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Separation and purification of Zr from a low-temperature LiCl–KCl–CsCl eutectic by the formation of dendritic crystal

  • Daoqing Ma , Jichen Xu , ZhiXuan Yi , Bin Ma , Ming Fang EMAIL logo and Xiaoli Tan EMAIL logo
Published/Copyright: August 12, 2025
Radiochimica Acta
From the journal Radiochimica Acta Volume 113 Issue 9

Abstract

Zirconium is widely used in the nuclear industry as a cladding material for nuclear reactors and loading nuclear fuel. From the perspective of safety and the economy, the recovery of zirconium from cladding waste at low temperatures is of strategic significance for nuclear energy. This work studied the electrochemical behavior of Zr(IV) and the separation of Zr metal in a low-temperature LiCl–KCl–CsCl molten salt system at 573 K (300 °C). Zr(IV) ion was reduced to metallic Zr through a two-step four-electron reaction process Zr(IV) → Zr(III) → Zr on the W electrode. The diffusion coefficients of Zr(IV) on the W electrode calculated by cyclic voltammetry and chronoamperometry were 5.805 × 10−5 cm2 s−1 and 2.861 × 10−5 cm2 s−1, respectively. Furthermore, the reaction activation energy of the Zr(III)/Zr(0) pair was measured to be 34.52 kJ mol−1 by the Tafel method. Then, the electrochemical recovery of Zr was accomplished on the W electrode by potentiostatic electrolysis at −2.0 V or galvanostatic electrolysis at 0.01 A, and two zirconium-containing products with the dendritic and flakes morphologies were obtained accordingly. This study provides a new low-temperature molten salt system for the reprocessing of zirconium cladding and shows the application potential of low-temperature molten salts LiCl–KCl–CsCl for spent fuel reprocessing.

Keywords: dendritic crystal; electrochemical behaviors; low-temperature melt; LiCl–KCl–CsCl; zirconium
Corresponding author: Ming Fang and Xiaoli Tan, MOE Key Laboratory of Resources and Environmental System Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing, 102206, P.R. China, E-mail: (M. Feng), (X. Tan)

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: The author states no conflict of interest.

  6. Research funding: This work is funded by the National Natural Science Foundation of China (U2267222).

  7. Data availability: Not applicable.

References

1. Zhang, Y.; Cai, Y.; Zhang, S.; Gao, F.; Lv, Z.; Fang, M.; Zhao, P.; Tan, X.; Hu, B.; Kong, M.; Wang, X. Super-Efficient Extraction of U(VI) by the Dual-Functional Sodium Vanadate (Na2V6O16·2H2O) Nanobelts. Chem. Eng. J. 2022, 446, 137230; https://doi.org/10.1016/j.cej.2022.137230.Search in Google Scholar

2. Rudisill, T. S. Decontamination of Zircaloy Cladding Hulls from Spent Nuclear Fuel. J. Nucl. Mater. 2009, 385, 193–195; https://doi.org/10.1016/j.jnucmat.2008.10.016.Search in Google Scholar

3. Collins, E. D.; DelCul, G. D.; Spencer, B. B.; Brunson, R. R.; Johnson, J. A.; Terekhov, D. S.; Emmanuel, N. V. Process Development Studies for Zirconium Recovery/Recycle from Used Nuclear Fuel Cladding. Procedia Chem 2012, 7, 72–76; https://doi.org/10.1016/j.proche.2012.10.013.Search in Google Scholar

4. Jung, H. S.; Choi, S.; Hwang, I. S.; Song, M. J. Environmental Assessment of Advanced Partitioning, Transmutation, and Disposal Based on Long-Term Risk-Informed Regulation: Pyrogreen. Prog. Nucl. Energy 2012, 58, 27–38; https://doi.org/10.1016/j.pnucene.2012.02.003.Search in Google Scholar

5. Wang, D.; Liu, Y.; Yang, D.; Zhong, Y.; Han, W.; Wang, L.; Chai, Z.; Shi, W. Separation of Uranium from Lanthanides (La, Sm) with Sacrificial Li Anode in LiCl-KCl Eutectic Salt. Sep. Purif. Technol. 2022, 292, 121025; https://doi.org/10.1016/j.seppur.2022.121025.Search in Google Scholar

