• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.1 no.1
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• pp.25-39
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• 2003

This study proposed a new electrolytic reduction technology that is based on the integration of simultaneous uranium oxide metallization and Li$_2$O electrowinning. In this electrolytic reduction reaction, electrolytically reduced Li deposits on cathode and simultaneously reacts with uranium oxides to produce uranium metal showing more than 99% conversion. For the verification of process feasibility, the experiments to obtain basic data on the metallization of uranium oxide, investigation of reaction mechanism, the characteristics of closed recycle of Li$_2$O and mass transfer were carried out. This evolutionary electrolytic reduction technology would give benefits over the conventional Li-reduction process improving economic viability such as: avoidance of handling of chemically active Li-LiCl molten salt increase of metallization yield, and simplification of process.

• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.379-384
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• 2017

An electrochemical reduction of a mixture of NiO and rare earth oxides has been conducted to increase the reduction degree of rare earth oxides. Cyclic voltammetry (CV) measurement was carried out to determine the electrochemical reduction behavior of the mixed oxide in molten LiCl medium. Constant voltage electrolysis was performed with various supplied charges to understand the mechanism of electrochemical reduction of the mixed oxide as a working electrode. After completion of the electrochemical reduction, crystal structure of the reaction intermediates was characterized by using an X-ray diffraction method. The results clearly demonstrate that the rare earth oxide was converted to RE-Ni intermetallics via co-reduction with NiO.

• Journal of Powder Materials
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• v.31 no.2
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• pp.163-168
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• 2024

As the demand for lithium-ion batteries for electric vehicles is increasing, it is important to recover valuable metals from waste lithium-ion batteries. In this study, the effects of gas flow rate and hydrogen partial pressure on hydrogen reduction of NCM-based lithium-ion battery cathode materials were investigated. As the gas flow rate and hydrogen partial pressure increased, the weight loss rate increased significantly from the beginning of the reaction due to the reduction of NiO and CoO by hydrogen. At 700 ℃ and hydrogen partial pressure above 0.5 atm, Ni and Li₂O were produced by hydrogen reduction. From the reduction product and Li recovery rate, the hydrogen reduction of NCM-based cathode materials was significantly affected by hydrogen partial pressure. The Li compounds recovered from the solution after water leaching of the reduction products were LiOH, LiOH·H₂O, and Li₂CO₃, with about 0.02 wt% Al as an impurity.

• Proceedings of the Korean Radioactive Waste Society Conference
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• 2005.11b
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• pp.39-50
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• 2005

Electrolytic reduction of uranium oxide to uranium metal was studied in a $LiCl-Li_{2}O$ molten salt system. The reduction mechanism of the uranium oxide to a uranium metal has been studied by means of a cyclic voltammetry. Effects of the layer thickness of the uranium oxide and the thickness of the MgO on the overpotential of the cathode and the anode were investigated by means of a chronopotentiometry. From the cyclic voltamograms, the decomposition potentials of the metal oxides are the determining factors for the mechanism of the reduction of the uranium oxide in a $LiCl-3\;wt{\%} Li_{2}O$ molten salt and the two mechanisms of the electrolytic reduction were considered with regards to the applied cathode potential. In the chronopotentiograms, the exchange current and the transfer coefficient based on the Tafel behavior were obtained with regard to the layer thickness of the uranium oxide which is loaded into the porous MgO membrane and the thickness of the porous MgO membrane. The maximum allowable currents for the changes of the layer thickness of the uranium oxide and the thickness of the MgO membrane were also obtained from the limiting potential which is the decomposition potential of LiCl.

