Significant role of nanoscale Bi-rich phase in optimizing thermoelectric performance of Mg₃Sb₂*

Mg3Sb1.5Bi0.5-based alloys have received much attention, and current reports on this system mainly focus on the modulation of doping. However, there lacks the explanation for the choice of Mg3Sb1.5Bi0.5 as matrix. Here in this work, the thermoelectric properties of Mg3Sb2−x Bi x (0.4 ≤ x ≤ 0.55) compounds are systematically investigated by using the first principles calculation combined with experiment. The calculated results show that the band gap decreases after Bi has been substituted for Sb site, which makes the thermal activation easier. The maximum figure of merit (ZT) is 0.27 at 773 K, which is attributed to the ultra-low thermal conductivity 0.53 W·m−1·K−1 for x = 0.5. The large mass difference between Bi and Sb atoms, the lattice distortion induced by substituting Bi for Sb, and the nanoscale Bi-rich particles distributed on the matrix are responsible for the reduction of thermal conductivity. The introduction of Bi into Mg3Sb2-based materials plays a vital role in regulating the transport performance of thermoelectric materials.