Li2O助烧的Gd0.1Ce0.9O1.95烧结过程及其电导性能研究

doi:10.15541/jim20140452

摘要/Abstract

摘要：

氧化铈基电解质是中低温固体氧化物燃料电池最常用的材料之一。本研究利用密度泛函理论计算方法阐述了Li₂O和CeO₂分子之间的相互作用, 计算结果表明Li₂O对CeO₂具有助烧作用。在此基础上, 在氧化铈基电解质Gd_0.1Ce_0.9O_1.95(GDC)中掺入不同比例(0~5mol%)Li₂O, 通过烧结曲线测试及扫描电镜分析了其实际烧结过程, 并对其电化学性能进行了研究。实验结果表明, 添加Li₂O后, GDC的烧结开始收缩温度明显向低温偏移, 随掺杂量的增加, 最大收缩速率的温度也逐渐降低, 其中掺入2.5mol%Li₂O-GDC在650 ℃就开始迅速收缩, 900 ℃时相对致密度在99%以上; 添加Li₂O后, GDC总电导率提高, 同时电池开路电压没有降低。因此, Li₂O是一种很好的燃料电池氧化铈基电解质的助烧剂, 具有很好的应用前景。

关键词: 氧化铈基电解质, 烧结助剂, 固体氧化物燃料电池

Abstract:

Cerium oxide-based materials are the most widely used electrolyte material for low-intermediate temperature Solid Oxide Fuel Cell (SOFC). In this study, the interaction between Li₂O and CeO₂ was calculated based on density functional theory (DFT). The results showed that the sintering of CeO₂ was positively affected by Li₂O. Based on this result, the actual sintering process of Gd_0.1Ce_0.9O_1.95(GDC) with different concentration (0-5mol%) of Li₂O additive was characterized through the sintering behavior and scanning electron microscope (SEM). The electrochemical performance was also being investigated simultaneously. The results show that the initial shrinkage temperature shifted to lower temperature significantly, and the temperature of the highest shrinkage rate also decreased with the increasing of the Li₂O additive content. The shrinking of GDC with 2.5mol% Li₂O started at 650 ℃, and the GDC electrolyte with higher than 99% relative density was obtained at a low sintering temperature of 900 ℃. The total electrical conductivity of GDC was improved with Li₂O additive. Meanwhile, the open circuit voltage of the corresponding single cell maintained nearly the same with pure GDC. These preliminary results indicate that Li₂O is a very effective sintering aid for cerium oxide-based electrolyte in SOFC.

Key words: cerium oxide-based electrolyte, sintering aid, solid oxide fuel cell

中图分类号:

TQ174

杨志宾, 朱腾龙, 项文龙, 于立安, 韩敏芳. Li₂O助烧的Gd_0.1Ce_0.9O_1.95烧结过程及其电导性能研究[J]. 无机材料学报, 2015, 30(4): 345-350.

YANG Zhi-Bin, ZHU Teng-Long, XIANG Wen-Long, YU Li-An, HAN Min-Fang. Sintering Behavior and Electrical Conductivity of Gd_0.1Ce_0.9O_1.95 with Li₂O Additives[J]. Journal of Inorganic Materials, 2015, 30(4): 345-350.

图/表 9

图1 BP86/TZVPP和TPSS/TZVPP(括号内数据)优化后计算结果

Fig. 1 Calculation results optimized by BP86/TZVPP and TPSS/TZVPP (in brackets)

图2 BP86/TZVPP和TPSS/TZVPP(括号内数据)优化后得到两个氧化铈分子与三个和四个氧化锂分子的可能结构

Fig. 2 Possible structures included 2CeO2+3Li2O and 2CeO2+ 4Li2O optimized by BP86/TZVPP and TPSS/TZVPP (in brackets)

图3 nmol% (n=0、0.5、1.5、2.5、5.0) Li2O-GDC的烧结曲线

Fig. 3 Sintering property of nmol% (n=0, 0.5, 1.5, 2.5, 5.0) Li2O-GDC

图4 烧结温度与nmol% (n=0、0.5、1.5、2.5、5.0) Li2O-GDC相对致密度的关系

Fig. 4 Relationship between relative density and sintering temperatures of nmol% (n=0, 0.5, 1.5, 2.5, 5.0) Li2O-GDC

表1 Li2O-GDC 开始收缩温度和最大收缩速率温度比较

Table 1 The temperature of initial shrinkage and the highest shrink rate of Li2O-GDC

Temperature/℃	GDC	0.5mol%Li₂O-GDC	1.5mol%Li₂O-GDC	2.5mol%Li₂O-GDC	5mol%Li₂O-GDC
Initial shrinkage	1000	700	670	650	600
Highest shrink rate	1175	1170	920	800	750

表2 nmol% (n=0、0.5、1.5、2.5、5.0) Li2O-GDC最低致密化温度比较

Table 2 The lowest densification temperature of nmol% (n=0, 0.5, 1.5, 2.5, 5.0) Li2O-GDC

	GDC	0.5mol%Li₂O-GDC	1.5mol%Li₂O-GDC	2.5mol%Li₂O-GDC	5mol%Li₂O-GDC
Densification temperature/℃	1400	1400	1250	900	850

图5 nmol% (n=1.5、2.5、5.0) Li2O-GDC最低致密化温度下烧结之后的微观形貌

Fig. 5 Microstructure of nmol% (n=1.5, 2.5, 5.0) Li2O-GDC sintered at the lowest densification transition temperature Surface and cross section of 5mol%Li2O-GDC (a, b), 2.5mol%Li2O-GDC (c, d), 1.5mol%Li2O-GDC(e, f)

图6 不同样品的电导性能对比

Fig. 6 Relationship of electrical conductivity with temperature of nmol% (n=0, 2.5, 5.0) Li2O-GDC samples

表3 NiO-GDC/2.5mol%Li2O-GDC/LSCF电池的开路电压

Table 3 OCV of NiO-GDC/2.5mol%Li2O-GDC/LSCF cell

Temperature/℃	2.5mol%Li₂O-GDC-900 ℃/V	GDC-1400℃/V
550	0.883	0.889
600	0.879	0.877
650	0.866	0.857
700	0.843	0.841

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Li₂O助烧的Gd_0.1Ce_0.9O_1.95烧结过程及其电导性能研究

Sintering Behavior and Electrical Conductivity of Gd_0.1Ce_0.9O_1.95 with Li₂O Additives

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