• Proceedings of the Korean Radioactive Waste Society Conference
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• 2009.11a
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• pp.346-346
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• 2009

산화물 형태 사용후핵연료의 효율적 처분 혹은 재활용을 위한 연구 가운데, 고온의 LiCl 용융염 중에서 전해환원하여 금속으로 환원시킨 후, 환원된 금속을 고온의 LiCl-KCl 용융염에서 전해정련하는 연구가 국내외적으로 활발하게 진행되고 있다. 전해환원을 위해 일정 농도 $Li_2O$가 LiCl 용융염에 첨가되며 $Li_2O$ 농도가 높으면 반응 재질의 부식성이 크게 증가하므로 일반적으로 우라늄 산화물은 1wt% 이하의 $Li_2O$ 농도에서 전해환원 된다. 우라늄 산화물의 전해환원 전위는 $Li_2O$의 전해환원 전위 보다 표준 상태를 기준으로 공정온도인 650 $^{\circ}C$ 에서 약 70 mV 정도 낮기 때문에 전해환원 과정에서 $Li_2O$ 의 환원으로 Li 금속이 생성될 가능성이 있으며 우라늄 산화물은 대부분 직접 전해환원 되지만 일부 Li에 의해 화학적으로 환원되기도 한다. 전해환원 공정에서 환원되지 않은 희토류 산화물은 전해정련 공정에서 $UCl_3$와 반응하여 $UO_2$를 생성시켜 공정 효율을 떨어뜨린다. 따라서 전해환원 공정에서 가능하연 최대한 희토류 산화물을 금속으로 환원시키는 조건을 찾아내는 것이 바람직하고 이를 위해서 우선 전해환원 공정에서 희토류 산화물의 화학적 거동의 이해가 요구된다. 본 연구에서 열역학적 검토를 통하여 희토류 산화물의 환원 조건을 조사한 결과 희토류 산화물은 매운 낮은 $Li_2O$ 농도에서 Li에 의해 환원되고, 1wt% 이하의 $Li_2O$ 농도에서는 Sc와 Lu의 산화물이 $Li_2O$와 복합산화물을 형성하고 이들 복합산화물은 Li에 의해 환원되지 않는 것으로 나타났다. 또한 희토류 원소 별로 희토류 원소 산화물의 Li에 의한 환원 조건으로서 평형상태에서의 $Li_2O$ 농도 즉 환원 임계 $Li_2O$ 농도를 실험적으로 측정하였으며 1wt% $Li_2O$ 농도 이하에서 열역학적 해석과 동일하게 Sc와 Lu만이 복합산화물을 형성하여 Li에 의해 직접환원 되지 않는 것으로 관찰되었다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1996.05a
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• pp.228-231
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• 1996

We prepared $LiCo_{1-x}Ni_{x}O_2$ by reacting stoichiometric mixture of LiOH.$H_2O$, $CoCO_3$.$xH_2O$ and $Ni(OH)_2$ (mole ratio respectively) and heating at $850^{\circ}C$ for 5h. We awared through XRD that from 0 to 0.5 at x in $LiCo_{1-x}Ni_{x}O_2$ is well formed for hexagonal structure, but the more $LiCo_{1-x}Ni_{x}O_2$ involve NI, the more hexagonal structure is not well formed. In the result of charge/discharge test, charge/discharge characteristic of $LiCo_{1-x}Ni_{x}O_2$ is similar to that of $LiCoO_2$. Therefore, $LiCo_{1-x}Ni_{x}O_2$ is superior to $LiCoO_2$ for Li secondary battery

• Journal of the Korean Ceramic Society
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• v.48 no.6
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• pp.531-536
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• 2011

Al doped $LiMn_2O_4$ ($LiMn_2O_4:Al$) synthesized by several Al doping process and Solid State method. The Al contents in $Mn_{1-x}Al_xO_2$ for $LiMn_2O_4:Al$ were analyzed 1.7 wt% by EDS. The $LiMn_2O_4:Al$ confirmed cubic spinel structure and approximately 5 ${\mu}m$ particles regardless of three kinds of doping process by solid state method. In the result of electrochemical performances, initial discharge capacity had 115 mAh/g in case of $LiMn_2O_4$ and 111 mAh/g of $LiMn_2O_4:Al$ after 100th cycle at room temperature. But the capacity retention results showed that $LiMn_2O_4$ and $LiMn_2O_4:Al$ were 44% and 69% respectively in the 100th cycle at 60$^{\circ}C$. Therefore we are confirmed that $LiMn_2O_4:Al$ increased the capacity retention about 25% than $LiMn_2O_4$, thus the effect of Al dopping on $LiMn_2O_4$ capacity retention.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.774-780
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• 1998

