铜阳极泥冶炼中的硒化银热力学分析

Thermodynamics of silver selenide in copper anode slime refining

铜阳极泥是阳极铜电解精炼的副产物,含有大量的银、硒、铜和金,通常通过熔炼的方法来回收其中的银和金,熔炼过程中,银会与硒结合为硒化银(Ag_(2)Se)和硒化银铜(AgCuSe)。硒化银被认为是一种高性价比的热电材料,这种富硒材料的熔炼热力学很少受到关注,本文用电动势法测定了以超快离子导体RbAg4I5为固体电解质的固态原电池中Ag_(2)Se(硒银矿)标准热力学函数的数值,并以真空石英玻璃安瓿中的纯元素为原料合成了Ag_(2)Se,并用扫描电镜和能谱仪检测其均质性。根据实验数据,得到了Ag_(2)Se多态形态的解析方程,实验测得α-Ag_(2)Se向β-Ag_(2)Se的相变温度为407.7 K,相变焓为6.06 kJ/mol,同时给出了Ag_(2)Se的生成吉布斯能驻ΔG_(α-Ag_(2)Se,J)=-(40869.14±0.58129)-(27.94759±1.53034)T,(350 K<T<408 K),ΔG_(β-Ag_(2)Se,J)=-(35062.17±0.09895)-(42.17847±0.21827)T,(408 K<T<500 K)。

Copper anode slime is a by-product of anode copper electrolytic refining,which contains a large amount of silver,selenium,copper and gold.Slime is usually melted to recover silver and gold.The melting thermodynamics of this selenium rich material has received little attention.This article uses the electromotive force method to measure the ultrafast ion conductor RbAg4 I5 in solid state primary batteries as solid electrolytes.The numerical value of the standard thermodynamic function for Ag_(2)Se was obtained.The silver selenide was synthesized using pure elements from vacuum quartz glass ampoules as raw materials,and its homogeneity was detected using scanning electron microscopy and energy dispersive spectroscopy.Based on experimental data,Analytical equation for Ag_(2)Se polymorphic forms was obtained.