固体氧化物燃料电池阳极材料成份的优化规律

doi:10.15541/jim20150132

摘要/Abstract

摘要：

本研究借助第一性原理总能量计算法, 针对可能用于固体氧化物燃料电池阳极材料的3~6周期金属元素及其氧化物, 进行了稳定性、电学性能及力学性能等方面的研究。对工作条件下(高温、还原性气氛)阳极的结构形态、综合性能等的演化情况进行了研究分析, 得到了金属/氧化物体系体模量、禁带宽度的变化趋势, 及其与稳定性的关系。结果显示, 位于生成趋势图中部区域的金属/氧化物稳定性适中, 易于发生氧化/还原反应, 可能是阳极工作条件下综合性能较优的原因, 其中靠近金属区的元素更能为体系提供电子电导和催化活性, 靠近氧化物区的元素更能为体系提供氧离子并增加稳定性, 这些结果为不同条件下的阳极选择提供了理论指导。

关键词: 固体氧化物燃料电池, 阳极材料, 第一性原理, 生成趋势图, 优化规律

Abstract:

Based on the first principle total energy calculation method, the structural stability, electronic performance as well as mechanical properties of the 3rd-6th period metals and their oxides, potential to be used as anode material for solid oxide fuel cells, were studied. Considering anode working condition (high temperature and reduction atmosphere), transformation of anode structure and its performance were analyzed, and the tendencies of bulk modulus and band gap of metal/oxide were obtained. The results indicated that the metal/oxides stabilized in middle area of the formation tendency diagram would be easy to take part in oxidation/reduction reactions, and therefore suitable for anode working environment. The element which was close to metal region could introduce electronic conduction and improve the catalytic performance, while the ones near the oxides region could enhance the anode stability. These results may benefit for selection of anode materials according to various anode working conditions.

Key words: solid oxide fuel cell anode, first principle, formation tendency diagram, changing laws

中图分类号:

TQ174

常希望, 陈宁, 王丽君, 卞刘振, 李福燊, 周国治. 固体氧化物燃料电池阳极材料成份的优化规律[J]. 无机材料学报, 2015, 30(10): 1043-1048.

CHANG Xi-Wang, CHEN Ning, WANG Li-Jun, BIAN Liu-Zhen, LI Fu-Shen, CHOU Kuo-Chih. Optimization Rule of Anode Materials for Solid Oxide Fuel Cells[J]. Journal of Inorganic Materials, 2015, 30(10): 1043-1048.

图/表 6

图1 SOFC中阳极、固体电解质和阴极三种关键材料的位置关系

Fig. 1 Position of anode, electrolyte and cathode in SOFCs

图2 金属氧化物生成趋势图

Fig. 2 Diagram of oxide formation tendency

图3 金属氧化物生成趋势图.

Fig. 3 Metal oxide formation tendency diagram. Black, green, blue, and red line indicate the position of C, CH4, H2, and CO at x and y axes, respectively. The red rectangle indicates optimized region.

表1 部分金属/氧化物阳极及电池性能a

Table 1 Performance of different SOFCs anode a

Anode ^b	catalyst	Operating temperature/℃	Power density/ (mW•cm²)
Ni0.5YSZ0.5^[10]	Ni	750	300
Ni0.5YSZ0.5^[10]	Ni	850	500
Cu0.1CeO₂0.2 YSZ^[11]	Cu	700	190
Fe0.1Ni0.9 YSZ^[12]	Ni, Fe	700	232
		750	522
		800	988
		850	1238
0.01Li₂O-0.05La₂O₃- 0.07Ni-Al₂O₃ /NiO0.6ScSZ0.4^[13]	Ni, Li₂O, La₂O₃	750	291
		800	390
		850	547
(Ni0.75-Co0.25)0.6 (0.1GDC)0.4^[14]	Ni, Co	800	62
Cu40.8-Co2.6- SDC56.6^[15]	Cu, Co	700	44.8
(Cu0.5-Ni0.5)0.4- CeO₂0.6-YSZ^[16]	Ni, Cu	750	185
(Cu0.5-Ni0.5)0.4- CeO₂0.6-YSZ^[16]	Ni, Cu	800	207
Ni0.05-Pd0.09- La_0.8Sr_0.2CrO₃- Ce_0.8Sm_0.2O_1.9^[17]	Ni, Pd	800	482
Pd0.09-La_0.8Sr_0.2CrO₃- Ce_0.8Sm_0.2O_1.9^[17]	Pd	800	446
Ni-0.5GDC-0.03Ru^[18]	Ni, Ru	600	769

图4 体模量-稳定性变化梯度图

Fig. 4 Diagram of bulk modulus-stability gradient

图5 禁带宽度-稳定性变化梯度图

Fig. 5 Diagram of band gap-stability gradient

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