For the stabilization of the spinel structured $LiMn_2O_4$, a fraction of manganese was substituted with various metals such as Mg, Fe, V, W, Cr, Mo with Mn that had a similar ionic radii ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$). The $LiM_xMn_{2-x}O_4$ showed a substantial improvement as lower capacity loss than that of the spinel structured $LiMn_2O_4$ when it was used as a cathode material. And with the partial substitution, the chemical diffusion coefficient for $LiMg_{0.05}Mn_{1.9}O_4$ and $LiCr_{0.1}Mn_{1.9}O_4$ was increased by and order of magnitude compared to that of the $LiMn_2O_4$ with spinel structure. The results showed that significant improvement can be made on the electrochemical characteristics as the structure of the $LiMn_2O_4$ electrode material was stabilized by the partial substitution.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.5
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• pp.398-402
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• 2012

Synthesis of $Li_2MnSiO_4$ was attempted by the conventional solid-state reaction method, and the phase formation behavior according to the change of the calcination condition was investigated. When the mixture of the three source materials, $Li_2O$, MnO and $SiO_2$ powders, were used for calcination in air, it was difficult to develop the $Li_2MnSiO_4$ phase because the oxidation number of $Mn^{2+}$ could not be maintained. Therefore, two-step calcination was applied: $Li_2SiO_3$ was made from $Li_2O$ and $SiO_2$ at the first step, and $Li_2MnSiO_4$ was synthesized from $Li_2SiO_3$ and MnO at the second step. It was easy to make $Li_2MnSiO_3$ from $Li_2O$ and $SiO_2$. $Li_2MnSiO_4$ single phase was developed by the calcination at $900^{\circ}C$ for 24 hr in Ar atmosphere as the oxidation of $Mn^{2+}$ was prevented. However, the $Li_2MnSiO_4$ was ${\gamma}-Li_2MnSiO_4$, one of the polymorph of $Li_2MnSiO_4$, which could not be used as the cathode materials in Li-ion batteries. By applying the additional low temperature annealing at $400^{\circ}C$, the single phase ${\beta}-Li_2MnSiO_4$ powder was synthesized successfully through the phase transition from ${\gamma}$ to ${\beta}$ phase.

• Journal of the Korean Ceramic Society
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• v.37 no.5
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• pp.466-472
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• 2000

As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.14 no.4
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• pp.309-315
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• 2001

Crystallized $LiMn_{2-y}Mg_{y}O_4$ powder was prepared by calcing the mixture of LiOH.$H_2O$, $MnO_2$ and MgO at $800^{\circ}C$ for 36h in an air atmosphere. The structure of $LiMn_{2-y}Mg_{y}O_4$ crystallites was analyzed from powder X-ray diffraction data as a cubic spinel, space group Fd3m. Though all cathode material showed spinel phase based on cubic phase in X-ray diffraction, other peaks gradually exhibited and became intense with increasing y value in $LiMn_{2-y}Mg_{y}O_4$. However, ununiform which calculated by (111) face and (222) face was constant in spite of the increase of y value, except pure $LiMn_2O_4$. AC impedance of Li/$LiMn_{2-y}Mg_{y}O_4$ cells revealed the similar resistance of about $70\Omega$ before cycling. In addition, The impedance of Li/$LiMn_{1.9}Mg_{0.1}O_4$ cell changed during charge and discharge or after cycling.

