Substitution in MxZn4-xSb3: Effect on Thermal Stability, Crystal Structure, Phase Transitions, and Thermoelectric Performance

The effects of Cd substitution in MxZn4-xSb3 on the high-temperature thermal stability, low-temperature phase transitions and thermoelectric properties have been studied on three samples with a substitution degree of 0.1, 1, and 2 at % Cd (x = 0.004, 0.04, 0.08). The high-temperature thermal stability in atmospheric air of a I % substituted sample is compared with an unsubstituted Zn4Sb3 sample. Multitemperature synchrotron powder diffraction data reveals that while only similar to 42 wt % of the original Zn4Sb3 phase remains in the unsubstituted sample after three heating cycles to 625 K, 78 wt % is preserved in the Cd-substituted sample. Thus, Cd-substitution provides a significant improvement of the thermal stability of Zn4Sb3. Multitemperature synchrotron powder diffraction data measured between 90 and 300 K reveal that Cd substitution has a suppressing effect on the alpha'-alpha-beta phase transitions. With increasing substitution, there is also a significant change in the individual Zn site occupancies. Differential scanning calorimetry shows an apparent correlation between Cd content and phase transition temperature. Thermoelectric properties have been measured from 2 to 400 K for all samples, and although some physical properties are significantly affected by doping, no immediate improvement of ZT was achieved.