6. Wang, D.; Liu, Y.; Zhong, Y.; Jiang, S.; Liu, Y.; Chen, J.; Han, W.; Wang, L.; Shi, W. Electrochemical Behavior and Reduction of UO22+ in LiCl-KCl Molten Salt. J. Electrochem. Soc. 2023, 170, 112507; https://doi.org/10.1149/1945-7111/ad0bb0.Search in Google Scholar

7. Chen, J.; Zhong, Y.; Wang, D.; Li, M.; Han, W.; Liu, Y.; Shi, W. Passivation Phenomenon and Variable Properties of Ytterbium in Different Lewis Acid AlCl3-NaCl Melts. J. Electroanal. Chem. 2023, 950, 117884; https://doi.org/10.1016/j.jelechem.2023.117884.Search in Google Scholar

8. Yang, M.; Zhong, Y.; Wang, D.; Wang, L.; Jiang, S.; Zhang, T.; Yan, Y.; Liu, Y.; Shi, W. Rapid and Efficient Extraction of Cerium by Forming Al-Ce Alloys in LiCl-KCl Molten Salts. Sep. Purif. Technol. 2024, 341, 126868; https://doi.org/10.1016/j.seppur.2024.126868.Search in Google Scholar

9. Lee, C. H.; Kang, K. H.; Jeon, M. K.; Heo, C. M.; Lee, Y. L. Electrorefining of Zirconium from Zircaloy-4 Cladding Hulls in LiCl-KCl Molten Salts. J. Electrochem. Soc. 2012, 159, D463–D468; https://doi.org/10.1149/2.012208jes.Search in Google Scholar

10. Fabian, C. P.; Luca, V.; Le, T. H.; Bond, A. M.; Chamelot, P.; Massot, L.; Caravaca, C.; Hanley, T. L.; Lumpkin, G. R. Cyclic Voltammetric Experiment-Simulation Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr4+ in LiCl-KCl Eutectic Molten Salt. J. Electrochem. Soc. 2013, 160, H81–H86; https://doi.org/10.1149/2.016302jes.Search in Google Scholar

11. Cai, Y.; Liu, H.; Xu, Q.; Song, Q.; Liu, H.; Xu, L. Electrochemical Behavior of Zirconium in an In-Situ Preparing LiCl-KCl-ZrCl4 Molten Slat. Int. J. Electrochem. Sci. 2015, 10, 4324–4334; https://doi.org/10.1016/s1452-3981(23)06625-7.Search in Google Scholar

12. Ghosh, S.; Vandarkuzhali, S.; Gogoi, N.; Venkatesh, P.; Seenivasan, G.; Reddy, B. P.; Nagarajan, K. Anodic Dissolution of U, Zr and U-Zr Alloy and Convolution Voltammetry of Zr4+/Zr2+ Couple in Molten LiCl-KCl Eutectic. Electrochim. Acta 2011, 24, 8204–8218.10.1016/j.electacta.2011.06.027Search in Google Scholar

13. Hoover, R. O.; Yoon, D.; Phongikaroon, S. Effects of Temperature, Concentration, and Uranium Chloride Mixture on Zirconium Electrochemical Studies in LiCl-KCl Eutectic Salt. J. Nucl. Mater. 2016, 476, 179–187; https://doi.org/10.1016/j.jnucmat.2016.04.037.Search in Google Scholar

14. Chen, Z.; Li, Y. J.; Li, S. J. Electrochemical Behavior of Zirconium in the LiCl-KCl Molten Salt at Mo Electrode. J. Alloys Compd. 2011, 509, 5958–5961; https://doi.org/10.1016/j.jallcom.2010.10.048.Search in Google Scholar

15. Guang Sen, C.; Okido, M.; Oki, T. Electrochemical Studies of Zirconium and Hafnium in Alkali Chloride and Alkali fluoride-chloride Molten Salts. J. Appl. Electrochem. 1990, 20, 77–84; https://doi.org/10.1007/bf01012474.Search in Google Scholar

16. Girginov, A.; Tzvetkoff, T. Z.; Bojinov, M. Electrodeposition of Refractory Metals (Ti, Zr, Nb, Ta) from Molten Salt Electrolytes. J. Appl. Electrochem. 1995, 25, 993–1003; https://doi.org/10.1007/bf00241947.Search in Google Scholar

