• 한국수소및신에너지학회논문집
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• 제15권1호
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• pp.62-71
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• 2004

$LiMn_{1.92}Co_{0.08}O_4-x\;wt.%LiNi_{0.7}Co_{0.3}O_2$를 단순화한 연소법에 의하여 합성하고, 그것들의 전기화학적 특성을 조사하였다. 또한 30분동안 밀링하여 준비한 $LiMn_{1.92}Co_{0.08}O_4-x\;wt.%LiNi_{0.7}Co_{0.3}O_2$ (x=9, 23, 33, 41 and 47) 혼합물 전극의 전기화학적 특성을 조사하였다. x=33 조성의 전극이 가장 큰 초기방전용량(132.0mAh/g at 0.1C)을 나타내었다. x=9조성의 전극은 비교적 큰 초기방전용량(109.9mAh/g at 0.1C)과 우수한 싸이클 특성을 나타내었다. 싸이클링에 따른 혼합물 전극의 방전용량의 감소는 주로 $LiNi_{0.7}Co_{0.3}O_2$의 퇴화에 기인한다고 생각된다. 그런데 $LiNi_{0.7}Co_{0.3}O_2$의 퇴화는 $LiMn_{1.92}Co_{0.08}O_4$로부터 용해된 Mn이 $LiNi_{0.7}Co_{0.3}O_2$를 둘러쌈(coating)으로써 야기되는 것으로 생각된다.

• 한국분말재료학회지
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• 제21권4호
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• pp.286-293
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• 2014

The electrochemical properties of cells assembled with the $LiNiO_2$ (LNO) recycled from cathode materials of waste lithium secondary batteries ($Li[Ni,Co,Mn]O_2$), were evaluated in this study. The leaching, neutralization and solvent extraction process were applied to produce high-purity $NiSO_4$ solution from waste lithium secondary batteries. High-purity NiO powder was then fabricated by the heat-treatment and mixing of the $NiSO_4$ solution and $H_2C_2O_4$. Finally, $LiNiO_2$ as a cathode material for lithium ion secondary batteries was synthesized by heat treatment and mixing of the NiO and $Li_2CO_3$ powders. We assembled the cells using the $LiNiO_2$ powders and evaluated the electrochemical properties. Subsequently, we evaluated the recycling possibility of the cathode materials for waste lithium secondary battery using the processes applied in this work.

• 전기화학회지
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• 제13권4호
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• pp.264-269
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• 2010

$LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$의 리튬이온 이차전지 양극 물질로의 특성을 연구하기 위해서 단순 연소합성법을 이용하여 합성했다. 합성된 물질의 구조적 특징을 분석하기 위하여 X-선 회절분석(XRD)과 주사전자현미경 (FE-SEM)을 측정하였다. X-선 회절분석을 통하여 합성된 $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$시료가 육방정계 층상구조가 형성된 것을 확인하였다. FE-SEM을 통해 측정한 결과 $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ 입자는 일정한 형태를 가지지 않았으며 크기는 대략 100~300 nm의 크기임을 확인할 수 있었다. 그리고 전기화학적 특성을 측정하기 위하여 충 방전 용량 측정과 CV(Cyclic Voltammetry)를 측정하였다. 2.8 V에서 4.3 V까지 충 방전 용량을 측정한 결과 ~162 mAh/g의 초기 방전 용량을 가졌다.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2001년도 춘계총회 및 학술발표회
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• pp.55-55
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• 2001

• 전기화학회지
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• 제8권2호
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• pp.82-87
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• 2005

