Variable-Temperature In Situ X-ray Diffraction Study of the Thermodynamic Evolution of AgSbTe2Thermoelectric Compound

Although AgSbTe2 compound has been intensively studied as a promising medium-temperature p-type thermoelectric (TE) material, its thermodynamic stability is still a controversial issue. We have prepared selenium-doped and pristine AgSbTe2 compounds from high-purity elements by a melt-quench-spark plasma sintering (Melt-SPS) or a melt spinning-SPS technique (MS-SPS). The influences of rapid solidification and selenium impurity on the thermodynamic evolution of AgSbTe2 TE compound have been studied by variable-temperature in situ x-ray diffraction over the temperature range from 25°C to 450°C. AgSbTe2 is a high-temperature metastable phase, and ultrahigh cooling rate in melt spinning is favorable to achieve phase-pure and homogeneous AgSbTe2 compound. The maximum possible short-time working temperature for AgSbTe2 TE compound is 250°C. Above 300°C, pristine AgSbTe2 is prone to slow decomposition to Sb2Te3, Ag5Te3, and β-Ag2Te binary compounds, regardless of preparation route. The MS-SPS sample underwent a nearly reversible phase transition on cooling to room temperature, while the Melt-SPS sample decomposed irreversibly after measurement. Selenium-doped specimen showed robust thermodynamic stability below 300°C, and experienced distinct phase transition compared with pristine specimen above 330°C, evidencing a profound influence of selenium doping on the thermodynamic stability of AgSbTe2 thermoelectric compound.