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This study shows that the design of copper-rich sulfides by mimicking natural minerals allows a new germanite-type sulfide Cu 22 Fe 8 Ge 4 S 32 with promising thermoelectric properties to be synthesized. The Mössbauer spectroscopy and X-ray diffraction analyses provide evidence that the structure of our synthetic compound differs from that of the natural germanite mineral Cu 26 Fe 4 Ge 4 S 32 by its much higher Cu + /Cu 2+ ratio and different cationic occupancies. The coupled substitution Cu/Fe in the Cu 26-x Fe 4+x Ge 4 S 32 series also appears as a promising approach to optimize the thermoelectric properties. The electrical resistivity, which decreases slightly as the temperature increases, shows that these materials exhibit a semiconducting behavior, but are at the border of a metallic state. The magnitudes of the electrical resistivity and Seebeck coefficient increase with x, which suggests that Fe for Cu substitution decreases the hole concentration. The thermal conductivity decreases as the temperature increases leading to a moderately low value of 1.2 W m -1 K -1 and a maximum ZT value of 0.17 at 575 K.

Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu22Fe8Ge4S32

Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu₂₂Fe₈Ge₄S₃₂