Advertisement

An Investigation on Electrodeposition of Titanium in Molten LiCl-KCl

  • Chenyao Li
  • Jianxun SongEmail author
  • Shaolong Li
  • Xuepeng Li
  • Yongchun Shu
  • Jilin He
Conference paper
Part of the The Minerals, Metals & Materials Series book series (MMMS)

Abstract

A molten LiCl-KCl (40.8:59.2, mol%) eutectic salt was used as an electrolyte due to its relatively low melting point. The molar ratio of fluoride ions and titanium ([F]/[Tin+] ratio) was employed as a parameter to illustrate the influence of fluoride anions on the electrochemical behaviors of Ti(III), and KF was used as a source of fluoride ions. A study on the electrochemical properties of Ti(III) was carried out in molten LiCl-KCl-KF. Results suggest that there are two steps for reducing Ti(III) in molten LiCl-KCl: Ti(III) → Ti(II) and Ti(II) → Ti. Ti(III) can be reduced directly to Ti in one step when KF was added in the melt in increasing amount. Metallic titanium was produced when [F]/[Tin+] equals to 10, and it is dendrites with a layer structure. The oxygen contents in the titanium crystal are 1200 ppm.

Keywords

LiCl-KCl Fluoride ions SWV Dendrites 

Notes

Acknowledgements

The authors thank support from Collaborative Innovation Center of Henan Resources and Materials Industry, Zhengzhou University and Startup Research Fund of Zhengzhou University (No. 32210804). The authors are grateful to the National Natural Science Foundation of China (No. 51804277) and Key Projects of Henan Province Department of Education (No. 19B450004).

