Mg3Sb2-based Zintl compound: a non-toxic, inexpensive and abundant thermoelectric material for power generation

The deployment of thermoelectric materials for deriving an enhanced figure of merit (ZT) for power generation in inexpensive, non-toxic and relatively abundant bulk homogeneous solid relies on the extent of achieving the "phonon-glass electron crystal" (PGEC) characteristics. Here, a proof of principal has been established experimentally in the present work for a Zintl compound of Mg3Sb2 and its derivative of isoelectronically Bi doped Bi; Mg3Sb2-xBix (0 <= x <= 0.4) alloys in Mg3Sb2. Single phase p-type Mg3Sb2 compounds, with Mg and Sb powders as starting materials, have been prepared directly by spark plasma sintering (SPS) in a one step process. The structural refinements of this hexagonal Zintl compound by X-ray diffraction analysis (XRD) and high resolution transmission electron microscopy (HRTEM) investigation reveal that they are single phase devoid of any oxides or Sb precipitates. Transport measurements indicate low thermoelectric figure of merit (ZT = 0.26 at 750 K) for Mg3Sb2. However, an optimum doping of 0.2 at% with iso-electronic Bi ions at the Sb site enhances the ZT to 0.6 at 750 K, which is comparable with the present day industrial materials such as Bi based tellurides and selenides which are toxic. We note that the system becomes metal with carrier density exceeding 15 x 10(20)/cm(3) for x >= 0.25. The substantial increase in ZT in Mg3Sb2-xBix (0 <= x <= 0.4) owes to a partial decoupling of the electronic and phonon subsystem, as expected for a Zintl phase compound. While the reduction in thermal conductivity in Mg3Sb2-xBix (0 <= x <= 0.4) accounts to mass fluctuations and grain boundary scattering, the enhancement in the electronic power-factor is attributed to the presence of heavy and light bands in its valence band structure. The latter has been confirmed by means of both X-ray photo electron spectroscopy studies and first-principles density functional based calculations. These measurements established that a high figure of merit can be achieved in this class of materials with appropriate doping. Further, relative abundance of the material ingredients combined with its one step synthesis leads to a cost effective production and less toxicity makes the material an environmentally benign system for thermoelectric power generation.