Abstract Stibnite mineral (mainly Sb2S3) has been employed for the synthesis of tetrahedrite Cu12Sb4S13 bulk material by spark plasma sintering. High purity Cu12Sb4S13 can be quickly obtained by two sintering procedures at temperatures from the range of 420 °C to 440 °C for 1 h. Appropriate reduction of Cu content (Cu12+xSb4S13, x ⩽ –0.05) or CuS content (Cu12−ySb4S13−y, y = 0.1 or 0.3) was beneficial to fabricate Cu12Sb4S13. The secondary resintering improved the purity of Cu12Sb4S13 material. The first-order magnetic phase transformation with magnetic hysteresis effect was confirmed by the behavior of susceptibility, heat capacity and resistivity. The magnetization showed a linear increase with increasing field (up to 7 T) and non-saturation behavior was observed. The impurities in stibnite mineral Sb2S3 had a weak influence on the transformation temperature but affected the low-temperature magnetization value (~0.15, close to natural tetrahedrite). Similar transformation was observed by the analysis of heat capacity. The properties such as electrical resistivity, Seebeck coefficient and thermal conductivity were also measured for Cu11:9Sb4S13 and Cu11:9Sb4S12:9. The maximum figure of merit ZT of Cu11:9Sb4S12:9 was 0.22 at 367 K.

中文翻译：

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辉锑矿自掺杂杂质对四面体Cu12Sb4S13制备、热容、磁性和输运性能的影响

摘要 辉锑矿矿物（主要是 Sb2S3）已被用于通过放电等离子烧结合成四面体 Cu12Sb4S13 块状材料。在 420 °C 至 440 °C 的温度范围内，通过两次烧结程序，持续 1 小时，可以快速获得高纯度的 Cu12Sb4S13。适当降低 Cu 含量（Cu12+xSb4S13，x ⩽ –0.05）或 CuS 含量（Cu12-ySb4S13-y，y = 0.1 或 0.3）有利于制造 Cu12Sb4S13。二次再烧结提高了 Cu12Sb4S13 材料的纯度。磁化率、热容和电阻率的行为证实了具有磁滞效应的一级磁相变。磁化强度随着磁场的增加（高达 7 T）呈线性增加，并观察到非饱和行为。辉锑矿矿物 Sb2S3 中的杂质对转变温度影响较弱，但影响低温磁化值（~0.15，接近天然四面体）。通过热容量分析观察到类似的转变。还测量了 Cu11:9Sb4S13 和 Cu11:9Sb4S12:9 的电阻率、塞贝克系数和热导率等特性。Cu11:9Sb4S12:9 的最大品质因数 ZT 在 367 K 时为 0.22。