• Korean Journal of Materials Research
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• v.14 no.11
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• pp.813-820
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• 2004

The electrolytic reduction of spent oxide fuel involves the liberation of oxygen in a molten LiCl electrolyte, which is a chemically aggressive environment that is very corrosive for typical structural materials. So, it is essential to choose the optimum material for the process equipment handling molten salt. In this study, corrosion behavior of Haynes 263, 75, and Inconel X-750, 718 in molten salt of $LiCl-Li_{2}O$ under oxidation atmosphere was investigated at $650^{\circ}C\;for\;72\sim360$ hours. At $3\;wt\%\;of\;Li_{2}O$, Haynes 263 alloy showed the highest corrosion resistance among the examined alloys, and up to $8\;wt\%\;of\;Li_{2}O$, Haynes 75 exhibited the highest corrosion resistance. Corrosion products were formed $Li(Ni,Co)O_2,\;LiNiO_2\;and\;LiTiO_2\;and\;Cr_{2}O_3$ on Haynes 263, $Cr_{2}O_3,\;NiFe_{2}O_4,\;LiNiO_2,\;Li_{2}NiFe_{2}O_4,\;Li_{2}Ni_{8}O_10$ and Ni on Haynes 75, $Cr_{2}O_3,\;(Al,Nb,Ti)O_2,\;NiFe_{2}O_4,\;and\;Li_{2}NiFe_{2}O_4$ on Inconel X-750 and $Cr_{2}O_3,\;NiFe_{2}O_4\;and\;CrNbO_4$ on Inconel 718, respectively. Haynes 263 showed local corrosion behavior and Haynes 75, Inconel X-750, 718 showed uniform corrosion behavior.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.399.1-399.1
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• 2016

p-type 반도체 물질로 알려진 $Cu_2O$에 Li 이온을 doping하면 Cu 이온 자리에 Li이온이 치환되어 p-type의 특성이 더욱 강하게 나타내는 것으로 알려져 있다. 이에 본 연구에서는 RF magnetron sputtering방법으로 성막한 p-type형 $Li:Cu_2O$박막의 특성을 연구하고 이를 $Li:Cu_2O-ZnO$ pn 접합 유연 나노제너레이터에 적용하였다. $Li:Cu_2O$ 성막시 $O_2$ 분압을 변수로 100nm 두께의 $Li:Cu_2O$ 박막을 성막하여 전기적, 광학적, 구조적, 표면 특성을 분석하였다. Hall measurement 측정 결과 $Li:Cu_2O$ 박막은 정공을 Major Carrier로 갖는 p-type 반도체임을 확인하였고, $O_2$의 분압이 증가할수록 Mobility 및 Carrier Concentration이 증가함을 확인하였다. 최적조건에서 광학적 투과도는 약 45%를 보였으며, 투과도를 통해 계산한 band gap은 약 2.03eV로써 일반적인 산화물 반도체의 작은 밴드갭을 가지고 있음을 알 수 있었다. 또한 Ellipsometer분석을 통해 $Ar:O_2$ 비가 $Li:Cu_2O$ 굴절률 및 흡광도에 미치는 영향을 연구하였으며, FE-SEM(Field Emission Scanning Electron Microscope)을 통해 표면을 분석하였다. 또한 XRD(X-ray diffractometer), TEM(Transmission Electron Microscope) 분석을 통하여 상온에서 성막한 $Li:Cu_2O$ 박막의 미세구조를 연구하였다. UPS(Ultraviolet Photoelectron Spectroscopy) 분석을 통해 일함수를 측정하였다. 이렇게 제작된 p 타입 $Li:Cu_2O$ 박막을 이용하여 $Li:Cu_2O-ZnO$ pn 접합을 구현하고 이를 이용해 유연 나노제너레이터를 제작하였다. 다양한 특성 분석을 통해p-type을 이용한 산화물 박막 기반 유연 나노 제너레이터 특성 향상 메커니즘을 제시하였다.

• Archives of Metallurgy and Materials
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• v.64 no.2
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• pp.481-485
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• 2019

This study was attempted to study for recovery of Li as Li₂CO₃ from cathode active material, especially NCA (LiNiCoAlO₂), recovered from spent lithium ion batteries. This consists of two major processes, carbonation using CO₂ and water leaching. Carbonation using CO₂ was performed at 600℃, 700℃ and 800℃, and NCA (LiNiCoAlO₂) was phase-separated into Li₂CO₃, NiO and CoO. The water leaching process using the differences in solubility was performed to obtain the optimum conditions by using the washing time and the ratio of the sample to the distilled water as variables. As a result, NCA (LiNiCoAlO₂) was phase-separated into Li₂CO₃ and NiO, CoO at 700℃, and Li₂CO₃ in water was recovered through vacuum filtration after 1 hour at a 1:30 weight ratio of the powder and distilled water. Finally, Li₂CO₃ containing Li of more than 98 wt.% was recovered.