17. Sakamura, Y. Zirconium Behavior in Molten LiCl-KCl Eutectic. J. Electrochem. Soc. 2004, 151, C187; https://doi.org/10.1149/1.1644605.Search in Google Scholar

18. Basin, A. S.; Kaplun, A. B.; Meshalkin, A. B.; Uvarov, N. F. The LiCl-KCl Binary System. Russ. J. Inorg. Chem. 2008, 53, 1509–1511; https://doi.org/10.1134/s003602360809026x.Search in Google Scholar

19. Burton, B. P.; Van, D.; Walle, A. First-Principles Phase Diagram Calculations for the System NaCl-KCl: The Role of Excess Vibrational Entropy. Chem. Geol. 2006, 225, 222–229.10.1016/j.chemgeo.2005.08.016Search in Google Scholar

20. Chen, J.; Zhong, Y.; Wang, D.; Li, M.; Han, W.; Liu, Y.; Shi, W. Selective Electro-Oxidative Separation of Sm, Yb, and Eu in Low-Temperature Molten Salt AlCl3-NaCl. Sep. Purif. Technol. 2024, 346, 127500; https://doi.org/10.1016/j.seppur.2024.127500.Search in Google Scholar

21. Liu, Y.; Liu, Y.; Wang, L.; Jiang, S.; Wang, D.; Liu, Z.; Li, M.; Shi, W. Electrochemical Behaviors and Extraction of Ln(III) (Ln = La, Ce, Nd) Ions in LiCl-KCl-CsCl Eutectic Salts at Low Temperatures. ACS Sustain. Chem. Eng. 2023, 11, 8161–8172; https://doi.org/10.1021/acssuschemeng.3c01474.Search in Google Scholar

22. Smolenski, V.; Novoselova, A.; Volkovich, V. A.; Ryzhov, A. A.; Yan, Y.; Xue, Y.; Ma, F. Speciation of Dysprosium in Molten LiCl-KCl-CsCl Eutectic: An Electrochemistry and Spectroscopy Study. J. Electroanal. Chem. 2022, 904, 115955; https://doi.org/10.1016/j.jelechem.2021.115955.Search in Google Scholar

23. Park, K. T.; Lee, T. H.; Jo, N. C.; Nersisyan, H. H.; Chun, B. S.; Lee, H. H.; Lee, J. H. Purification of Nuclear Grade Zr Scrap as the High Purity Dense Zr Deposits from Zirlo Scrap by Electrorefining in LiF-KF-ZrF4 Molten Fluorides. J. Nucl. Mater. 2013, 436, 130–138; https://doi.org/10.1016/j.jnucmat.2013.01.310.Search in Google Scholar

24. Ito, H.; Hasegawa, Y.; Ito, Y. Densities of Eutectic Mixtures of Molten Alkali Chlorides Below 673 K. J. Chem. Eng. Data 2001, 46, 1203–1205; https://doi.org/10.1021/je010092n.Search in Google Scholar

25. De Levie, R.; De Levie, R. How to Use Excel in Analytical Chemistry and in General Scientific Data Analysis; Cambridge University Press: Cambridge, 2001; p. 487.10.1017/CBO9780511808265Search in Google Scholar

26. Liu, K.; Liu, Y. L.; Chai, Z. F.; Shi, W. Q. Evaluation of the Electroextractions of Ce and Nd from LiCl-KCl Molten Salt Using Liquid Ga Electrode. J. Electrochem. Soc. 2017, 164, D169–D178; https://doi.org/10.1149/2.0511704jes.Search in Google Scholar

27. Marsden, K. C.; Pesic, B. Evaluation of the Electrochemical Behavior of CeCl3 in Molten LiCl-KCl Eutectic Utilizing Metallic Ce as an Anode. J. Electrochem. Soc. 2011, 158, F111; https://doi.org/10.1149/1.3575637.Search in Google Scholar

28. Liu, S.; Wang, L.; Chou, K.; Kumar, R. V. Electrolytic Preparation and Characterization of VCr Alloys in Molten Salt from Vanadium Slag. J. Alloys Compd. 2019, 803, 875–881; https://doi.org/10.1016/j.jallcom.2019.06.366.Search in Google Scholar

