Baláž Peter, Guilmeau Emmanuel, Achimovičová Marcela, Baláž Matej, Daneu Nina, Dobrozhan Oleksandr, Kaňuchová Mária
Institute of Geotechnics, Slovak Academy of Sciences, 04001 Košice, Slovakia.
CRISMAT, CNRS, Normandy University, ENSICAEN, UNICAEN, 14000 Caen, France.
Nanomaterials (Basel). 2021 May 25;11(6):1386. doi: 10.3390/nano11061386.
In this study, we demonstrate the feasibility of Bi-doped tetrahedrite CuSbBiS (x = 0.02-0.20) synthesis in an industrial eccentric vibratory mill using Cu, Sb, Bi and S elemental precursors. High-energy milling was followed by spark plasma sintering. In all the samples, the prevailing content of tetrahedrite CuSbS (71-87%) and famatinite CuSbS (13-21%), together with small amounts of skinnerite CuSbS, have been detected. The occurrence of the individual Cu-Sb-S phases and oxidation states of bismuth identified as Bi and Bi are correlated. The most prominent effect of the simultaneous milling and doping on the thermoelectric properties is a decrease in the total thermal conductivity () with increasing Bi content, in relation with the increasing amount of famatinite and skinnerite contents. The lowest value of was achieved for x = 0.2 (1.1 W m K at 675 K). However, this sample also manifests the lowest electrical conductivity , combined with relatively unchanged values for the Seebeck coefficient () compared with the un-doped sample. Overall, the lowered electrical performances outweigh the benefits from the decrease in thermal conductivity and the resulting figure-of-merit values illustrate a degradation effect of Bi doping on the thermoelectric properties of tetrahedrite in these synthesis conditions.
在本研究中，我们展示了使用铜、锑、铋和硫元素前驱体在工业偏心振动磨中合成铋掺杂黝铜矿CuSbBiS（x = 0.02 - 0.20）的可行性。高能球磨后进行放电等离子烧结。在所有样品中，均检测到了主要成分黝铜矿CuSbS（71 - 87%）和硫锑铜矿CuSbS（13 - 21%），以及少量的硫铜铋矿CuSbS。已确定的各个铜 - 锑 - 硫相的出现与铋的氧化态（Bi和Bi）相关。同时进行球磨和掺杂对热电性能最显著的影响是，随着铋含量的增加，总热导率（）降低，这与硫锑铜矿和硫铜铋矿含量的增加有关。对于x = 0.2的样品，在675 K时达到了最低的热导率值（1.1 W m K）。然而，该样品的电导率也最低，与未掺杂样品相比，塞贝克系数（）的值相对不变。总体而言，电性能的降低超过了热导率降低带来的益处，所得的优值表明在这些合成条件下铋掺杂对黝铜矿热电性能具有降解作用。
