Cyclic Voltammetric Experiment - Simulation Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr<sup>4+</sup>in LiCl-KCl Eutectic Molten Salt

Fabian, Cesimiro; Luca, Vittorio; Le, Thanh‐Hai; Bond, Alan M.; Chamelot, Pierre; Massot, Laurent; Caravaca, C.; Hanley, Tracey; Lumpkin, Gregory R.

doi:10.1149/2.016302jes

Cited by 27 publications

(14 citation statements)

References 18 publications

(39 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Lee et al [7] proposed a three step reduction mechanism whose redox couples are: Zr (IV)/Zr (II); Zr (II)/Zr and Zr(I)/Zr. Other authors showed a two step reduction mechanism whose redox couples differ [6,8,9]. For the first step, the authors agree on the reaction:…”

Section: Introductionmentioning

confidence: 88%

See 1 more Smart Citation

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Quaranta

Massot

Gibilaro

et al. 2018

Electrochimica Acta

View full text Add to dashboard Cite

Zirconium has a large number of properties that make it very attractive for different applications in several activity fields (nuclear, pyrotechnics, armament …). This article is devoted to the study of zir conium electrochemical behavior and crystallization phenomena on silver electrode in the LiF NaF eutectic mixture in the 690 900 C temperature range, using cyclic voltammetry, square wave vol tammetry and chronoamperometry. The result showed that Zr(IV) is reduced into Zr in a simple step exchanging four electrons and that zirconium nucleation is progressive whatever the temperature and the overvoltage. Nuclei growth takes place in all three dimensions and is limited by diffusion of Zr(IV) ions. The influence of overvoltage on the zirconium nucleation rate was also studied.

show abstract

Section: Introductionmentioning

confidence: 88%

“…a combination of two reactions: ZrðIVÞ þ 4e À $Zrð0Þ and ZrðIVÞ þ Cl À þ 3e À $ZrCl for Sakamura et al [8]. a combination of three reactions: ZrðIIÞ þ 2e À $Zrð0Þ, ZrðIVÞ þ 4e À $Zrð0Þ and ZrðIVÞ þ Cl À þ 3e À $ZrCl for Fabian et al [9].…”

Section: Introductionunclassified

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Quaranta

Massot

Gibilaro

et al. 2018

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

“…Although the experimental system is LiCl-KCl-ZrCl 4 , electrochemical behaviors of zirconium ions are quite different due to differences in experimental temperature, concentration of zirconium ions, or the electrode material. It is generally believed that Zr(IV) will directly converted to Zr (II) without Zr(III), [14][15][16][17][18][19][20][21][22] while H. L. Cha 23 confirmed the formation of Zr(III) by XPS and square wave voltammetry.…”

mentioning

confidence: 99%

Electrochemical Studies on the Redox Behavior of Zr(IV) in the LiCl-KCl Eutectic Molten Salt and Separation of Zr and Hf

Che

Song

et al. 2020

J. Electrochem. Soc.

View full text Add to dashboard Cite

Electrochemical behavior of Zr(IV) in LiCl-KCl-ZrCl 4 molten salt on molybdenum electrode was systematically studied by a series of electrochemical techniques such as cyclic voltammetry, square wave voltammetry and chronopotentiometry. It was investigated that the Zr(IV) was first reduced to Zr(III) in this system, which is different from most studies in which Zr(IV) is first reduced to Zr (II). The activation energy of Zr(IV) converted to Zr(III) was calculated to be 24.6 kJ mol −1 by measuring the diffusion coefficients of Zr(IV) at 450 °C, 500 °C, and 550 °C. Through research, the nucleation of zirconium belongs to the progressive nucleation on molybdenum electrode in LiCl-KCl-ZrCl 4 (0.0359 mol L −1 ) at 500 °C at −3.0 V vs Cl 2 /Cl − . Constant current electrolysis (Current density 0.52 A cm −2 , duration 500 min) was carried out in LiCl-KCl-ZrCl 4 system and the electrolytic product was porous metallic zirconium. More importantly, it is found that the difference in decomposition potential between Zr(II) and Hf(II) is the largest by calculation and test compared with their trivalent and tetravalent states, and they may be separated by electrolysis, which provides a theoretical reference for the electrolytic preparation of nuclear grade zirconium.

