NH4HCO3用量对Ni/La10Si5.8Mg0.2O26.8阳极微观结构的影响

doi:10.15541/jim20140021

摘要/Abstract

摘要：

磷灰石型硅酸镧是新型的氧离子导体。本研究采用柠檬酸-硝酸盐溶胶-凝胶法制备磷灰石型硅酸镧(La₁₀Si_5.8Mg_0.2O_26.8)纳米粉末, 将其与NiO纳米粉末按4:6的质量比、并添加不同量的NH₄HCO₃造孔剂进行混合, 通过在1400℃温度下烧结及在600℃氢气中还原制备Ni/La₁₀Si_5.8Mg_0.2O_26.8多孔复合阳极。采用XRD和SEM对样品进行了物相和表面微观形貌表征。采用阿基米德排水法和交流阻抗谱测定了样品的孔隙率和阳极片的室温电阻。实验结果表明, 多孔复合阳极片不含微观裂纹, 未还原陶瓷样品的平均热膨胀系数为10.7×10^-6K^-1。随着NH₄HCO₃造孔剂加入量的增加, Ni、磷灰石型硅酸镧的晶粒尺寸及气孔尺寸减小, 孔隙率增加, 孔隙率为30%~45%; 阳极电阻先降低后增加。综合考虑阳极片的物相、表面微观形貌、孔隙率和电阻, 以加入30wt% NH₄HCO₃造孔剂所制得的阳极片最佳。

关键词: 溶胶-凝胶, 磷灰石型硅酸镧, 阳极, 孔隙率, 固体氧化物燃料电池

Abstract:

Apatite-type lanthanum silicates are a new type of oxide-ion conductors. In the present research, nanosized apatite-type lanthanum silicate (La₁₀Si_5.8Mg_0.2O_26.8) powder was prepared through Sol-Gel method by using citric acid and nitrates. The nanosized lanthanum silicate powder was mixed with nanosized NiO powder according to weight ratio of 4:6, and with different amounts of NH₄HCO₃as pore-forming agent. Porous composite anodes of Ni/La₁₀Si_5.8Mg_0.2O_26.8 were fabricated through sintering at 1400℃ and then reduced in H₂ atmosphere at 600℃. Phases, surface morphology and porosity of the samples were characterized by XRD, FE-SEM and Archimedes method, respectively. Resistance of the anodes at room temperature was determined by ac impedance spectroscopy. The results show that the prepared Ni/ La₁₀Si_5.8Mg_0.2O_26.8 porous composite anodes are micro-crack free and the mean thermal expansion coefficient before reduction is 10.7×10^-6 K^-1. With increasing amount of pore-forming agent NH₄HCO₃, sizes of Ni grains, apatite-type silicate grains and pores decrease, but the porosity increases within the range of 30%-45%. The resistance of the anodes decreases at first and then increases as the amount of NH₄HCO₃ increases. Considering all these characteristics, including phases, surface morphology, porosity and resistance, the anode made with the pore-forming agent NH₄HCO₃ at ratio of 30wt% is the best.

Key words: Sol-Gel, apatite-type lanthanum silicate, anode, porosity, SOFCs

中图分类号:

TQ174

项礼, 丁小芳. NH₄HCO₃用量对Ni/La₁₀Si_5.8Mg_0.2O_26.8阳极微观结构的影响[J]. 无机材料学报, 2014, 29(9): 924-930.

XIANG Li, DING Xiao-Fang. Influence of NH₄HCO₃ on Microstructure of Ni/La₁₀Si_5.8Mg_0.2O_26.8 Anode[J]. Journal of Inorganic Materials, 2014, 29(9): 924-930.

图/表 11

表1 阳极片配料质量比

Table 1 Weight ratio of start materials for anode samples

Sample	Start materials	Weight ratio
0	La₁₀Si_5.8Mg_0.2O_26.8:NiO:NH₄HCO₃	4:6:0
1	La₁₀Si_5.8Mg_0.2O_26.8:NiO:NH₄HCO₃	4:6:1
2	La₁₀Si_5.8Mg_0.2O_26.8:NiO:NH₄HCO₃	4:6:2
3	La₁₀Si_5.8Mg_0.2O_26.8:NiO:NH₄HCO₃	4:6:3
4	La₁₀Si_5.8Mg_0.2O_26.8:NiO:NH₄HCO₃	4:6:4

图1 原始粉末的XRD图谱

Fig. 1 XRD patterns of start powders

图2 La10Si5.8Mg0.2O26.8粉末的透射电镜照片

Fig. 2 TEM image of La10Si5.8Mg0.2O26.8 powder

图3 60% NiO/La10Si5.8Mg0.2O26.8陶瓷片(不含NH4HCO3)表面微观形貌FE-SEM照片

Fig. 3 FE-SEM surface micrographs of 60% NiO/La10Si5.8 Mg0.2O26.8 ceramic without NH4HCO3 (a) SEM image; (b) BE image

图4 60% NiO/La10Si5.8Mg0.2O26.8陶瓷片(不含NH4HCO3)的热膨胀曲线

Fig. 4 Thermal expansion coefficient curve of 60% NiO/La10Si5.8Mg0.2O26.8 ceramic without NH4HCO3 Insert is the thermal expansion curve

图5 加入不同量NH4HCO3所制未还原样品的XRD图谱

Fig. 5 XRD patterns of samples with different amounts of NH4HCO3 before reduction (a) 10wt% NH4HCO3; (b) 20wt% NH4HCO3; (c) 30wt% NH4HCO3; (d) 40wt% NH4HCO3

图6 加入不同量NH4HCO3所制样品在还原状态下的XRD图谱

Fig. 6 XRD patterns of samples with different amounts of NH4HCO3 after reduction (a) 10wt% NH4HCO3; (b) 20wt% NH4HCO3; (c) 30wt% NH4HCO3; (d) 40wt% NH4HCO3

图7 加入不同量NH4HCO3所制未还原样品的表面微观FE-SEM照片

Fig. 7 FE-SEM surface micrographs of samples with different amount of NH4HCO3 before reduction (a) 10wt% NH4HCO3; (b) 20wt% NH4HCO3; (c) 30wt% NH4HCO3; (d) 40wt% NH4HCO3

图8 加入不同量NH4HCO3所制已还原样品的表面微观FE-SEM照片

Fig. 8 FE-SEM surface micrographs of samples with different amount of NH4HCO3 after reduction (a) 10wt% NH4HCO3; (b) 20wt% NH4HCO3; (c) 30wt% NH4HCO3; (d) 40wt% NH4HCO3

图9 NH4HCO3用量与孔隙率的关系图

Fig. 9 Relationship between porosity and amount of NH4HCO3

Table 2 Resistance of anodes with different amount of NH4HCO3

Amount of NH₄HCO₃	10wt%	20wt%	30wt%	40wt%
Resistance/Ω	2.38	2.17	1.78	1.4×10⁷

参考文献 25

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NH₄HCO₃用量对Ni/La₁₀Si_5.8Mg_0.2O_26.8阳极微观结构的影响

Influence of NH₄HCO₃ on Microstructure of Ni/La₁₀Si_5.8Mg_0.2O_26.8 Anode

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