• 한국전기화학회:학술대회논문집
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• 1998.10a
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• pp.95-95
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• 1998

• Nuclear Engineering and Technology
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• v.42 no.2
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• pp.183-192
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• 2010

An electrochemical reduction of a mixture of metal oxides was conducted in a LiCl molten salt containing 3 wt% $Li_2O$ at $650^{\circ}C$. The oxide reduction was carried out by applying a current to an electrolysis cell, and the $Li_2O$ concentration was analyzed during each run. The concentration of $Li_2O$ in the electrolyte bulk phase gradually decreases according to Faraday's law due to a slow diffusion of the $O^{2-}$ ions. A hindrance effect of the unreduced metal oxides was observed for the reduction of the uranium oxide. Cs, Sr, and Ba of high heat-load fission products were diffused into and accumulated in the salt phase as predicted with thermodynamic consideration.

• Journal of the Korean Electrochemical Society
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• v.6 no.3
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• pp.178-182
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• 2003

The oxygen reduction and NiO dissolution behaviors in Li-Na-K three component carbonate melts have been investigated with various compositions through electrochemical and chemical ways. The oxygen reduction currents and NiO solubilities were measured at $650^{\circ}C$ and atmospheric condition in Li-Na-K =47.4-32.6-20, 60-20-20, 50-40-10, $40-40-20 mol\%$ carbonate melts. The oxygen reduction currents showed dependence on the composition, indicating oxygen solubility is a function of carbonate composition. At the composition of $ Li-Na-K=50-40-10 mol%$, a broader peak was observed, suggesting different oxygen reduction mechanism probably prevails in this composition. In contrast, insignificant differences of NiO solubility were obtained among the compositions.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.19-32
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• 2010

Electrolytic reduction technology is essential for the purpose of adopting pyroprocessing into spent oxide fuel as an alternative option in a back-end fuel cycle. Spent fuel consists of various metal oxides, and each metal oxide releases an oxygen element depending on its chemical characteristic during the electrolytic reduction process. In the present work, an electrolytic reduction behavior was estimated for voloxidized spent fuel based on the assumption that each metal-oxygen system is independent and behaves as an ideal solid solution. The electrolytic reduction was considered as a combination of a Li recovery and chemical reactions between the metal oxides such as uranium oxide and the produced Li metal. The calculated result revealed that most of the metal oxides were reduced by the process. It was evaluated that a reduced fraction of lanthanide oxides increased with a decreasing $Li_2O$ concentration. However, most of the lanthanides were expected to be stable in their oxide forms. In addition, a semi-empirical model for describing $U_3O_8$ electrolytic reduction behavior was proposed by considering Li diffusion and a chemical reaction between $U_3O_8$ and Li. Experimental data was used to determine model parameters and, then, the model was applied to calculate the reduction yield with time and to estimate the required time for a 99.9% reduction.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.4
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• pp.229-236
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• 2012

A molten salt technology using $Li_2O$-LiCl has been extensively investigated to recover uranium metal from spent fuels in the field of nuclear energy. In the reduction process, it is an important point to maintain the concentration of $Li_2O$. $ZrO_2$ is inevitably contained in the spent fuels because Zr is one of the main components of fuel rod hulls. Therefore, the fate of $ZrO_2$ in $Li_2O$-LiCl molten salt has been investigated. It was found that $Li_2ZrO_3$ and $Li_4ZrO_4$ were formed chemically and electrochemically and they were not reduced to Zr. The recycling of $Li_2O$ is the key mechanism ruling the total reaction in the electrolytic reduction process. However, $ZrO_2$ will have a role as a $Li_2O$ sink.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.8 no.1
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• pp.77-84
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• 2010

Reduction of oxides has been investigated for the volume reduction and recycling of the spent oxide fuel from commercial nuclear power plants. Various oxide reduction methods were proposed and KAERI (Korea Atomic Energy Research Institute) is currently developing an electrochemical reduction process using a LiCl-$Li_2O$ molten salt as a reaction medium. The electrochemical reduction process, the front end of the pyroprocessing, can connect the PWR (Pressurized Water Reactor) oxide fuel cycle to a metal fuel cycle of the sodium cooled fast reactor. This paper summarizes KAERI efforts on the development, improvement, and scale-up of the oxide reduction process.