Skip to main content
SpringerLink
Log in

Yttria-Stabilized Zirconia Aided Electrochemical Investigation on Ferric Ions in Mixed Molten Calcium and Sodium Chlorides

  • Published:
Metallurgical and Materials Transactions B Aims and scope Submit manuscript

Abstract

Electrolytic reduction of dissolved iron oxide to metal iron in molten salts with an inert anode is an alternative short route for steelmaking without CO2 emissions. A novel and simple integrated yttria-stabilized zirconia (YSZ) cell was constructed from a YSZ tube with a closed end. The YSZ tube played multiple functions, including the container for the molten salts, the solid electrolyte membrane in the O2−|YSZ|Pt|O2 (air) reference electrode (RE), and the solid electrolyte membrane between the working and counter electrodes (WE and CE). Electrochemical behavior of ferric ions (Fe3+) that were formed by dissolution of 0.5 wt pct Fe2O3 in the molten CaCl2-NaCl eutectic mixture was investigated on a Pt WE at 1273 K by various electrochemical techniques including cyclic voltammetry, linear scan voltammetry, square wave voltammetry, chronopotentiometry, chronoamperometry, and potentiostatic electrolysis. Analysis of the mechanism of electrode reactions was further assisted by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Some electrochemical parameters were obtained, including the number of exchanged electrons and the diffusion coefficient of ferric ions in the mixed molten salts. The results from various electrochemical techniques are in good agreement with each other, and show that the electrochemical reduction of Fe3+ to Fe in the molten salt mixture could be a single three-electron transfer step and diffusion-controlled reaction that was also possibly reversible. This work may form the foundation for extraction of iron and alloys from molten salts and also provide a stable O2−|YSZ|Pt|O2 (air) RE with wide applicability for investigation on electrochemical properties of other electroactive metal oxides in molten salts.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Y. Castrillejo, A. M. Martinez, M. Vega and P. S. Batanero: J. Appl. Electrochem., 1996, vol. 26, pp. 1279-85.

    Article  CAS  Google Scholar 

  2. A. Lugovskoy, M. Zinigrad, D. Aurbach and Z. Unger: Electrochim. Acta, 2009, vol. 54, pp. 1904-08.

    Article  CAS  Google Scholar 

  3. G. M. Haarberga and M. Keppertb: Ecs. Trans., 2009, vol. 16, pp. 309-15.

    Article  Google Scholar 

  4. S. Licht and H. Wu: J. Phys. Chem. C., 2011, vol. 115, pp. 25138-47.

    Article  CAS  Google Scholar 

  5. H. Yin, D. Tang, H. Zhu, Y. Zhang and D. Wang: Electrochem. Commun., 2011, vol. 13, pp. 1521-24.

    Article  CAS  Google Scholar 

  6. C. Donath, E. Neacsu and N. Ene: Rev. Roum. Chim., 2011, vol. 56, pp. 763-69.

    CAS  Google Scholar 

  7. G. M. Haarberg, E. Kvalheim, S. Rolseth, T. Murakami, S. Pietrzyk and S. Wang: Ecs. Trans., 2007, vol. 3, pp. 341-45.

    Article  CAS  Google Scholar 

  8. L. Li, X. Liu and S. Wang: in Energy Technology 2014: Carbon Dioxide Management and Other Technologies, Eds.: C Wang, J Bakker, C. K. Belt, A. Jha, N. R. Neelameggham, S. Pati, L. H. Prentice, G. Tranell and K. S. Brinkman, John Wiley & Sons, Inc. 2014, pp. 135-40.

