All Cubic-Phase δ-TAGS Thermoelectrics Over the Entire Mid-Temperature Range

GeTe-based pseudo-binary (GeTe)_x(AgSbTe₂)_100−x (TAGS–x) is recognized as a promising p-type mid-temperature thermoelectric material with outstanding thermoelectric performance; nevertheless, its intrinsic structural transition and metastable microstructure (due to Ag/Sb/Ge localization) restrict the long-time application of TAGS-x in practical thermoelectric devices. In this work, a series of non-stoichiometric (GeTe)_x(Ag_1-δSb_1+δTe_2+δ)_100−x (x = 85∼50; δ = ≈0.20–0.23), referred to as δ-TAGS-x, with all cubic phase over the entire testing temperature range (300-773 K), is synthesized. Through optimization of crystal symmetry and microstructure, a state-of-the-art ZT_max of 1.86 at 673 K and average ZT_avg of 1.43 at ≈323–773 K are realized in δ-TAGS-75 (δ = 0.21), which is the highest value among all reported cubic-phase GeTe-based thermoelectric systems so far. As compared with stoichiometric TAGS-x, the remarkable thermoelectric achieved in cubic δ-TAGS-x can be attributed to the alleviation of highly (electrical and thermal) resistive grain boundary Ag₈GeTe₆ phase. Moreover, δ-TAGS-x exhibits much better mechanical properties than stoichiometric TAGS-x, together with the outstanding thermoelectric performance, leading to a robust single-leg thermoelectric module with η_max of ≈10.2% and P_max of ≈0.191 W. The finding in this work indicates the great application potential of non-stoichiometric δ-TAGS-x in the field of mid-temperature waste heat harvesting.