References

  1. 1.
    Chen GZ, Fray DJ, Farthing TW (2000) Direct electrochemical reduction of titanium dioxide to titanium in molten calcium chloride. Nature 407:361CrossRefGoogle Scholar
  2. 2.
    Suzuki RO (2007) Direct reduction processes for titanium oxide in molten salt. JOM 1:67Google Scholar
  3. 3.
    Zheng H, Ito H, Okabe TH (2007) TH Production of titanium powder by the calciothermic reduction of titanium concentrates or ore using the preform reduction process. Mater Trans 48(8):2244CrossRefGoogle Scholar
  4. 4.
    Ferry DM, Picard GS, Tremillon BL (1988) Pulse and AC impedance studies of the electrochemical systems of titanium in LiCl-KCl eutectic melt at 743 K. J Electrochem Soc 135(6):1443CrossRefGoogle Scholar
  5. 5.
    Popov BN, Kimble MC, White RE (1991) Electrochemical behaviour of titanium(II) and titanium(III) compounds in molten lithium chloride potassium chloride eutectic melts. J Appl Electrochem 21:351CrossRefGoogle Scholar
  6. 6.
    Wei D, Okido M, Oki T (1994) Characteristics of titanium deposits by electrolysis in molten chloride-fluoride mixture. J Appl Electrochem 24:923CrossRefGoogle Scholar
  7. 7.
    Stafford GR, Moffat TP (1995) Electrochemistry of titanium in molten 2AlCl3-NaCl. J Electrochem Soc 142(10):3288Google Scholar
  8. 8.
    Ene N, Zuca S (1995) Role of free F- anions in the electrorefining of titanium in molten alkali halide mixtures. J Appl Electrochem 25:671Google Scholar
  9. 9.
    Tsuda T, Hussey CL, Stafford GR, Bonevich JE (2003) Electrochemistry of titanium and the electrodeposition of Al-Ti alloys in the Lewis acidic aluminum chloride-1-Ethyl-3-methylimidazolium chloride melt. J Electrochem Soc 150(4):C234CrossRefGoogle Scholar
  10. 10.
    Robin A (2005) Influence of temperature on the reduction mechanism of Ti(III) ions on iron in the LiF-NaF-KF eutectic melt and on the electrochemical behavior of the resultant titanium coatings. Mater Chem Phys 89:438CrossRefGoogle Scholar
  11. 11.
    Song J, Huang X, Wu J, Zhang X (2017) Electrochemical behaviors of Ti(III) in molten NaCl-KCl under various contents of fluoride. Electrochim Acta 256:252CrossRefGoogle Scholar
  12. 12.
    Wang Q, Song J, Hu G, Zhu X, Hou JG, Jiao S, Zhu H (2013) The equilibrium between titanium ions and titanium metal in NaCl-KCl equimolar molten salt. Metall Mater Trans B 44B:906CrossRefGoogle Scholar
  13. 13.
    Zhu X, Wang Q, Song J, Hou JG, Jiao S, Zhu H (2014) The equilibrium between metallic titanium and titanium ions in LiCl-KCl melts. J Alloys Compd 587:349CrossRefGoogle Scholar
  14. 14.
    Song J, Wang Q, Kang M, Jiao S, Zhu H (2014) The equilibrium between titanium ions and metallic titanium in the molten binary mixtures of LiCl. Electrochemistry 82:1047CrossRefGoogle Scholar
  15. 15.
    Song J, Wang Q, Wu J, Jiao S, Zhu H (2016) The influence of fluoride ions on the equilibrium between titanium ions and titanium metal in fused alkali chloride melts. Faraday Discuss 190:421CrossRefGoogle Scholar
  16. 16.
    Song J, Mukherjee A (2016) Influence of F- on electrochemical properties of titanium ions and Al-Ti alloy electrodeposition in molten AlCl3-NaCl. RSC Adv 6:82049CrossRefGoogle Scholar
  17. 17.
    Song J, Wang Q, Hu G, Zhu X, Jiao S, Zhu H (2014) Equilibrium between titanium ions and high-purity titanium electrorefining in a NaCl-KCl melt. Int J Min. Metall Mater 21(7):660CrossRefGoogle Scholar
  18. 18.
    Song J, Wang Q, Zhu X, Hou J, Jiao S, Zhu H (2014) The influence of fluoride anion on the equilibrium between titanium ions and electrodeposition of titanium in molten fluoride chloride salt. Mater Trans 55:1299Google Scholar
  19. 19.
    Song J, Wang Q, Kang M, Jiao S (2015) Novel synthesis of high pure titanium trichloride in molten CaCl2. Int J Electrochem Sci 10:919Google Scholar
  20. 20.
    Kang M, Song J, Zhu H, Jiao S (2014) Electrochemical behavior of titanium(II) ion in a purified calcium chloride melt. Metall Mater Trans B 46(1):162CrossRefGoogle Scholar
  21. 21.
    Song J, Xiao J, Zhu H (2017) Electrochemical behavior of titanium ions in various molten alkali chlorides. J Electrochem Soc 164(12):E321CrossRefGoogle Scholar
  22. 22.
    Polyakova LP, Stangrit PT, Polyakov EG (1986) Electrochemical study of titanium in chloride-fluoride melts. Electrochim Acta 31(2):159CrossRefGoogle Scholar
  23. 23.
    Chen G, Okido M, Oki T (1987) Electrochemical studies of titanium ions (Ti4+) in equimolar KCl-NaCl molten salts with 1 wt % K2TiF6. Electrochim Acta 32(11):1637Google Scholar
  24. 24.
    Wurm JG, Gravel L, Potvin RJA (1957) The mechanism of titanium production by electrolysis of fused halide baths containing titanium salts. J Electrochem Soc 104:301CrossRefGoogle Scholar
  25. 25.
    Lantelme F, Salmi A (1995) Electrochemistry of titanium in NaCl-KCl mixtures and influence of dissolved fluoride ions. J Electrochem Soc 142:3451CrossRefGoogle Scholar
  26. 26.
    Song J, Zhang X, Mukherjee A (2016) Electrochemical behaviors of Ce(III) in molten AlCl3-NaCl under various contents of fluoride. J Electrochem Soc 163(14):D757CrossRefGoogle Scholar
  27. 27.
    Sridharan K (2012) Thermal properties of LiCl-KCl molten salt for nuclear waste separation. Doctoral thesis. University of Wisconsin, MadisonGoogle Scholar
  28. 28.
    Gao P, Jin X, Wang D, Hu X, Chen GZ (2005) A quartz sealed Ag/AgCl reference electrode for CaCl2 based molten salts. J Electroanal Chem 579(2):321CrossRefGoogle Scholar
  29. 29.
    Yasuda K, Nohira T, Ogata YH, Ito Y (2005) Electrochemical window of molten LiCl-KCl-CaCl2 and the Ag+/Ag reference electrode. Electrochim Acta 51:561CrossRefGoogle Scholar
  30. 30.
    Sekimoto H, Nose Y, Uda T, Sugimura H (2010) Quantitative analysis of titanium ions in the equilibrium with metallic titanium in NaCl-KCl equimolar molten salt. Mater Trans 51(11):2121CrossRefGoogle Scholar
  31. 31.
    Kado Y, Kishimoto A, Uda T (2013) Electrolysis of TiO2 or TiCl2 using Bi liquid cathode in molten CaCl2. J Electrochem Soc 160(10):E139Google Scholar
  32. 32.
    Lantelme F, Kuroda K, Barhoun A (1998) A Electrochemical and thermodynamic properties of titanium chloride solutions in various alkali chloride mixtures. Electrochim Acta 44:421CrossRefGoogle Scholar
  33. 33.
    Clayton FR, Mamantov G (1973) Electrochemical studies of titanium in molten fluorides. J Electrochem Soc 120(9):1199CrossRefGoogle Scholar
  34. 34.
    Wendt H, Reuhl K, Schwartz V (1992) Cathodic deposition of refractory intermetallic compounds from FLiNaK melts I. voltammetric investigation of Ti, Zr, B, TiB2 and ZrB2. Electrochim Acta 37:237CrossRefGoogle Scholar

Copyright information

© The Minerals, Metals & Materials Society 2019

Authors and Affiliations

  • Chenyao Li
    • 1
  • Jianxun Song
    • 1
    Email author
  • Shaolong Li
    • 1
  • Xuepeng Li
    • 2
  • Yongchun Shu
    • 1
  • Jilin He
    • 1
  1. 1.Henan Province Industrial Technology Research Institute of Resources and MaterialsZhengzhou UniversityZhengzhouChina
  2. 2.National Engineering Laboratory for Vacuum MetallurgyKunming University of Science and TechnologyKunmingChina

Personalised recommendations