    Chapter  Google Scholar 

  9. S. L. Wang,G. M. Haarberg and E. Kvalheim: J. Iron Steel. Res. Int., 2008, vol. 15, pp. 48-51.

    Article  CAS  Google Scholar 

  10. M. A. Quader, S. Ahmed, S. Z. Dawal and Y. Nukman: Renew. Sust. Energ. Rev., 2016, vol. 55, pp. 537-49.

    Article  Google Scholar 

  11. S. Jahanshahi, J. G. Mathieson and H. Reimink: J. Sustain. Metall., 2016, vol. 2, pp. 185-90.

    Article  Google Scholar 

  12. A. Allanore, L. Yin and D. R. Sadoway: Nature, 2013, vol. 497, pp. 353-56.

    Article  CAS  Google Scholar 

  13. D. H. Wang, A. J. Gmitter and D. R. Sadoway: J. Electrochem. Soc., 2011, vol. 158, pp. E51-54.

    Article  CAS  Google Scholar 

  14. A. H. C. Sirk, D. R. Sadoway and L. Sibille: Ecs. Trans., 2010, vol. 28, pp. 367-73.

    Article  CAS  Google Scholar 

  15. A. Allanore: Electrochim. Acta, 2013, vol. 110, pp. 587-592.

    Article  CAS  Google Scholar 

  16. A. Allanore: J. Electrochem. Soc., 2015, vol. 162, pp. E13-E22.

    Article  CAS  Google Scholar 

  17. G. Z. Chen, D. J. Fray and T. W. Farthing: Nature, 2000, vol. 407, pp. 361-64.

    Article  CAS  Google Scholar 

  18. H. Gao, X. Jin, S. Zou, F. Ling, J. Peng, Z. Wang and G. Z. Chen: Electrochim. Acta, 2013, vol. 107, pp. 261-68.

    Article  CAS  Google Scholar 

  19. G. Li, D. Wang and Z. Chen: J. Mater. Sci. Technol., 2009, vol. 25, pp. 767-71.

    CAS  Google Scholar 

  20. D. Tang, H. Yin, W. Xiao, H. Zhu, X. Mao and D. Wang: J. Electroanal. Chem., 2013, vol. 689, pp. 109-16.

    Article  CAS  Google Scholar 

  21. A. Cox and D. J. Fray: J. Appl. Electrochem., 2008, vol. 38, pp. 1401-07.

    Article  CAS  Google Scholar 

  22. Y. Berghoute, A. Salmi and F. Lantelme: J. Electroanal. Chem., 1994, vol. 365, pp. 171-77.

    Article  CAS  Google Scholar 

  23. K. K. Kasem and S. Jones: Platinum Metals Rev., 2008, vol. 52, pp. 100-06.

    Article  CAS  Google Scholar 

  24. D. J. Fray: Metall. Mat. Trans. B, 2003, vol. 34, pp. 589-94.

    Article  Google Scholar 

  25. M.J.U.T. Van Wijngaarden, R. J. Dippenaar and P. M. Van Den Heever: J. S. Afr. Inst. Min. Metall., 1987, vol. 87, pp. 269-78.

    Google Scholar 

  26. Y. M. Gao, J. X. Song, Y. Q. Zhang and X. M. Guo: Acta Metall. Sin., 2010, vol. 46, pp. 277-81.

    Article  CAS  Google Scholar 

  27. R. Ganesan, T. Gnanasekaran and R. S. Srinivasa: J. Nucl. Mater., 2006, vol. 349, pp. 133-49.

    Article  CAS  Google Scholar 

  28. T. Ogura, R. Fujiwara, R. Mochizuki, Y. Kawamoto, T. Oishi and M. Iwase: Metall. Trans. B, 1992, vol. 23B, pp. 459-66.

