-section of the single cell after testing

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中温固体氧化物燃料电池Nd₂NiO₄₊_δ-Ce_0.8Gd_0.2O_2-_δ复合阴极性能研究

Performance of Nd₂NiO₄₊_δ-Ce_0.8Gd_0.2O_2-_δ Composite Cathodes for Intermediate Temperature Solid Oxide Fuel Cells

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