Designing shape-memory-like microstructures in intercalation materials (2206.14948v1)

Abstract: During the reversible insertion of ions, lattices in intercalation materials undergo structural transformations. These lattice transformations generate misfit strains and volume changes that, in turn, contribute to the structural decay of intercalation materials and limit their reversible cycling. In this paper, we draw on insights from shape-memory alloys, another class of phase transformation materials, that also undergo large lattice transformations but do so with negligible macroscopic volume changes and internal stresses. We develop a theoretical framework to predict structural transformations in intercalation compounds and establish crystallographic design rules necessary for forming shape-memory-like microstructures in intercalation materials. We use our framework to systematically screen open-source structural databases comprising n > 5000 pairs of intercalation compounds. We identify candidate compounds, such as Li$_x$Mn$_2$O$_4$ (Spinel), Li$_x$Ti$_2$(PO$_4$)$_3$ (NASICON), that approximately satisfy the crystallographic design rules and can be precisely doped to form shape-memory-like microstructures. Throughout, we compare our analytical results with experimental measurements of intercalation compounds. We find a direct correlation between structural transformations, microstructures, and increased capacity retention in these materials. These results, more generally, show that crystallographic designing of intercalation materials could be a novel route to discovering compounds that do not decay with continuous usage.