Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Extraction of Metals by Molten Salt Electrolysis: Chemical Fundamentals and Design Factors

  • 385 Accesses

  • 7 Citations


The chemical fundamentals of electrolyte, solute, and cell reactions in molten salt electrowinning and types of electrolysis cells used for this process are discussed. Emphasis is given to the basic physicochemical and electrochemical factors in the optimum design of electrowinning processes. Examples of practical and fundamental limitations encountered in molten salt electrowinning are given. Ways to avoid those limitations are also discussed.

This is a preview of subscription content, log in to check access.


  1. 1.

    P.M.J. Gray, “The Role of Electrolysis in Metal Extraction Today,” in Energy Considerations in Electrolytic Processes, Society of Chemical Industry, London, 1980, pp. 15–19.

  2. 2.

    W.B. Darlington and M.Y.C. Woo, “Report of the Electrolytic Industries for the Year 1981,” J. Electro-chem. Soc, 129 (1982), pp. 275C–294G.

  3. 3.

    H. Bloom and J.O.M. Bockris, “Structural Aspects of Ionic Liquids,” in Fused Salts, edited by B.R. Sundheim, McGraw-Hill, New York, 1964, pp. 1–62.

  4. 4.

    N.Q. Minh and N.P. Yao, “The Extraction of Metals by Molten Salt Electrolysis of Sulfides,” in Advances in Molten Salt Chemistry, Vol. 5, edited by G. Mamantov, Elsevier, Amsterdam, 1983, pp. 231–276.

  5. 5.

    G.J. Janz, Molten Salt Handbook, Academic Press, New York, 1967.

  6. 6.

    J.M. Skeaff, “Electrowinning of Aluminum, Magnesium, Lead, and Zinc from Molten Chloride Electrolytes: A Survey,” Inst. Min. Metall. Trans. Sect. C, 89 (1980), pp. C71–C82.

  7. 7.

    K. Grjotheim, C. Krohn, M. Malinovsky, K. Matiaśovský, and J. Thonstad, “Aluminium Electrolysis, the Chemistry of the Hall-Héroult Process,” Aluminium-Verlag GmbH, Düsseldorf, 1977.

  8. 8.

    S.N. Flengas and A. Block-Bolten, “Solubilities of Reactive Gases in Molten Salts,” in Advances in Molten Salt Chemistry, Vol. 2, edited by J. Braunstein, G. Mamantov, and G.P. Smith, Plenum Press, New York, 1973, pp. 27–81.

  9. 9.

    E.A. Ukshe and N.G. Bukun, “The Dissolution of Metals in Fused Salts,” Russ. Chem. Rev., 30 (1961), pp. 90–107.

  10. 10.

    K. Grjotheim and B.J. Welch, “Aluminium Smelter Technology, a Pure and Applied Approach,” Alumi-nium-Verlag GmbH, Düsseldorf, 1980.

  11. 11.

    K. Grjotheim and J.B. See, “The Hall-Heroult Process and Alternative Processes for the Manufacture of Metallic Aluminium,” Miner. Sci. Eng., 11 (1979), pp. 80–98.

  12. 12.

    H. Winterhager, W. Krajewski, and T. Nawab-Teherani, “Magnesium Production by Molten Electrolysis of Magnesium Sulfide,” Metall. (Berlin), 30 (1976), pp. 547–551.

  13. 13.

    T.A. Henri, “Electrowinning Rare-Earth and Uranium Metals from their Oxides,” J. Metals, 16 (1964), pp. 978–981.

  14. 14.

    H.T. Fullam and J.N. Hartley, “Zinc Production by the Direct Electrolysis of Sphalerite Dissolved in a Molten Salt. Phase 1,” Battelle Pacific Northwest Labs, Richland, Washington, 1978.

  15. 15.

    A. Bonomi, C. Gentaz, M. Parodi, and J.L. Hermin, “Electrowinning of Calcium Metal by Electrolysis of a Molten Salt Solution of Calcium Carbide,” in Molten Salt Electrolysis in Metal Production, The Institution of Mining and Metallurgy, London, 1977, pp. 14–20.

