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固体氧化物燃料电池中 Ni-GDC 金属陶瓷阳极的结构形成和变化。

Superstructure formation and variation in Ni-GDC cermet anodes in SOFC.

机构信息

Global Research Center for Environment and Energy based on Nanomaterials Science, National Institute for Materials Science, Tsukuba, Ibaraki 305-0044, Japan.

出版信息

Phys Chem Chem Phys. 2011 May 28;13(20):9685-90. doi: 10.1039/c1cp20296k. Epub 2011 Apr 15.

Abstract

The microstructures and spatial distributions of constituent elements at the anode in solid oxide fuel cells (SOFCs) have been characterized by analytical transmission electron microscopy (TEM). High resolution TEM observations demonstrate two different types of superstructure formation in grain interiors and at grain boundaries. Energy-filtered TEM elemental imaging qualitatively reveals that mixture zones exist at metal-ceramic grain boundaries, which is also quantitatively verified by STEM energy dispersive X-ray spectroscopy. It was apparent that both metallic Ni and the rare-earth elements Ce/Gd in gadolinium-doped ceria can diffuse into each other with equal diffusion lengths (about 100 nm). This will lead to the existence of mutual diffusion zones at grain boundaries, accompanied by a change in the valence state of the diffusing ions, as identified by electron energy-loss spectroscopy (EELS). Such mutual diffusion is believed to be the dominant factor that gives rise to superstructure formation at grain boundaries, while a different superstructure is formed at grain interiors, as a consequence solely of the reduction of Ce(4+) to Ce(3+) during H(2) treatment. This work will enhance the fundamental understanding of microstructural evolution at the anode, correlating with advancements in sample preparation in order to improve the performance of SOFC anodes.

摘要

采用分析型透射电子显微镜(TEM)对固体氧化物燃料电池(SOFC)阳极中各组成元素的微观结构和空间分布进行了表征。高分辨率 TEM 观察表明,在晶粒内部和晶界处存在两种不同类型的超结构形成。能谱 TEM 元素成像定性揭示了金属-陶瓷晶粒边界处存在混合区,这也通过 STEM 能量色散 X 射线光谱得到了定量验证。显然,金属 Ni 和掺杂铈中的稀土元素 Ce/Gd 可以以相等的扩散长度(约 100nm)相互扩散。这将导致在晶界处存在相互扩散区,同时扩散离子的价态也会发生变化,这可以通过电子能量损失光谱(EELS)来识别。这种相互扩散被认为是导致晶界处超结构形成的主要因素,而在晶粒内部形成的是另一种超结构,这是由于在 H2 处理过程中 Ce(4+)还原为 Ce(3+)所致。这项工作将增强对阳极微观结构演化的基本认识,并与样品制备的进展相关联,以提高 SOFC 阳极的性能。

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