物理化学学报 >> 2005, Vol. 21 >> Issue (06): 663-667.doi: 10.3866/PKU.WHXB20050617

研究论文 上一篇    下一篇

碱土金属氧化物掺杂氧化铈基电解质材料中的晶格缺陷

马志芳; 梁广川; 梁金生   

  1. 河北工业大学能源与环保材料研究所,天津 300130
  • 收稿日期:2004-11-04 修回日期:2005-02-07 发布日期:2005-06-15
  • 通讯作者: 梁广川 E-mail:nyhbyjs@eyou.com

Crystal Defect Behaviors in CeO2-based Electrolyte Doped with Alkaline Earth Oxides

MA Zhi-fang; LIANG Guang-chuan; LIANG Jin-sheng   

  1. Institute of Power Source & Ecomaterials Science, Hebei University of Technology, Tianjin 300130
  • Received:2004-11-04 Revised:2005-02-07 Published:2005-06-15
  • Contact: LIANG Guang-chuan E-mail:nyhbyjs@eyou.com

摘要: 基于能量最小化算法,对碱土金属氧化物(MgO、CaO、SrO、BaO)掺杂的氧化铈基电解质缺陷进行模拟计算. 研究了掺杂离子与空位缺陷形成能和氧空位跃迁能之间的关系. 结果说明,在碱土金属氧化物掺杂氧化铈的固溶反应中,氧空位缺陷是电荷补偿缺陷的首选形式,CaO和SrO较MgO和BaO 易溶于CeO2; Ca2+掺杂离子与氧空位缺陷对[CaCe″•VO••]×的结合能最高;复合缺陷[VO•••MCe″•VO••]••在CeO2中的状态不稳定;氧空位在次近邻间的跃迁能最低,因此最容易实现跃迁.

关键词: 能量最小化算法, 氧化铈, 固体电解质, 晶格缺陷, 碱土金属氧化物

Abstract: The defect behaviors, such as defect complex formation and oxygen vacancy migration in ceria doped with alkaline earth oxides, including MgO, CaO, SrO, and BaO, were studied on the basis of energy minimization calculations. The result showed that CaO and SrO dissolve in CeO2 easier than MgO and BaO via an oxygen vacancy compensation mechanism. The association energy of neutral [CaCe″•VO••]× pair is the highest. The [VO•••MCe″•VO••]•• defect complex is not stable in ceria. The favorable route for oxygen vacancy, with the lowest migration energy, is between the second neighbor sites.

Key words: Energy minimization, Ceria, Solid electrolyte, Crystal defect, Alkaline earth oxide