Chemical bonding origin of the unexpected isotropic physical properties in thermoelectric Mg3Sb2 and related materials

The Mg3Sb2 structure is currently being intensely scrutinized due to its outstanding thermoelectric properties. Usually, it is described as a layered Zintl phase with a clear distinction between covalent [Mg2Sb2]2− layers and ionic Mg2+ layers. Based on the quantitative chemical bonding analysis, we unravel instead that Mg3Sb2 exhibits a nearly isotropic three-dimensional bonding network with the interlayer and intralayer bonds being mostly ionic and surprisingly similar, which results in the nearly isotropic structural and thermal properties. The isotropic three-dimensional bonding network is found to be broadly applicable to many Mg-containing compounds with the CaAl2Si2-type structure. Intriguingly, a parameter based on the electron density can be used as an indicator measuring the anisotropy of lattice thermal conductivity in Mg3Sb2-related structures. This work extends our understanding of structure and properties based on chemical bonding analysis, and it will guide the search for and design of materials with tailored anisotropic properties.