Measurement of oxide ion (O2-) concentration is a basic technology required in molten salt fields, from energy storage systems to electrolytic reduction of rare earth elements or spent nuclear fuels. In a molten salt reactor, O2- ions react with actinide elements to form their oxides or oxy-chlorides to induce actinide precipitation, and promote metal corrosion to cause a failure of structural material. For these reasons, removal of O2- ions and monitoring of the O2- concentration in molten salt reactors are essential. In this study, methods using chemical and electrochemical methods were investigated for measuring the concentration of O2- ions in a molten salts. The acid-base neutralization reaction was used as a chemical analysis method. And electrochemical methods using the O2- diffusion limit current and YSZ (yttria stabilized zirconia) indicator electrode were used for measuring the O2- concentration. Finally, a modified method using porous membrane electrode was applied to monitor the O2- concentration. The O2- concentration was measured up to about 2wt% of Li2O by the method using the O2- diffusion current, up to about 4wt% by the YSZ indicator electrode, and about 6wt% by the porous membrane electrode in LiCl molten salts.

Spin-off pyroprocessing technology and inert anode materials to replace the conventional carbon-based smelting process for critical materials were introduced. Efforts to select inert anode materials through numerical analysis and selected experimental results were devised for the high-throughput reduction of oxide feedstocks. The electrochemical properties of the inert anode material were evaluated, and stable electrolysis behavior and CaCu generation were observed during molten salt recycling. Thereafter, CuTi was prepared by reacting rutile (TiO2) with CaCu in a Ti crucible. The formation of CuTi was confirmed when the concentration of CaO in the molten salt was controlled at 7.5mol%. A laboratory-scale electrorefining study was conducted using CuTi(Zr, Hf) alloys as the anodes, with a Ti electrodeposit conforming to the ASTM B299 standard recovered using a pilot-scale electrorefining device.

Separation of high heat generating-radioactive isotopes from spent nuclear fuel is an important issue because it can reduce the final disposal area. As one of the technologies that can selectively separate only high heat generating-radioactive isotopes without dissolving spent fuel, the methods using molten salt have recently attracted attention. Although studies on chemical changes of Sr oxides in molten salts have been reported, they have limitation in that alternative oxide reagents rather than oxide fuel were used. In this study, the separation behaviors of Sr from simulated oxide fuel using various molten salts were investigated. A powder type containing 95.7wt% of U and 0.123wt% of Sr was used as the simulated oxide fuel. LiCl, LiCl-CaCl2, MgCl2, LiCl-KCl-MgCl2 and NaCl-MgCl2 were used as molten chloride salts. The separation of Sr from the simulated oxide fuel was conducted by loading it in porous alumina basket and immersing it in a salt. The concentration of Sr in the salt was measured by ICP analysis after sampling the salt outside the basket using dip-stick technique. The separation efficiencies of Sr from simulated oxide fuel using the salts were compared. Furthermore, the causes of their separation efficiency were systematically investigated.

To estimate the removal efficiency of TRU and rare earth elements in an oxide spent fuel, basic dissolution experiments were performed for the reaction of rare earth elements from the prepared simfuel with chlorination reagents in LiCl-KCl molten salt. Based on the literature survey, NH4Cl, UCl3, and ZrCl4 were selected as chlorination reagent. CeO2 and Gd2O3 powders were mixed with uranium oxide as a representative material of rare earth elements. Simfuel pellets were prepared through molding and sintering processes, and mechanically pulverized to a powder form. The experiments for the reaction of the simfuel powder and chlorination reagents were carried out in a LiCl-KCl molten salt at 500°C. To observe the dissolution behavior of rare earth elements, molten salt samples were collected before and after the reactions, and concentration analysis was performed using ICP. After the reaction completed, the remaining oxide was washed with water and separated from the molten salt, and XRD was used for structural analysis. As a result of salt concentration analysis, the dissolution performance of rare earth elements was confirmed in the reaction experiments of all chlorination reagents. In an experiment using NH4Cl and ZrCl4, the uranium concentration in the molten salt was also measured. In other words, it seemed that not only rare elements but also uranium oxide, which is a main component of simfuel, was dissolved. Therefore, it is thought that the dissolution of rare earth elements is also possible due to the collapse of the uranium oxide structure of the solid powder and the reaction with the oxide of rare earth elements exposed to molten salt. As a result of analyzing the concentration changes of Simfuel before and after each reaction, there was little loss of uranium and rare earth elements (Ce/Gd) in the NH4Cl experiment, but a significant amount of rare earth elements were found to be reduced in the UCl3 experiment, and a large amount of rare earth elements were reduced in the ZrCl4 reaction.

Electrochemical reduction has previously been reported for uranium oxide and mixed oxide nuclear fuel (uranium oxide, plutonium oxide). The laboratory scale electrochemical reduction of plutonium oxide powder is demonstrated in CaCl2- 1wt%CaO. The plutonium oxide contained within a permeable steel basket cathode is sacrificed during the process. A graphite anode is also employed during the reduction, leading to a significant contamination of the product.

650의 LiCl-LiO 용융염계에서 10 g UO/batch 규모의 장치를 이용해서 우라늄산화물의 전해환원 특성에 대한 평가를 수행하였다. 일체형 음극은 고체전극, 우라늄산화물과 우라늄산화물을 담아주는 다공성 용기(멤브레인)로 구성된다. 멤브레인 재료로는 325-mesh 스테인레스강막과 다공성 마그네시아 도가니를 사용하였다. 일체형 음극의 재질에 따른 LiCl-3 wt LiO계와 UO-LiCl-3 wt LiO계의 순환 전압측정법 결과로부터 전해환원 반웅 메커니즘을 규명하였다. 일체형 음극의 재질에 따른 우라늄산화물의 직접 및 간접 전해환원에 대한 실험을 수행하였다. 그 결과, 325-mesh스테인레스강막을 사용하여 직접 및 간접 전해환원으로 금속전환을 수행하였을 때 낮은 전류효율로 인해 우라늄산화물을 금속우라늄으로 환원시키지 못했으며, 마그네시아 다공성 도가니를 사용하여 간접 전해환원으로 금속전환을 수행하였을 때는 높은 전류효율로 인해 우라늄산화물을 금속우라늄으로 환원시킬 수 있었다

본 연구에서는 고온의 LiCl-LlO 용융염계에서 우라늄 산화물의 금속전환과 LiO의 전해반응이 동시에 진행되는 통합 반응 메카니즘을 기초로 한 전기화학적 금속전환기술을 제안하였다. 본 실험에서는 전기화학적 환원반응에 의해 생성된 Li 금속이온이 음극에 전착과 동시에 우라늄 산화물과 반응하여 금속전환율 99 % 이상의 우라늄 감속을 생성하는 통합 반응 메카니즘을 확인할 수 있었다. 또한 전기화학적 금속전환기술의 공정 적용성 평가 일환으로 우라늄 산화물의 금속전환성, 반응 메카니즘 규명, LiO의 closed recycle rate 및 물질전달 특성 등의 기초 데이터를 확보하였다 향후 전기화학적 금속전환기술은 LiCl-Li 용융염계의 금속전환공정의 반응조건 제한성 해소, 금속전환율 향상 및 공정의 단순화 등의 기술성과 경제성 향상 측면에서 획기적인 방안으로 고려될 수 있을 것으로 판단된다.