Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

In this work, we demonstrate the direct growth of cubic Li₅La₃Nb₂O₁₂ crystal layer on the LiCoO₂ substrate through the conversion of ultra-Thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with ∑3 (2-1-1) = (1-21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb₂O₅ thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.