4.6 Article

Electrochemical Separation of Ag2S and Cu2S from Molten Sulfide Electrolyte

Journal

JOURNAL OF THE ELECTROCHEMICAL SOCIETY
Volume 169, Issue 6, Pages -

Publisher

ELECTROCHEMICAL SOC INC
DOI: 10.1149/1945-7111/ac7101

Keywords

Electrodeposition-Copper; Electrodeposition-Silver; Molten Salts-High Temperature Molten Salts; Selectivity; Liquid metal; Thermodynamics

Funding

  1. US DOE-AMO-EERE Office [DE-EE0008316]
  2. US National Science Foundation [1760025]
  3. Div Of Civil, Mechanical, & Manufact Inn
  4. Directorate For Engineering [1760025] Funding Source: National Science Foundation

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The behavior of copper and silver in molten sulfide electrolytes was studied, and it was found that the solubility of Ag2S in the supporting electrolyte is higher than that of Cu2S. Electrolysis experiments in molten sulfide were conducted to validate the thermodynamic model, and it was found that the cathode chemistry of Ag-Cu influences the electrochemical selectivity in the Ag-Cu-Ba-La-S system.
The production of precious metals from Cu-rich sources such as ore products or secondary sources is slow and complex largely due to limited solubility in aqueous electrolytes. This results in sequential processing with various electrolytes and chemistries, where first Cu is electrorefined, followed by Ag, followed by Au and the platinum group metals. These are separate processes, often conducted in separate electrorefining and electrowinning facilities. The chemical properties of molten sulfides, and their ability to operate at a temperature where liquid metal cathodes are used, suggest the possibility of an alternative, streamlined processing route for Cu and precious metals. Unfortunately, little thermodynamic or electrochemical information is available regarding the behavior of Cu and precious metal sulfides in molten sulfide electrolytes. Herein, the relative activity of the Cu2S-Ag2S pseudobinary dissolved in a BaS-La2S3 supporting electrolyte is measured at 1523 K. It was found that the supporting electrolyte favors mixing with Ag2S over Cu2S. Molten sulfide electrolysis of Cu and Ag was conducted, with results in good agreement with the thermodynamic model. It is found that the Ag-Cu cathode chemistry will influence the electrochemical selectivity in the Ag-Cu-Ba-La-S system.

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