    Article  CAS  Google Scholar 

  29. E.T. Turkdogan: Ironmaking Steelmaking, 2000, vol. 27, pp. 32-36.

    Article  CAS  Google Scholar 

  30. P. Soral, U. Pal, H. R. Larson and B. Schroeder: Metall. Mat. Trans. B, 1999, vol. 30B, pp. 307-21.

    Article  CAS  Google Scholar 

  31. W. Kim, D. J. Min, Y. S. Lee and J. H. Park: ISIJ Int., 2009, vol. 49, pp. 1882-88.

    Article  CAS  Google Scholar 

  32. X. Guan, S. Su,U. B. Pal and A. C. Powell: Metall. Mat. Trans. B, 2014, vol. 45B, pp. 2138-44.

    Article  Google Scholar 

  33. A. Krishnan, X.G. Lu and U.B. Pal: Metall. Mat. Trans. B, 2005, vol. 36B, pp. 463-73.

    Article  CAS  Google Scholar 

  34. E. S. Gratz, X. Guan, J. D. Milshtein, U. B. Pal and A. C. Powell, Metall. Mat. Trans. B, 2014, 45B, pp. 1325-36.

    Article  Google Scholar 

  35. Y. M Gao, C. Duan, Y. B. Yang, D. Ruan, C. H. Yang and C. Hong: ISIJ Int., 2015, vol. 55, pp. 2273-82.

    Article  CAS  Google Scholar 

  36. Y. M. Gao, B. Wang, S. B. Wang and S. Peng: J. Min. Metall. Sect. B, 2013, vol. 49, pp. 49-55.

    Article  CAS  Google Scholar 

  37. C. Mallika, O. M. Sreedharan and R. Subasri: J. Eur. Ceram. Soc., 2000, vol. 20, pp. 2297-2313.

    Article  CAS  Google Scholar 

  38. S. C. Britten and U. B. Pal: Metall. Mater. Trans. B, 2000, vol. 31B, pp. 733-53.

    Article  CAS  Google Scholar 

  39. C. Z. Wang: Solid Electrolyte and Chemical Sensors, Metallurgical Industry Press, Beijing, 2000.

    Google Scholar 

  40. N. Otsuka: ECS Transactions, 2012, vol. 41, pp. 13-19.

    Article  CAS  Google Scholar 

  41. S. H. Cho, D. Y. Kim, S. Kwon, B. H. Yoon and J. H. Lee: J. Nucl. Sci. Technol., 2018, vol. 55, pp.97-103.

    Article  CAS  Google Scholar 

  42. S.H. Cho, S.W. Kim, D.Y. Kim, J.H. Lee and J.M. Hur: J. Nucl. Mater., 2017, vol. 490, pp.85-93.

    Article  CAS  Google Scholar 

  43. Y. Gao, C. Yang, C. Zhang, Q. Qin and G. Z. Chen: Phys. Chem. Chem. Phys., 2017, vol. 19, pp. 15876-90.

    Article  CAS  Google Scholar 

  44. Y. Gao, C. Hong and C. Yang: J. Electrochem. Soc., 2015, vol. 162, pp. E362-69.

    Article  CAS  Google Scholar 

  45. K. Igarashi, H. Ohtani and J. Mochinaga: Z. Für Naturforsch. A, 1987, vol. 42A, pp. 1421-24.

    Google Scholar 

  46. X.Y. Chen: Solubility of Oxides in Molten Salts and the Preparation of Carbide-Derived Carbon by Fused Salt Electrolysis Process (Master’s Thesis), Northeastern University, Shenyang, 2012.

  47. G. M. Haarberg, E. Kvalheim and S. Rolseth: Electrochemical behaviour of dissolved iron species in molten salts, in Molten Salts XIV-Proc. Int. Symp., R.A. Mantz et al, eds., PV 2004-24, The Electrochemical Society Proceedings Series, Pennington, NJ, 2004, p. 890.

  48. Factsage 7.1 (Centre for Research in Computational Thermochemistry (CRCT) and GTT-Technologies, 2017), http://www.factsage.com/. Accessed 2 Aug 2017.

  49. J. Yu, W. Yi, B. Chen and H. Chen: Binary Alloy Phase Diagrams, Shanghai Scientific and Technical Publishers, Shanghai, 1987, pp. 371.

