A New Lithium‐Ion Conductor LiTaSiO5: Theoretical Prediction,Materials Synthesis,and Ionic Conductivity

Owing to the nonleakage and incombustibility, solid electrolytes are crucial for solving the safety issues of rechargeable lithium batteries. In this work, a new class of solid electrolyte, acceptor‐doped LiTaSiO₅, is designed and synthesized based on the concerted migration mechanism. When Zr⁴⁺ is doped to the Ta⁵⁺ sites in LiTaSiO₅, the high‐energy lattice sites are partly occupied by the introduced lithium ions, and the lithium ions at those sites interact with the lithium ions placed in the low‐energy sites, thereby favoring the concerted motion of lithium ions and lowering the energy barrier for ion transport. Therefore, the concerted migration of lithium ions occurs in Zr‐doped LiTaSiO₅, and a 3D lithium‐ion diffusion network is established with quasi‐1D chains connected through interchain channels. The lithium‐ion occupation, as revealed by ab initio calculations, is validated by neutron powder diffraction. Zr‐doped LiTaSiO₅ electrolytes are successfully synthesized; Li_1.1Ta_0.9Zr_0.1SiO₅ shows a conductivity of 2.97 × 10^?5 S cm^?1 at 25 °C, about two orders of magnitude higher than that of LiTaSiO₅, and it increases to 3.11 × 10^?4 S cm^?1 at 100 °C. This work demonstrates the power of theory in designing new materials.