Lithium Ion Conduction in LiTi2(PO4)3 and Related Compounds Based on the NASICON Structure: A First-Principles Study

Abstract

LiTi2(PO4)3 (LTP) and related materials based on the structure of NaZr2(PO4)3 (NZP) belong to a family of Li ion conducting compounds for applications in Li ion batteries. Because of their three-dimensional framework of TiO6 octahedra and PO4 tetrahedra, which provide several positions for mobile charge carriers, and the large number of possible compounds crystallizing in this type of structure, they are promising ion conducting materials. In this work, we investigate the migration barriers for an interstitial Li ion and a Li vacancy in the rhombohedral structure of these compounds using density functional theory. Our results show that the substitution of Ti atoms in LTP by a variety of tri-, tetra-, and pentavalent cations X (LXTP) leads to structural changes influencing the Li mobility. The calculated activation energies for migrating vacancies vary between 0.29 and 0.75 eV and are related to the sizes of LiO6 octahedra in the structure. For migrating interstitials in bulk LTP, the calculated activation...