29. Krause, M. S.; Ramaley, L. Analytical Application of Square Wave Voltammetry. Anal. Chem. 1969, 41, 1365–1369; https://doi.org/10.1021/ac60280a008.Search in Google Scholar

30. O’Dea, J. J.; Osteryoung, J.; Osteryoung, R. A. Theory of Square Wave Voltammetry for Kinetic Systems. Anal. Chem. 1981, 53, 695–701; https://doi.org/10.1021/ac00227a028.Search in Google Scholar

31. Cha, H. L.; Yun, J. I. Redox Behaviors of Zirconium in Molten LiCl-KCl Eutectic Salt Based on the Comproportionation Reaction Between Zr(0) and Zr(IV). Electrochem. Commun. 2017, 84, 86–89; https://doi.org/10.1016/j.elecom.2017.10.010.Search in Google Scholar

32. Su, Y.; Kuijpers, K.; Hessel, V.; Noël, T. A Convenient Numbering-Up Strategy for the Scale-Up of Gas-Liquid Photoredox Catalysis in Flow. React. Chem. Eng. 2016, 1, 73–81; https://doi.org/10.1039/c5re00021a.Search in Google Scholar

33. Lee, C. H.; Kang, K. H.; Jeon, M. K.; Heo, C. M.; Lee, Y. L. Electrorefining of Zirconium from Zircaloy-4 Cladding Hulls in LiCl-KCl Molten Salts. J. Electrochem. Soc. 2012, 159, D463–D468; https://doi.org/10.1149/2.012208jes.Search in Google Scholar

34. Lee, C. H.; Kang, K. H.; Jeon, M. K.; Heo, C. M.; Lee, Y. L. Electrorefining of Zirconium from Zircaloy-4 Cladding Hulls in LiCl-KCl Molten Salts. ECS Trans. 2013, 50, 491–496; https://doi.org/10.1149/05011.0491ecst.Search in Google Scholar

35. Liu, H.; Cai, Y.; Xu, Q.; Song, Q.; Liu, H. A Novel Preparation of Zr-Si Intermetallics by Electrochemical Reduction of ZrSiO4 in Molten Salts. New J. Chem. 2015, 39, 9969–9975; https://doi.org/10.1039/c5nj01896j.Search in Google Scholar

36. Zhang, S.; Gao, F.; Fang, M.; Liu, B.; Zhang, B.; Zhong, Z.; Yu, L.; Zhang, Y.; Tan, X.; Wang, X. Catalyst‐Free Extraction of U(VI) in Solution by Tribocatalysis. Adv. Sci. 2024, 2404397; https://doi.org/10.1002/advs.202404397.Search in Google Scholar PubMed PubMed Central

37. Tan, J.; He, X.; Yin, F.; Liang, X.; Li, G.; Li, Z. Zr-Doped α-FeOOH with High Faradaic Efficiency for Electrochemical Nitrogen Reduction Reaction. Appl. Surf. Sci. 2021, 567, 150801; https://doi.org/10.1016/j.apsusc.2021.150801.Search in Google Scholar

38. Aldaz, A.; Feliu, J. M. Book Review. J. Electroanal. Chem. 2012, 670, 78; https://doi.org/10.1016/j.jelechem.2012.01.002.Search in Google Scholar

39. Janata, J. Physical Electrochemistry. Fundamentals, Techniques and Applications. Von Eliezer Gileadi. Angew. Chem. 2011, 123, 9710; https://doi.org/10.1002/ange.201104618.Search in Google Scholar

40. Han, W.; Li, W.; Chen, J.; Li, M.; Li, Z.; Dong, Y.; Zhang, M. Electrochemical Properties of Yttrium on W and Pb Electrodes in LiCl-KCl Eutectic Melts. RSC Adv. 2019, 9, 26718–26728; https://doi.org/10.1039/c9ra05496k.Search in Google Scholar PubMed PubMed Central

41. Han, W.; Wang, W.; Li, H.; Zhao, Y.; Wang, Y.; Liu, R.; Li, M. Electrochemical Recovering Zr from Molten Salt Using an Fe Electrode. ACS Sustain. Chem. Eng. 2021, 9, 17393–17402; https://doi.org/10.1021/acssuschemeng.1c06931.Search in Google Scholar

