ABSTRACT
Understanding the mechanisms that connect heat and electron transport with crystal structures and defect chemistry is fundamental to develop materials with thermoelectric properties. In this work, we synthesized a series of self-doped compounds Cu2+x Mn1-x GeS4 through Cu for Mn substitution. Using a combination of powder X-ray diffraction, high resolution transmission electron microscopy and precession-assisted electron diffraction tomography, we evidence that the materials are composed of interconnected enargite- and stannite-type structures, via the formation of nanodomains with a high density of coherent interfaces. By combining experiments with ab initio electron and phonon calculations, we discuss the structure-thermoelectric properties relationships and clarify the interesting crystal chemistry in this system. We demonstrate that excess Cu+ substituted for Mn2+ dopes holes into the top of the valence band, leading to a remarkable enhancement of the power factor and figure of merit ZT.
ABSTRACT
For the first time, Na3SbS4·9H2O, also known as Schlippe's salt, has been synthesized through high-energy ball milling. This innovative synthesis way allows for obtaining high purity thioantimonate nonahydrate with around 90% yield in only approximately four hours. To validate the synthesis route described herein, the crystal structure has been refined, at room temperature, through high-resolution X-ray diffraction, pair distribution function analysis and energy dispersive spectrometry. Dehydration and rehydration of the compound have also been studied by thermogravimetric analysis and differential scanning calorimetry.
