Effect of cathode material on the electrorefining of U in LiCl-KCl molten salts

Lee, Chang Hwa; Kim, Tack-Jin; Park, Sung-Bin; Lee, Sung-Jai; Paek, Seungwoo; Ahn, Do-Hee; Cho, Sung-Ki

doi:10.1016/j.jnucmat.2017.03.023

Cited by 29 publications

(22 citation statements)

References 13 publications

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“…2Zr 2+ , as referred in prior studies. 6,8,11 However, additional investigation on the exact cause of electrical loss is required.…”

Section: Distinguishing Zr Metal and Zro 2 Via Raman Spectroscopymentioning

confidence: 99%

“…Electrorefining using chloride salts and related fundamental electrochemical investigations have been widely performed to understand how high-purity Zr metal can be separated from radioactive Zr alloys. [6][7][8] Previous studies have shown that ZrCl is deposited at approximately À1.1 V (vs Ag/AgCl, À2.3 V vs Cl 2 /Cl À ) under the LiCl-KCl environment at 773 K, such that a highly negative potential above À1.5 V (vs Ag/AgCl, À2.7 V vs Cl 2 /Cl À ) is required to transform the deposited ZrCl to Zr metal. The Zr metal recovered in this manner has a sparse and weak structure that can be detached spontaneously from the cathode and fallen at the bottom of the cell during the electrorefining operation.…”

Section: Introductionmentioning

confidence: 99%

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Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Hur

Jeon

Jeong

et al. 2021

Intl J of Energy Research

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Summary Chloride salt–based decontamination methods for neutron‐irradiated radioactive zirconium alloys have been designed to directly recover metallic Zr. Previous studies have shown that ZrCl is co‐deposited with Zr at a low current density on the cathode, while sparse and low‐purity Zr is obtained with the application of a high current density. We propose a process to prepare high‐purity Zr metal involving the electrochemical recovery of ZrCl and thermal decomposition of ZrCl to Zr. Electrodeposition of ZrCl in a LiCl‐KCl‐ZrCl4 system by controlling the cathode potential at −1.1 V (vs Ag/AgCl, −2.3 V vs Cl2/Cl−) was performed at 723 K to produce ZrCl and confirm the morphology of deposition. Dense and layered depositions adhered to the cathode were introduced to a vacuum distillation furnace after washing with pyridine solvent. The optimized condition of the thermal decomposition process was deduced by experimental results using X‐ray diffraction, scanning electron microscopy, Raman spectroscopy, and inductively coupled plasma‐optical emission spectrometry. Furthermore, the crystallographic phase transition of Zr into a face‐centered cubic structure during the thermal decomposition was also observed by crystallographic analysis. Quantitative evaluation of electrodeposition of ZrCl and production Zr by thermal decomposition was discussed.

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“…2Zr 2+ , as referred in prior studies. 6,8,11 However, additional investigation on the exact cause of electrical loss is required.…”

Section: Distinguishing Zr Metal and Zro 2 Via Raman Spectroscopymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Hur

Jeon

Jeong

et al. 2021

Intl J of Energy Research

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“…For this reason, electrorefining using molten halide electrolytes has been studied for the volumetric treatment of metallic radioactive waste [11][12][13][14][15][16][17][18][19]. Previous electrorefining tests in fluorides have shown that it is possible to recover metallic Zr deposits as a dendrite from on the cathode with high purity due to the single-step Zr reduction reaction in fluorides [11][12][13]. Park et al conducted the electrorefining of Zirlo, containing Nb of 1 wt.…”

Section: Introductionmentioning

confidence: 99%

“…Fujita et al conducted the electrorefining of a BWR channel box in molten LiCl-KCl-ZrCl 4 -ZrF salt at 923 K to separate Co-60 [12]. Lee et al conducted the electrorefining of Zirlo in fluoride-added chloride salt to recover pure Zr, with a coarse deposit formed at the cathode [13]. Despite this advantage, fluorides have high corrosivity to structural materials, and it is required that a high operating temperature is used due to its melting point, which can potentially lead to scale-up issues.…”

Section: Introductionmentioning

confidence: 99%

Separation of Zr from Zr-2.5Nb by Electrorefining in LiCl-KCl for Volumetric Decontamination of CANDU Pressure Tube

et al. 2021

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This study presents an experimental investigation on Zr separation from Zr-2.5Nb by anode potentiostatic electrorefining in LiCl-KCl-ZrCl4 0.5 wt. % at 773 K for irradiated CANDU pressure tube decontamination. By the ORIGEN-2 code calculation, radioactive characteristics were investigated to show that Nb-94 was the most significant radionuclide with an aspect of waste level reduction by electrorefining. Three electrorefining tests were performed by fixing the applied potential as −0.9 V (vs. Ag/AgCl 1 wt. %) at the anode to dissolve only Zr. A cathode basket was installed to collect detached deposits from the cathode. Electrorefining results showed Zr was deposited on the cathode with a small amount of Nb and other alloying elements. The chemical form of the cathode deposits was shown to be only Zr metal or a mixture of Zr metal and ZrCl, depending on the experimental conditions related to the surface area ratio of the cathode to the anode. It was determined that the Zr metal reduction at the cathode was attributed to the two-step reduction reaction of Zr4+/ZrCl and ZrCl/Zr.

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“…21 The influence of the cathode material on uranium electrorefining process was examined using electrochemical measurements and SEM-EDX observations. 22 Stainless steel (STS), Mo, and W electrodes exhibited similar U reduction/oxidation behavior at 500 o C in LiCl-KCl-UCl 3 molten salt. 22 The electrochemical reduction of uranium (III) ions to metal in a molten salt electrolyte was also studied on solid and liquid cathodes.…”

mentioning

confidence: 97%

Mechanism of Metallic Uranium and Bimetallic U-Ga, U-Cd Alloys Electrodeposition in Molten LiCl–KCl–CsCl Eutectic

Новоселова

Smolenski

Volkovich

et al. 2023

J. Electrochem. Soc.

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Speciation and behavior of uranium (III) chloride in the ternary low melting LiCl–KCl–CsCl eutectic was studied by electrochemistry and spectroscopy techniques. Cathodic reduction of U(III) ions on inert (tungsten) and reactive (gallium, cadmium) electrodes was investigated at 623-923 K using cyclic and square wave voltammetry. The potential scan rate was changed from 0.075 to 0.5 V/s in all experiments. It was established that the electrochemical reduction process on the inert electrode was irreversible, proceeded in one stage, and was controlled by the charge transfer. Formation of uranium alloys with gallium and cadmium was studied using active liquid Ga and Cd electrodes. Reduction of uranium ions of the reactive electrodes proceeded with considerable depolarization. The effect of current density on the composition of the cathodic product was considered. Conditions for the electrochemical production of alloys of a given composition were determined.

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Effect of cathode material on the electrorefining of U in LiCl-KCl molten salts

Cited by 29 publications

References 13 publications

Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Zirconium metal recovery from irradiated radioactive zirconium alloy via chloride‐basedelectrorefining and thermal decomposition ofZrCl

Separation of Zr from Zr-2.5Nb by Electrorefining in LiCl-KCl for Volumetric Decontamination of CANDU Pressure Tube

Mechanism of Metallic Uranium and Bimetallic U-Ga, U-Cd Alloys Electrodeposition in Molten LiCl–KCl–CsCl Eutectic

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