42. Gao, F.; Fang, M.; Zhang, S.; Ni, M.; Cai, Y.; Zhang, Y.; Tan, X.; Kong, M.; Xu, W.; Wang, X. Symmetry-Breaking Induced Piezocatalysis of Bi2S3 Nanorods and Boosted by Alternating Magnetic Field. Appl. Catal. B Environ. 2022, 316, 121664; https://doi.org/10.1016/j.apcatb.2022.121664.Search in Google Scholar

43. Kim, G. Y.; Yoon, D.; Paek, S.; Kim, S. H.; Kim, T. J.; Ahn, D. H. A Study on the Electrochemical Deposition Behavior of Uranium Ion in a LiCl-KCl Molten Salt on Solid and Liquid Electrode. J. Electroanal. Chem. 2012, 682, 128–135; https://doi.org/10.1016/j.jelechem.2012.07.025.Search in Google Scholar

44. Tang, H.; Pesic, B. Electrochemistry and the Mechanisms of Nucleation and Growth of Neodymium During Electroreduction from LiCl-KCl Eutectic Salts on Mo Substrate. J. Nucl. Mater. 2015, 458, 37–44; https://doi.org/10.1016/j.jnucmat.2014.11.084.Search in Google Scholar

45. Ding, L.; Wang, X.; Yang, S.; Xu, W.; Yan, Y.; Xue, Y.; Ma, F. Electrochemical Extraction Mechanism of Nd on Ga-Al Alloy Electrode. Sep. Purif. Technol. 2023, 306, 122543; https://doi.org/10.1016/j.seppur.2022.122543.Search in Google Scholar

Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/ract-2024-0355).

Received: 2024-09-29
Accepted: 2024-12-19
Published Online: 2025-08-12
Published in Print: 2025-09-25

© 2025 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Original Papers
  3. Separation and purification of Zr from a low-temperature LiCl–KCl–CsCl eutectic by the formation of dendritic crystal
  4. Particle-reinforced ion exchange resin for selective separation and recovery of cesium from highly acidic water
  5. Green synthesis of MnFe2O4 nanoparticles using Elaeis guineensis Jacq. leaves and empty fruit bunches extract and its radiolabeling with 99mTc as a potential agent for dual-modality imaging SPECT/MRI
  6. Mn(II) and Cu(II) metal complexes with bisamine based bidentate ligand. Spectroscopic investigation, biological activity and gamma ray irradiation impact
  7. Synergistic influence of carbon black and montmorillonite nano clay on mechanical, electrical, and acoustic properties of nitrile butadiene rubber nanocomposites via gamma radiation
  8. Erbium-borate modified glass with lead and barium: new composite materials for gamma ray shielding
  9. Gamma and neutron radiation shielding properties of Al2O3–B2O3–SiO2–ZnO–BaO glasses
https://doi.org/10.1515/ract-2024-0355
Keywords for this article
dendritic crystal; electrochemical behaviors; low-temperature melt; LiCl–KCl–CsCl; zirconium

Articles in the same Issue

  1. Frontmatter
  2. Original Papers
  3. Separation and purification of Zr from a low-temperature LiCl–KCl–CsCl eutectic by the formation of dendritic crystal
  4. Particle-reinforced ion exchange resin for selective separation and recovery of cesium from highly acidic water
  5. Green synthesis of MnFe2O4 nanoparticles using Elaeis guineensis Jacq. leaves and empty fruit bunches extract and its radiolabeling with 99mTc as a potential agent for dual-modality imaging SPECT/MRI
  6. Mn(II) and Cu(II) metal complexes with bisamine based bidentate ligand. Spectroscopic investigation, biological activity and gamma ray irradiation impact
  7. Synergistic influence of carbon black and montmorillonite nano clay on mechanical, electrical, and acoustic properties of nitrile butadiene rubber nanocomposites via gamma radiation
  8. Erbium-borate modified glass with lead and barium: new composite materials for gamma ray shielding
  9. Gamma and neutron radiation shielding properties of Al2O3–B2O3–SiO2–ZnO–BaO glasses
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