  16. 16.

    A. Bonomi, M. Hadate, F. Breda, and C. Gentaz, “Exploratory Studies on Electrolysis of A1N Dissolved in Molten Salts,” J. Electrochem. Soc, 129 (1982), pp. 102–106

  17. 17.

    W.D. Jamrack, Rare Metal Extraction by Chemical Engineering Techniques, MacMillan Company, New York, 1963.

  18. 18.

    D.M. Liddell, “Magnesium and Beryllium,” in Handbook of Nonferrous Metallurgy, Recovery of the Metals, edited by D.M. Liddell, McGraw-Hill Book Company, New York, 1945, pp. 44–72.

  19. 19.

    A.K. Suri and C.K. Gupta, “Electrolytic Production of Molybdenum from a Molten Chloride Bath Using Molybdenum Dioxide Carbon Anodes,” J. Less. Common Met, 31 (1973), pp. 389–392.

  20. 20.

    A.K. Suri, D.K. Bose, and C.K. Gupta, “Electro-Extraction of Molybdenum from Mo2C-Type Carbide,” Met. Trans., 5 (1974), pp. 451–455.

  21. 21.

    W.E. Haupin, “Oxide Solubility in Lithium Chloride-Aluminum Chloride Melts,” in Light Metals 1979, edited by W.S. Peterson, TMS-AIME Publications, Warrendale, Pennsylvania, 1979, pp. 353–361.

  22. 22.

    R. Boen and J. Bouteillon, “The Electrodeposition of Silicon in Fluoride Melts,” J. Appl. Electrochem., 13 (1983), pp. 277–288.

  23. 23.

    F. Basile, E. Chassaing, and G. Lorthioir, “Electro-chemical Reduction of ZrCl4 in Molten NaCl, CsCl, and KCl-LiCl and Chemical Reactions Coupled to the Electrodeposition of Zirconium,” J. Appl. Electrochem., 11 (1981), pp. 645–651.

  24. 24.

    D. Inman and S.H. White, “Production of Refractory Metals by Electrolysis in Molten Salts: Design Factors and Limitations,” in Molten Salt Electrolysis in Metal Production, The Institution of Mining and Metallurgy, London, 1977, pp. 51–61.

  25. 25.

    S. Senderoff, “Electrodeposition of Refractory Metals,” Metall. Rev., 11 (1966), pp. 97–112.

  26. 26.

    W.E. Cowley, “The Alkali Metals,” in Molten Salt Technology, edited by D.G. Lovering, Plenum Press, J New York, 1982, pp. 57–90.

  27. 27.

    B. Lott, “Electrolytic Production of Sodium,” in Energy Considerations in Electrolytic Processes, Society of Chemical Industry, London, 1980, pp. 113–121.

  28. 28.

    R.B. MacMullin, “Building a Better Electrochemical Mousetrap,” J. Electrochem. Soc, 123 (1976), pp. 359C–368C.

  29. 29.

    Y. Ito and S. Yoshizawa, “Some New Molten Salt Electrolytic Processes,” in Advances in Molten Salt Chemistry, Vol. 4, edited by G. Mamantov and J. Braunstein, Plenum Press, New York, 1981, pp. 391–435.

  30. 30.

    K. Billehaug and H.A. Øye, “Aluminium-Mono graph: Inert Cathodes and Anodes for Aluminium Electrolysis,” Aluminium-Verlag GmbH, Düsseldorf, 1981.

Download references

Additional information

Dr. Nguyen Quang Minh received his Ph.D. from the University of New South Wales in Sydney, Australia. He is engaged in research for the Chemical Technology Division of the Argonne National Laboratory in Argonne, Illinois.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Minh, N.Q. Extraction of Metals by Molten Salt Electrolysis: Chemical Fundamentals and Design Factors. JOM 37, 28–33 (1985). https://doi.org/10.1007/BF03257510

Download citation


  • Current Efficiency
  • Molten Salt
  • Bipolar Cell
  • Cryolite
  • Metal Extraction