Domain boundary structures in lanthanum lithium titanates†
Xiang Gao,Craig A. J. Fisher,Teiichi Kimura,Yumi H. Ikuhara,Akihide Kuwabara,Hiroki Moriwake,Takeshi Tojigamori,Keiichi Kohama,Yuichi Ikuhara
Journal of Materials Chemistry A Pub Date : 11/04/2013 00:00:00 , DOI:10.1039/C3TA13726K
Abstract

Perovskite-type lanthanum lithium titanate (LLTO) is attracting extensive interest because of its high intrinsic ionic conductivity. The material exhibits a complex microstructure with domains of various sizes and orientations that vary with the lithium content. Based on a systematic examination of both Li-poor and Li-rich LLTO compounds using state-of-the-art scanning transmission electron microscopy (STEM), we reveal the structures and composition of the domain boundaries (DBs) and consider their effect on Li-ion mobility and ionic conductivity, in the process positing the origin of the microstructural variations. DBs in this material are shown to consist essentially of two types: frequently occurring 90째 rotation DBs and a much less common antiphase-type boundary. It is found that the 90째 DBs are coherent interfaces consisting of interconnected steps that share La sites, with occupancies of La sites higher than in the domain interiors. The origin of microstructural variations in the two compounds is associated with different degrees of lattice mismatch strain at DBs in Li-poor and Li-rich materials. The lattice strain and associated O vacancies, as well as the high La occupancies, at DBs are expected to result in lower interdomain Li-ion mobility, which will have a deleterious effect on the overall ion conductivity.

Graphical abstract: Domain boundary structures in lanthanum lithium titanates