Electronic Orbital Alignment and Hierarchical Phonon Scattering Enabling High Thermoelectric Performance p-Type Mg3Sb2 Zintl Compounds

Abstract

Environmentally friendly Mg3Sb2-based materials have drawn intensive attention owing to their promising thermoelectric performance. In this work, the electrical properties of p-type Mg3Sb2 are dramatically optimized by the regulation of Mg deficiency. Then, we, for the first time, found that Zn substitution at the Mg2 site leads to the alignment of px,y and pz orbital, resulting in a high band degeneracy and the dramatically enhanced Seebeck coefficient, demonstrated by the DFT calculations and electronic properties measurement. Moreover, Zn alloying decreases Mg1 (Zn) vacancies formation energy and in turn increases Mg (Zn) vacancies and optimizes the carrier concentration. Simultaneously, the Mg/Zn substitutions, Mg vacancies, and porosity structure suppress the phonon transport in a broader frequency range, leading to a low lattice thermal conductivity of ~0.47 W m-1 K-1 at 773 K. Finally, a high ZT of ~0.87 at 773 K was obtained for Mg1.95Na0.01Zn1Sb2, exceeding most of the previously reported p-type Mg3Sb2 compounds. Our results further demonstrate the promising prospects of p-type Mg3Sb2-based material in the field of mid-temperature heat recovery.