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Factors that Influence Cation Segregation at the Surfaces of Perovskite Oxides

机译:影响钙钛矿氧化物表面阳离子离析的因素

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As the oxygen reduction reaction (ORR) becomes more critical for development of solid oxide fuel cells (SOFCs) that operate at 500-700 °C, the correlation between the surface chemistry and electrochemical performance is important to understand and enable design of cathode materials with optimal surface chemistry. Recently we demonstrated that elastic and electrostatic interactions of the dopant with the host lattice drive dopant segregation, a detrimental process on the surface of perovskite cathodes (1). Motivated by those results, here we investigated the effects of A-site stoichiometry in La_(0.8)Sr_(0.2)MnO_3 (LSM) thin films on the surface chemistry and electrochemical activity. Angle-resolved X-ray photoelectron spectroscopy was employed to identify the surface cation content and chemical bonding states. A-site deficient LSM films showed higher chemical stability against Sr segregation and secondary phase formation upon annealing. This was correlated with a higher electrochemical activity measured by AC impedance spectroscopy. Given the insulating nature of secondary phases created on the surface upon annealing, observed higher electrochemical stability in A-site deficient LSM films can be ascribed to the suppressed surface segregation and phase separation.
机译:随着氧还原反应(ORR)对于在500-700°C下运行的固体氧化物燃料电池(SOFC)的开发变得越来越关键,表面化学和电化学性能之间的相关性对于理解和实现阴极材料的设计非常重要。最佳表面化学。最近,我们证明了掺杂剂与主体晶格的弹性和静电相互作用驱动了掺杂剂的偏析,这对钙钛矿阴极表面是有害的(1)。根据这些结果,在这里我们研究了La_(0.8)Sr_(0.2)MnO_3(LSM)薄膜中A位化学计量对表面化学和电化学活性的影响。用角分辨X射线光电子能谱法鉴定表面阳离子含量和化学键合状态。 A位缺陷的LSM膜对Sr偏析和退火后形成第二相的化学稳定性更高。这与通过交流阻抗谱法测得的较高的电化学活性有关。考虑到退火时在表面上产生的次级相的绝缘性质,在A位置缺陷LSM膜中观察到的更高的电化学稳定性可以归因于抑制的表面偏析和相分离。

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