Study of thermal stability of CoSb ₃ skutterudite by Knudsen effusion mass spectrometry

Thermoelectric materials play an important role in the field of renewable energy for their ability of thermal energy conversion into electricity (thermoelectric generator) and reversibly electric energy conversion into thermal energy (thermoelectric heat pump or Peltier cooling). Doped CoSb 3 based skutterudites represent one of the very promising categories for the development of highly efficient thermoelectric materials for the conversion of waste heat to electricity. The thermoelectric efficiency, however, is closely related to thermal and phase stability as the current materials contain volatile elements (Sb, Sr, Yb, etc.), which can evaporate at operation conditions and thus cause structure changes and damage the thermoelectric properties. For a better understanding of the thermal behaviour of complex multicomponent CoSb 3 based skutterudite systems, a study of the thermal stability of primary CoSb 3 skutterudite is necessary. In this work, the thermal and phase stability of primary CoSb 3 skutterudite prepared by ball milling and hot pressing was investigated using thermal analysis and Knudsen effusion mass spectrometry performed on a Netzsch STA 409 CD/3/403/5/G apparatus, a specially-adapted type of the commercial STA 409 CD - QMS 403/5 Skimmer Coupling Instrument. Results, including data on phase transformations and those from vapour pressure measurements of antimony, supported by measurements of diffusion profiles and microstructure observations are summarized and used for evaluation of the long term thermal stability of the material.