    Google Scholar 

  50. H. E. Ghallali, H. Groult, A. Barhoun, K. Draoui and D. Krulic: Electrochim. Acta, 2009, vol. 54, pp. 3152-60.

    Article  Google Scholar 

  51. A. J. Bard and L. R. Faulkner: Electrochemical Methods Fundamentals and Applications, 2nd Ed., John Wiley & Sons, Inc, New York, 2001, pp. 226-61.

    Google Scholar 

  52. A. J. Bard and L.R. Faulkner: Electrochemical Methods Fundamentals and Applications, 2nd Ed., John Wiley & Sons, Inc, New York, 2001, pp. 669-76.

    Google Scholar 

  53. H. Tang and B. Pesic: Electrochim. Acta, 2014, vol. 119, pp. 120-30.

    Article  CAS  Google Scholar 

  54. M. Gibilaro, L. Massot, P. Chamelot, L. Cassayre and P. Taxil: Electrochim. Acta, 2013, vol. 95, pp. 185-91.

    Article  CAS  Google Scholar 

  55. M. Jayakumar, K. A. Venkatesan and T. G. Srinivasan: Electrochim. Acta. 2008, vol. 53, pp. 2794-2801.

    Article  CAS  Google Scholar 

  56. T. Sakurada, H. Maekawa and T. Yokokawa: Mater. Trans., 2007, vol. 39, pp. 740-46.

    Article  Google Scholar 

  57. Q. R. Shi, S. Z. Duan and S. M. Wu: J. Univ. Sci. Technol. B., 1994, vol. 16, pp. 599-603.

    CAS  Google Scholar 

  58. W. Huang, L. Tian, C. She, F. Jiang, H. Zheng, W. Li, G. Wu, D. Long and Q. Li: Electrochim. Acta, 2014, vol. 147, pp. 114-20.

    Article  CAS  Google Scholar 

  59. Z. Chen, Y. J. Li and S. J. Li: J. Alloys Compd., 2011, vol. 509, pp. 5958-61.

    Article  CAS  Google Scholar 

  60. C. Nourry, P. Souček, L. Massot, R. Malmbeck, P. Chamelot and J.-P. Glatz: J. Nucl. Mater., 2012, vol. 430, pp. 58-63.

    Article  CAS  Google Scholar 

  61. F. H. Hu: Molten Salt Physical Chemistry, China Industry Press, Beijing, 1963, pp.73-96.

    Google Scholar 

  62. D. Shuzhen, P. Dudley and D. Inman: J. Electroanal. Chem. Interf. Electrochem., 1982, vol. 142, pp. 215-28.

    Article  CAS  Google Scholar 

  63. B. Khalaghia, E. Kvalheima, M. Tokushigeb, L. Teng, S. Seetharamanc and G. M. Haarbergd: ECS Trans., 2014, vol. 64, pp. 301-10.

    Article  Google Scholar 

  64. Z. Guangwen, L. Yupin and Z. Yuankai: Journal of Beijing iron and steel institute, 1983, 53: 68-78.

    Google Scholar 

  65. L. Massot, P. Chamelot and F. Bouyer: Electrochim. Acta, 2002, vol. 47, pp. 1949-57.

    Article  CAS  Google Scholar 

  66. S. Frangini and S. Scaccia: J. Electrochem. Soc., 2005, vol.152, pp. A2155-58.

    Article  Google Scholar 

  67. V. A. Volkovich, T. R. Griffiths, D. J. Fray and R. C. Thied: J. Nucl. Mater., 2000, vol. 282, pp. 152-58.

    Article  CAS  Google Scholar 

  68. M. Hayyan, M. A. Hashim and I. M. AlNashef: Chem. Rev., 2016, vol. 116, pp. 3029-85.

    Article  CAS  Google Scholar 

  69. P. G. Zambonin: J. Phys. Chem., 1974, vol. 78, pp. 1294-98.

    Article  CAS  Google Scholar 

  70. M. Chandra, S. Vandarkuzhali, S. Ghosh, N. Gogoi, P. Venkatesh, G. Seenivasan, B. P. Reddy and K. Nagarajan: Electrochim. Acta, 2011, vol. 58, pp. 150-56.

