Synthetic versatility, reaction pathway, and thermal stability of tetrahedrite nanoparticles
Synthetic versatility, reaction pathway, and thermal stability of tetrahedrite nanoparticles
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DOI：
10.1039/d0tc03599h
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发表时间：
2020-10-28
影响因子：
6.4
通讯作者：
Anderson, Mary E.
中科院分区：
文献类型：
--
作者：
Fasana, Christine D.;Jensen, Mitchel S.;Anderson, Mary E.
铜锑硫化物化合物具有理想的地球丰富成分，可用于可再生能源技术，例如太阳能和废热回收。这些化合物可以通过自下而上的溶液相技术合成，这种技术比传统的固态方法更节能、更省时。溶液相方法通常生产纳米结构材料，这增加了控制光学、电学和热材料性能的另一个维度。本研究重点关注四面体 (Cu12Sb4S13) 的改性多元醇溶液相合成，四面体是一种很有前途的热电材料，也具有光伏应用的潜力。为了掺杂四面体并调整材料性能，改进的多元醇合成方法已被证明是生产纯相四面体的一种策略，该方法结合了过渡金属（Fe、Co、Ni、Zn、Ag）掺杂剂作为 Cu，Te 掺杂剂作为 Sb，Se 掺杂剂作为 S。其中六种已报道的四面体化合物以前尚未通过溶液相方法制备。对于四面体纳米材料的自下而上的形成，化学相的演变是通过研究反应进程作为温度和时间的函数来确定的。 Digenite (Cu1.8S)、蓝铜矿 (CuS) 和铁锰矿 (Cu3SbS4) 被认为是关键中间体，并且在未掺杂和掺杂的四面体中均得到一致观察。研究了纳米结构和掺杂四面体对热性能的影响。研究发现，相对于固态方法制备的样品，纳米结构未掺杂四面体的热稳定性降低，而铜掺杂剂的添加提高了材料的热稳定性。通过粉末 X 射线衍射、具有能量色散 X 射线光谱的扫描电子显微镜和透射电子显微镜对产物和中间体的结晶度、组成和纳米结构进行了表征。通过差示扫描量热法和热重分析研究热性能。这项热性质分析的合成研究证明了改进的多元醇方法生产用于热电和光伏应用的四面体和其他铜锑硫化物化合物的潜力。
Copper-antimony-sulfide compounds have desirable earth-abundant compositions for application in renewable energy technologies, such as solar energy and waste heat recycling. These compounds can be synthesized by bottom-up, solution-phase techniques that are more energy and time efficient than conventional solid-state methods. Solution-phase methods typically produce nanostructured materials, which adds another dimension to control optical, electrical, and thermal material properties. This study focuses on a modified-polyol, solution-phase synthesis for tetrahedrite (Cu12Sb4S13), a promising thermoelectric material with potential also for photovoltaic applications. To dope the tetrahedrite and tune material properties, the utility of the modified polyol synthetic approach has been demonstrated as a strategy to produce phase-pure tetrahedrite that incorporates transition metal (Fe, Co, Ni, Zn, Ag) dopants for Cu, Te dopant for Sb, and Se for S. Six of these reported tetrahedrite compounds have not previously been made by solution-phase methods. For the bottom-up formation of the tetrahedrite nanomaterials, the evolution of the chemical phases has been determined by an investigation of the reaction progress as a function of temperature and time. Digenite (Cu1.8S), covellite (CuS), and famatinite (Cu3SbS4) are identified as key intermediates and are consistently observed for both undoped and doped tetrahedrites. The effect of nanostructuring and doping tetrahedrite on thermal properties has been investigated. It was found that nanostructured undoped tetrahedrite has reduced thermal stability relative to samples made by solid-state methods, while the addition of dopants for Cu increased the thermal stability of the material. Crystallinity, composition, and nanostructure of products and intermediates were characterized by powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy, and transmission electron microscopy. Thermal properties were investigated by differential scanning calorimetry and thermal gravimetric analysis. This synthetic study with thermal property analysis demonstrates the potential of the modified polyol method to produce tetrahedrite and other copper-antimony-sulfide compounds for thermoelectric and photovoltaic applications.