Recent Strategies for Lithium-Ion Conductivity Improvement in Li7La3Zr2O12 Solid Electrolytes.

Abstract

The development of solid electrolytes with high conductivity is one of the key factors in the creation of new power-generation sources. Lithium-ion solid electrolytes based on Li7La3Zr2O12 (LLZ) with a garnet structure are in great demand for all-solid-state battery production. Li7La3Zr2O12 has two structural modifications: tetragonal (I41/acd) and cubic (Ia3d). A doping strategy is proposed for the stabilization of highly conductive cubic Li7La3Zr2O12. The structure features, density, and microstructure of the ceramic membrane are caused by the doping strategy and synthesis method of the solid electrolyte. The influence of different dopants on the stabilization of the cubic phase and conductivity improvement of solid electrolytes based on Li7La3Zr2O12 is discussed in the presented review. For mono-doping, the highest values of lithium-ion conductivity (~10-3 S/cm at room temperature) are achieved for solid electrolytes with the partial substitution of Li+ by Ga3+, and Zr4+ by Te6+. Moreover, the positive effect of double elements doping on the Zr site in Li7La3Zr2O12 is established. There is an increase in the popularity of dual- and multi-doping on several Li7La3Zr2O12 sublattices. Such a strategy leads not only to lithium-ion conductivity improvement but also to the reduction of annealing temperature and the amount of some high-cost dopant. Al and Ga proved to be effective co-doping elements for the simultaneous substitution in Li/Zr and Li/La sublattices of Li7La3Zr2O12 for improving the lithium-ion conductivity of solid electrolytes.