    Article  CAS  Google Scholar 

  71. C. Hamel, P. Chamelot and P. Taxil: Electrochim. Acta, 2004, vol. 49, pp. 4467-76.

    Article  CAS  Google Scholar 

  72. A. Wiedenroth and C. Rüssel: J. Non-Cryst. Solids, 2004, vol. 347, pp. 180-86.

    Article  CAS  Google Scholar 

  73. A. Wiedenroth and C. Rüssel: J. Non-Cryst. Solids, 2001, vol. 290, pp. 41-48.

    Article  CAS  Google Scholar 

  74. E. Freude: Voltammetrische Untersuchung des Redoxverhaltens Polyvalenter Ionen in Glasschmelzen, Insbesondere von Technetium,Thesis Erlangen, 1989.

  75. C. Rüssel and E. Freude: Glastech. Ber., 1990, vol. 63, pp. 149-53.

    Google Scholar 

  76. O. Claussen and C. Rüssel: Glastech. Ber. Glass Sci. Technol., 1996, vol. 69, pp. 95-100.

    CAS  Google Scholar 

  77. A.W.M. Wondergem-de Best: Redox Behaviour and Fining of Molten Glass (Doctoral Thesis), Technische Universiteit Eindhoven, 1994, pp. 126.

  78. K. Serrano and P. Taxil: J. Appl. Electrochem., 1999, vol. 29, pp. 505-10.

    Article  CAS  Google Scholar 

  79. A. J. Bard and L. R. Faulkner: Electrochemical Methods Fundamentals and Applications, 2nd Ed., John Wiley & Sons, Inc, New York, 2001, pp. 161-65.

    Google Scholar 

  80. J. De Strycker, P. Westbroek and E. Temmerman: J. Electroanal. Chem., 2004, vol. 565, pp.149-58.

    Article  Google Scholar 

  81. Y. M. Kan, S. L. Li, P. L. Wang, G. J. Zhang, O. V. de Biest and J. Vleugels: Solid State Ionics, 2008, vol. 179, pp. 1531-1534.

    Article  CAS  Google Scholar 

  82. Z. G. Lv, P. Yao, R. S. Guo and F.Y. Dai: Mat. Sci. Eng. A, 2007, vol. 458, pp. 355-360.

    Article  Google Scholar 

Download references

Acknowledgments

The authors acknowledge funding provided by the National Natural Science Foundation of China (Grant No. 51174148) and the Key Program of Joint Funds of the National Natural Science Foundation of China and the Government of Liaoning Province (Grant No. U1508214).

Author information

Authors and Affiliations

  1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan, 430081, China

    Hongbo Hu, Yunming Gao, Yigui Lao, Qingwei Qin, Guangqiang Li & George Z. Chen

  2. Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan, 430081, China

    Hongbo Hu, Yunming Gao, Yigui Lao, Qingwei Qin, Guangqiang Li & George Z. Chen

  3. Department of Chemical and Environmental Engineering, and Energy Engineering Research Group, Faculty of Science Engineering, University of Nottingham Ningbo China, Ningbo, 315100, China

    George Z. Chen

Authors
  1. Hongbo Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yunming Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yigui Lao
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Qingwei Qin
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Guangqiang Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. George Z. Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yunming Gao.

Additional information

Manuscript submitted August 16, 2017.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hu, H., Gao, Y., Lao, Y. et al. Yttria-Stabilized Zirconia Aided Electrochemical Investigation on Ferric Ions in Mixed Molten Calcium and Sodium Chlorides. Metall Mater Trans B 49, 2794–2808 (2018). https://doi.org/10.1007/s11663-018-1371-z

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11663-018-1371-z

Keywords

Search

Navigation