Compositional Tailoring for Realizing High Thermoelectric Performance in Hafnium-Free n-Type ZrNiSn Half-Heusler Alloys.

Compositional tailoring enables fine-tuning of thermoelectric (TE) transport parameters by synergistic modulation of electronic and vibrational properties. In the present work, the aspects of compositionally tailored defects have been explored in ZrNiSn-based half-Heusler (HH) TE materials to achieve high TE performance and cost effectiveness in n-type Hf-free HH alloys. In off-stoichiometric Ni-rich ZrNiSn alloys in a low Ni doping limit ( < 0.1), excess Ni induces defects (Ni/vacancy antisite + interstitials), which tend to cause band structure modification. In addition, the structural similarity of HH and full-Heusler (FH) compounds and formation energetics lead to an intrinsic phase segregation of FH nanoscale precipitates that are coherently dispersed within the ZrNiSn HH matrix as nanoclusters. A consonance was achieved experimentally between these two competing mechanisms for optimal HH composition having both FH precipitates and Ni/vacancy antisite defects in the HH matrix by elevating the sintering temperature up to the solubility limit range of the ZrNiSn system. Defect-mediated optimization of electrical and thermal transport via carrier concentration tuning, energy filtering, and possibly all scale-hierarchical architecture resulted in a maximum ≈ 1.1 at 873 K for the optimized ZrNiSn composition. Our findings highlight the realistic prospect of enhancing TE performance via compositional engineering approach for wide applications of TE.