Theoretical Design of Defects as a Driving Force for Ion Transport in Li_(3)OBr Solid Electrolyte

Due to ever-increasing concerns about safety issues in using Li ionic batteries,solid electrolytes have extensively explored.The Li-rich antiperovskite Li_(3)OBr has been considered as a promising solid electrolyte candidate,but it still suffers challenges to achieve a high ionic conductivity owing to the high intrinsic symmetry of the crystal lattice.Herein,we presented a design strategy that introduces various point defects and grain boundaries to break the high lattice symmetry of Li_(3)OBr crystal,and their effect and microscopic mechanism of promoting the migration of Li-ion were explored theoretically.It has been found that Li_(i)are the dominant defects responsible for the fast Li-ion diffusion in bulk Li_(3)OBr and its surface,but they are easily trapped by the grain boundaries,leading to the annihilating of the Frenkel defect pair V'_(Li)+Li_(i),and thus limits the V'_(Li)diffusion at the grain boundaries.The V_(Br)defect near the grain boundaries can effectively drive V'_(Li)across the grain boundary,thereby converting the carrier of Li^(+)migration from Li,in the bulk and surface to V'_(Li)at the grain boundary,and thus improving the ionic conductivity in the whole Li_(3)OBr crystal.This work provides a comprehensive insight into the Li^(+)transport and conduction mechanism in the Li_(3)OBr electrolyte.It opens a new way of improving the conductivity for all-solid-state Li electrolyte material through the defect design.