Solid-State Electrolytes: Revealing the Mechanisms of Li-Ion Conduction in Tetragonal and Cubic LLZO by First-Principles Calculations

Citations Over TimeTop 10% of 2014 papers

Abstract

In this study, we applied first-principles-based calculations, such as ab-initio molecular dynamics simulation, metadynamics, and nudged-elastic band calculations, to successfully identify the mechanisms responsible for the considerable difference in ionic conductivity between the tetragonal and the cubic phases of LLZO (Li7La3Zr2O12)—a promising candidate for use as a highly Li-ion conductive solid-state electrolyte in Li-based batteries. Whereas in tetragonal LLZO the motion of Li ions is of fully collective nature or synchronous, we identified an asynchronous mechanism dominated by single-ion jumps and induced collective motion in cubic LLZO. The latter mechanism is possible at considerably lower energetic cost. The calculated energetic barriers that represent the two distinct mechanisms show good agreement with experimental values. Moreover, we were able to map the different mechanisms to the structural features of the particular polymorphs.

Related Papers

• → A novel NASICON-based glass-ceramic composite electrolyte with enhanced Na-ion conductivity(2019)172 cited
• → Conductivity measurements on nasicon and nasicon-modified materials(1999)150 cited
• → Improving ionic conductivity of Nasicon (Na3Zr2Si2PO12) at intermediate temperatures by modifying phase transition behavior(2018)80 cited
• → Na3Zr2(SiO4)2PO4 NASICON-type solid electrolyte: Influence of milling duration on microstructure and ionic conductivity mechanism(2022)30 cited
• → Ionic conductivity of the solid solution(1990)4 cited