The modification of the Ba content within the pseudo hollandite Ba xCr 5Se 8 leads to remarkable variations of the transport properties.
The structure of Ba 0.5Cr 5Se 8 has been recently resolved, and its thermoelectric and magnetic properties have been studied. A ZT of 0.12 was found at around 800 K. Here, we report a study on the pseudo-hollandite Ba xCr 5Se 8 solid-solution with 0.5 ≤ x ≤ 0.55 and its thermoelectric and magnetic properties. There is no significant impact either on the cell parameters depending on the cation content or on the magnetic properties. However, thermoelectric properties are radically changed depending on x content. While the low thermal conductivity, around 0.8 W m −1 K −1, remains similar for all samples, a respective increase and decrease of the resistivity and the Seebeck coefficient are observed with increasing Ba content. The maximum Seebeck coefficient is found with Ba 0.5Cr 5Se 8 at around 635 K with 315 μV K −1, and the Seebeck coefficient then decreases and is correlated with an activation of minority charge carriers confirmed by Hall measurements. A similar but steeper behavior is observed for the Ba 0.55Cr 5Se 8 temperature dependence plot at around 573 K. Finally, the best thermoelectric performances are found using the lowest content of Ba, unlike when x tends to 0.55, ZT approaches a tenth of the initial best value. Ba xCr 5Se 8 compounds are antiferromagnetic with T N = 58 K. A large peak in thermal conductivity is observed around the antiferromagnetic transition for all stoichiometry.