Origin of Poor Cyclability in Li2NInSiO4 from First-Principles Calculations: Layer Exfoliation and Unstable Cycled Structure

Abstract

Good cyclability is essential for the potential application of cathode materials. Here, we investigate the structural stability of two-dimensional (2D) Li-layered and three-dimensional (3D) structured polymorphs of Li 2FeSiO4 and Li2MnSiO4 using the density functional theory calculations. We find that all 2D Li-layered polymorphs of both materials are unstable upon full delithiation owing to layer exfoliation, which can lead to an amorphous structure. However, in contrast to the fact that the amorphization of Li2FeSiO4 can be prevented by the formation of the 3D cycled structure that is energetically stable, the 3D cycled structure of Li2MnSiO4 is found to be unstable during delithiationlithiation cycling. As a result, Li 2MnSiO4 easily undergoes amorphization and shows a poor cyclability.