Unexpected high-temperature stability of β-Zn4Sb3 opens the door to enhanced thermoelectric performance.

β-Zn4Sb3 has one of the highest ZT reported for binary compounds, but its practical applications have been hindered by a reported poor stability. Here we report the fabrication of nearly dense single-phase β-Zn4Sb3 and a study of its thermoelectric transport coefficients across a wide temperature range. Around 425 K we find an abrupt decrease of its thermal conductivity. Past this point, Zn atoms can migrate from crystalline sites to interstitial positions; β-Zn4Sb3 becomes metastable and gradually decomposes into Zn(hcp) and ZnSb. However, above 565 K it recovers its stability; in fact, the damage caused by decomposition can be repaired completely. This is key to its excellent thermoelectric performance at high temperature: the maximum ZT reaches 1.4. Molecular dynamics simulations are used to shed light on the microscopic behavior of the material.