Lithium Atom and A-Site Vacancy Distributions in Lanthanum Lithium Titanate
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- 作者：Xiang Gao ; Craig A. J. Fisher ; Teiichi Kimura ; Yumi H. Ikuhara ; Hiroki Moriwake ; Akihide Kuwabara ; Hideki Oki ; Takeshi Tojigamori ; Rong Huang ; Yuichi Ikuhara
- 刊名：Chemistry of Materials
- 出版年：2013
- 出版时间：May 14, 2013
- 年：2013
- 卷：25
- 期：9
- 页码：1607-1614
- 全文大小：560K
- 年卷期：v.25,no.9(May 14, 2013)
- ISSN：1520-5002
文摘
Lanthanum lithium titanate (LLTO) is one of the most promising electrolyte materials for all-solid-state lithium-ion batteries. Despite numerous studies, the detailed crystal structure is still open to conjecture because of the difficulty of identifying precisely the positions of Li atoms and the distribution of intrinsic cation vacancies. Here we use subangstrom resolution scanning transmission electron microscopy (STEM) imaging methods and spatially resolved electron energy loss spectroscopy (EELS) analysis to examine the local atomic structure of LLTO. Direct annular bright-field (ABF) observations show Li locations on O4 window positions in Li-poor phase La0.62Li0.16TiO3 and near to A-site positions in Li-rich phase La0.56Li0.33TiO3. Local clustering of A-site vacancies results in aggregation of Li atoms, enhanced octahedral tilting and distortion, formation of O vacancies, and partial Ti4+ reduction. The results suggest local LLTO structures depend on a balance between the distribution of A-site vacancies and the need to maintain interlayer charge neutrality. The associated local clustering of A-site vacancies and aggregation of Li atoms is expected to affect the Li-ion migration pathways, which change from two-dimensional in Li-poor LLTO to three-dimensional in Li-rich LLTO. This study demonstrates how a combination of advanced STEM and EELS analysis can provide critical insights into the atomic structure and crystal chemistry of solid ionic conductors.