Understanding Oxidation Resistance of Half-Heusler Alloys for in-Air High Temperature Sustainable Thermoelectric Generators.

High temperature waste heat recovery has gained tremendous interest to generate useful electricity while reducing the harmful impact on the environment. Thermoelectric (TE) solid-state materials enable direct conversion of heat into electricity with high efficiency, thereby offering a practical solution for waste heat recovery. Half-Heusler (hH) alloys are the leading TE materials for medium to high temperature applications, as they exhibit a high figure of merit and mechanical strength at temperatures as high as 973 K. Here we investigate the most promising hH alloys represented as MNiSn, MCoSb, and NbFeSb systems (M = Hf, Zr, and Ti) and provide fundamental understanding of their in-air thermal stability at high temperatures under realistic operating conditions required for energy generation. The understanding of oxidation resistance of TE materials is crucial for their practical deployment in extreme environments without vacuum sealing. The n-type MNiSn and p-type NbFeSb compounds are found to exhibit excellent oxidation resistance at a high temperature of 873 K. The oxidation resistance is enhanced through the presence of an intermetallic Ni-Sn layer for MNiSn and Nb-TiO2 double layer for (Nb,Ti)FeSb. A unicouple thermoelectric generator (TEG) fabricated from thermally stable materials demonstrated consistent performance for more than 150 h at 873 K in air. These results demonstrate the significance of TE materials in waste heat recovery systems.