show abstract

“…Factors such as temperature, concentration of zirconium, salt composition have been considered. In chloride-based salt mixtures such as LiCl-KCl-ZrCl 4 , 2,4,[7][8][9][10][11][12][13][14][15][16][17] NaCl-KCl-ZrCl 4 , 18 NaCl-ZrCl 4 , 8 it was believed that the reduction of Zr(IV) followed a multi-step mechanism, two soluble states of Zr(IV) and Zr(II) and two insoluble states of Zr(I) and Zr were confirmed. In fluoride-based salt mixtures, the reduction was thought to be less complicated, a single-step reduction of Zr(IV) to Zr(0) was approved in LiF-NaF-ZrF 4 , 19 LiF-CaF 2 -ZrF 4 , 20 and LiF-KF-ZrF 4 , 21 and a two-step reduction was endorsed in LiF-NaF-K 2 ZrF 6 , 22 LiF-KF-ZrF 4 .…”

mentioning

confidence: 99%

Raman and Electrochemical Study of Zirconium in LiCl-KCl-LiF-ZrCl₄

Yao

Liu

Yuan

et al. 2018

J. Electrochem. Soc.

View full text Add to dashboard Cite

In this work, Raman measurements were performed with quenched LiCl-KCl-LiF-ZrCl 4 /ZrF 4 /K 2 ZrF 6 salt mixtures for deciphering the coordination chemistry of zirconium(IV) in the presence of fluoride ion in the melt. The occurrence of ZrCl 6 2− , ZrCl 4 F 2 2− , ZrF 6 2− , ZrF 7 3− and ZrF 8 4− in melt at different F/Zr molar ratios was confirmed by Raman spectra. The electrochemical redox behaviors of zirconium in LiCl-KCl-LiF-ZrCl 4 were also examined at 773 K. Transient methods such as cyclic voltammetry and square wave voltammetry were used. In LiCl-KCl-LiF-ZrCl 4 with LiF concentration less than 1.27 wt% (molar ratio F/Zr < 9.1), the reduction behavior was found to be largely dependent on the formed Zr(I) species; In LiCl-KCl-8.0 wt% LiF (F/Zr > 101), the reduction of Zr(IV) followed a two-step mechanism of Zr(IV)/Zr(III) and Zr(III)/Zr(0) at the potentials of about −0.85 and −1.40 V versus Pt, respectively.

show abstract

Cyclic Voltammetric Experiment - Simulation Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr⁴⁺in LiCl-KCl Eutectic Molten Salt

Cited by 27 publications

References 18 publications

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Electrochemical Studies on the Redox Behavior of Zr(IV) in the LiCl-KCl Eutectic Molten Salt and Separation of Zr and Hf

Raman and Electrochemical Study of Zirconium in LiCl-KCl-LiF-ZrCl₄

Contact Info

Product

Resources

About

Cyclic Voltammetric Experiment - Simulation Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr4+in LiCl-KCl Eutectic Molten Salt

Cited by 27 publications

References 18 publications

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Zirconium(IV) electrochemical behavior in molten LiF-NaF

Electrochemical Studies on the Redox Behavior of Zr(IV) in the LiCl-KCl Eutectic Molten Salt and Separation of Zr and Hf

Raman and Electrochemical Study of Zirconium in LiCl-KCl-LiF-ZrCl4

Contact Info

Product

Resources

About

Cyclic Voltammetric Experiment - Simulation Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr⁴⁺in LiCl-KCl Eutectic Molten Salt

Raman and Electrochemical Study of Zirconium in LiCl-KCl-LiF-ZrCl₄