• 방사성폐기물학회지
• /
• 제3권2호
• /
• pp.105-112
• /
• 2005

650$^{\circ}C$의 LiCl-Li$_{2}$O 용융염계에서 10 g U$_{3}$O$_{8}$/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$\%$ Li$_{2}$O계와 U$_{3}$O$_{8}$-LiCl-3 wt$\%$ Li$_{2}$O계의 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

• 한국방사성폐기물학회:학술대회논문집
• /
• 한국방사성폐기물학회 2004년도 학술논문집
• /
• pp.268-277
• /
• 2004

사용후핵연료 차세대 관리공정의 주된 단위 공정인 전기 환원에 의한 금속 전환 공정에서의 핵종 거동 및 분포에 관한 기초 연구의 일환으로 고방열성 핵종인 알카리, 알카리토 금속 산화물들의 고온 용융염에서의 전기 화학적 특성을 측정 분석함으로서 전기 환원 공정에서의 거동을 예상하였다. LiCl-$Li_2O$ 용융염계에서 Cs, Sr 및 Ba은 Li 보다 높은 진위에서 환원되며 환원 전위는 서로 근접해 있는 것으로 측정되었다. 이에 따라 사용후핵연료의 전기 환원 과정에 Li 환원을 매개로 한 반응 메카니즘에 저해를 일으키지 않을 것으로 예측되었다. 알카리, 알카리토 금속의 환원조건에서 공정이 운전될 경우 자유에너지 변화의 계산을 통해 알자리, 알카리토 금속이 용융염으로 재순환됨을 확인 하였으며 전류 범위에 따른 금속 원소의 농도 변화를 측정하여 알카리, 알카리토 금속의 물질 전달에 대한 전류의 영향을 평가하였다.

• 방사성폐기물학회지
• /
• 제18권3호
• /
• pp.415-420
• /
• 2020

Strontium is known as a salt-soluble element during the electrolytic oxide reduction (EOR) process. The chemical behavior of SrO during EOR was investigated via thermodynamic calculations to provide quantitative data on the chemical status of Sr. To achieve this, thermodynamic calculations were conducted using HSC chemistry software for various EOR conditions. It was revealed that SrO reacts with LiCl salt to produce SrCl₂, even in the presence of Li₂O, and that the ratio of SrCl₂ depends on the initial concentration of Li₂O dissolved in LiCl. It was found that SrO reacts with Li to produce Sr during EOR and that the reduced Sr reacts with LiCl salt to produce SrCl₂. As a result, the proportions of metallic forms were lower in Sr than in La and Nd under various EOR conditions. The thermodynamic calculations indicated that the three chemical forms of SrO, SrCl₂, and Sr co-exist in the EOR system under an equilibrium with Li, Li₂O, and LiCl.

• 한국세라믹학회지
• /
• 제51권1호
• /
• pp.25-31
• /
• 2014

New green phosphor is synthesized by reducing $LiAlO_2:xEu^{3+}$ phosphors in a low pressure $H_2$ atmosphere. The $LiAlO_2:xEu^{3+}$ prepared by a solid state reaction method is reported as red phosphor. The effect of the reduction treatment on the $LiAlO_2:xEu^{3+}$ on the crystalline phase change and photoluminescence (PL) property are characterized. The reduced phosphor had a broad green light spectrum centered at 524 nm. The PL intensity of the reduced phosphor increased to a maximum at the reduction temperature of $1100^{\circ}C$. The PL intensity decreased with a further increase in the reduction temperature. The crystalline phase constituting the reduced phosphor varied with the temperature. A new crystalline phase $Li_2Al_4O_7$ was observed at $1100^{\circ}C$. The origin of the green-light emission is discussed in relation to the crystalline phase change.

• 전기화학회지
• /
• 제16권3호
• /
• pp.138-144
• /
• 2013

Electrochemical reductions of $UO_2$ at various anode-to-cathode distances (1.3, 2.3, 3.2, 3.7 and 5.8 cm) were carried out to investigate the effect of the anode-to-cathode distance on the electrochemical reduction rate. The geometry of the electrolysis cell in this study, apart from the anode-to-cathode distance, was identical for all of the electrolysis runs. Porous $UO_2$ pellets were electrolyzed by controlling a constant cell voltage in molten $Li_2O-LiCl$ at $650^{\circ}C$. A steel basket containing the porous $UO_2$ pellets and a platinum plate were used as the cathode and anode, respectively. The metallic products were characterized by means of a thermogravimetric analyzer, an X-ray diffractometer and a scanning electron microscope. The electrolysis runs conducted during this study revealed that a short anode-to-cathode distance is advantageous to achieve a high current density and accelerate the electrochemical reduction process.