고전압 용 양극산화물 $LiNi_{0.5}Mn_{1.5}O_4$는 고온에서 합성 시, 입자 내에 산소결함에 의한 불순물상을 만들게 된다. 불순물상은 불완전한 스피넬 구조를 형성하며 리튬이온의 삽입$\cdot$탈리를 방해하여 전극의 성능을 감소시킨다. 본 연구에서는 고온 열처리 시 생성되는 이러한 불순물상의 거동을 파악하기 위해 크롬을 치환한 $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$를 졸$\cdot$겔법을 이용하여 합성하여 고온 열분석을 실시하였다. 열분석 결과 크롬이 치환되지 않은 양극활물질은 산소결함에 의한 $2\%$의 무게 감소를 보였으나, 크롬이 치환된 경우 무게 감소분이 줄어들어 불순물 생성이 억제됨을 알 수 있었다. XRD 분석에서도 크롬이 치환된 경우 불순물 상이 억제됨을 나타내었으며 불순물상의 감소로 인해 크롬을 첨가한 양극활물질 $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$를 사용한 경우 충·방전 실험 시 가역 용량과 싸이클 안정성이 향상됨을 볼 수 있었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2006년도 하계학술대회 논문집 Vol.7
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• pp.348-349
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• 2006

$LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode material was synthesized by a mixed hydroxide methode. The surface of the $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ was coated with a carbon by using a sol-gel method to improve further its electrochemical properties. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. OSC (differential scanning calorimetry) data showed that exothermic reactions of charged to 4.3V vs. Li was suppressed in the carbon-coated materials. The carbon-coated $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ showed the improved rate capability and thermal stability.

• Bulletin of the Korean Chemical Society
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• 제23권5호
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• pp.679-682
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• 2002

Layered Na0.7[Ni0.05Mn0.95]O2 compounds have been synthesized by a sol-gel method, using glycolic acid as a chelating agent. Na0.7[Ni0.05Mn0.95]O2 precursors w ere used to prepare layered lithium manganese oxides by ion exchange for Na by Li, using LiBr in hexanol. Powder X-ray diffraction shows the layered Na0.7[Ni0.05Mn0.95]O2 has an O3 type structure, which exhibits a large reversible capacity of approximately 190 mA h g-1 in the 2.4-4.5 V range. Na0.7[Ni0.05Mn0.95]O2 powders undergo transformation to spinel during cycling.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2603-2607
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• 2009

$LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ (x = 0, 0.1, 1/6, 1.2, 0.3) were synthesized by the solid-state reaction method. The crystal structure was analyzed by X-ray powder diffraction and Rietveld refinement. $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ samples give single phases of hexagonal layered structures with a space group of R-3m for x = 0.1, 1/6, 0.2, and 0.3. The lattice constants of a and c-axis were decreased with the increase in Co contents in samples. The thickness of MO2 slab was decreased and inter-slab distance was increased with the increase in Co contents in $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$. According to XPS analysis, the valence states of Mn, Co, and Ni in the sample are mainly +4, +3, and +3, respectively. The discharge capacity of 202 mAh/g at 0.1C-rate in the potential range of 4.7 - 3.0 V was obtained in $LiNi_{0.3}Co_{0.4}Mn_{0.3}O_2$ sample, and $LiNi_{0.4}Co_{0.2}Mn_{0.4}O_2$ gives excellent cycle performance in the same potential range.

• 한국세라믹학회지
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• 제38권5호
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• pp.424-430
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• 2001

Cut-off 전압 변화에 따른 충방전 특성을 알아보기 위하여 Mn을 다른 전이 금속이 Co와 Ni로 소량 치환시킨 Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$(M=Ni, Co, $\delta$=0, 0.05, 0.1, 0.2)를 고상 반응법으로 80$0^{\circ}C$에서 48시간 동안 유지하여 합성하였다. 충방전의 cut-off 전압은 2.5~4.4V, 3.0~4.5V, 3.5~4.5V, 3.5V~4.7V의 네 가지 전압범위고 하였다. 충방전 실험결과, Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$의 용량은 각각 Co와 Ni의 $\delta$=0.1에서 최대를 보였다. Co 치환 조성 재료와 순물질 모두에서 최대의 용량을 보인 cut-off 전압대는 3.5~4.5V 이었는데 이때의 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$와 LiM $n_2$ $O_4$의 초기 충전용량과 초기 방전용량은 각각 118, 119mAh/g과 114, 104mAh/g 이었다. 또한 모든 cut-off 전압대에서 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$는 순수한 LiM $n_2$ $O_4$보다 더 높은 용량과 우수한 싸이클 성능을 보였으며 그 결과는 밀착형 전지구성에서도 일치하였다.하였다.