• 전기화학회지
• /
• 제18권4호
• /
• pp.156-160
• /
• 2015

파이로프로세싱 전해환원은 사용후핵연료의 재활용을 위해 우라늄산화물을 금속으로 전환하는 공정으로 핵물질을 사용하기 이전에 대체 금속산화물을 이용한 실험을 통해 환원 장치의 성능을 평가하고 개선한다. 본 연구에서는 전해환원 장치 개발을 위한 대체 금속산화물로 타이타늄 산화물(TiO와 $TiO_2$)을 선정하고 $650^{\circ}C$의 $Li_2O$-LiCl 용융염에서의 용해도 및 전해환원 특성을 평가하였다. 1.0 wt.% $Li_2O$-LiCl 용융염에서 TiO와 $TiO_2$의 침지 실험을 통해 두 산화물 모두 염에 일부 용해됨을 확인하였는데, $TiO_2$(2100 ppm)가 TiO(156 ppm)에 비해 더 높은 용해도를 보였다. 1.0 wt.% $Li_2O$-LiCl 용융염에서 TiO와 $TiO_2$의 전해환원을 각각 수행하여 Ti 금속을 성공적으로 제조하였다. 그러나 염 내 용해도가 낮은 TiO는 환원에 사용된 백금 양극 표면에서 Ti이 검출되지 않은 반면 $TiO_2$의 백금 표면에서는 Ti이 검출되었다.

• 한국응용과학기술학회지
• /
• 제20권1호
• /
• pp.33-43
• /
• 2003

$LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

• Nuclear Engineering and Technology
• /
• 제53권5호
• /
• pp.1534-1539
• /
• 2021

This study reports on the dissolution behavior of SrO in LiCl at varying SrO concentrations from low concentrations to excess. The amount of SrO dissolved in the molten salt and the species present upon cooling were determined. The thermal behavior of LiCl containing various concentrations of SrO was investigated. The experimental results were compared with results from the simulated results using the HSC Chemistry software package. Although the reaction of SrO with LiCl in the standard state at 650 ℃ has a slightly positive Gibbs free energy, SrO was found to be highly soluble in LiCl. Experimentally determined SrO concentrations were found to be considerably higher than those present in used nuclear fuel (<2 g/kg). As Sr-90 is one of the most important heat-generating nuclides in used nuclear fuel, this finding will be impactful in the development of fast, simple, and proliferation-resistant heat reduction processes for used nuclear fuel without the need for separating nuclear materials. Heat reduction is important as it decreases both the volume necessary for final disposal and the worker handling risk.

• Bulletin of the Korean Chemical Society
• /
• 제8권3호
• /
• pp.162-165
• /
• 1987

The reduction rate of borohydride exchange resin (BER) was greatly enhanced in the presence of lithium salts. Thus 2-heptanone was reduced completely with BER-LiCl in 1 h at room temperature. However, no reduction was observed with BER alone under the same conditions. With this system, organic compounds containing various fuctional groups were examined in ethanol at room temperature. This study revealed that BER-LiCl system exhibits an excellent chemoselectivity for carbonyl group in the presence of other functional groups. Keto esters and epoxy ketones were reduced with BER-LiCl to give the corresponding hydroxy esters and epoxy alcohols with excellent yields. Selective reductions of carbonyl groups were also possible in the presence of other organic compounds containing functional groups such as 1-idooctane, 1-bromooctane, caproamide, hexanenitrile, nitrobenzene, n-butyl disulfide, dimethyl sulfoxide and 1-dodecene.

• Journal of Electrochemical Science and Technology
• /
• 제5권3호
• /
• pp.87-93
• /
• 2014

The fluorine-substituted $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode materials were synthesized by using the transition metal precursor, $LiOH{\cdot}H_2O$ and LiF. This was to facilitate the movement of lithium ions by forming more compact SEI layer and to reduce the dissolution of transition metals. The $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode material was sphere-shaped and each secondary particle had $10{\sim}15{\mu}m$ in size. The fluorine-substituted cathodes initially delivered low discharge capacity, but it gradually increased until 50th charge-discharge cycles. These results indicated that fluorine substitution gave positive effects on the structural stabilization and resistance reduction in materials.