• 한국결정학회:학술대회논문집
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• 한국결정학회 2002년도 정기총회 및 추계학술연구발표회
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• pp.16-16
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• 2002

The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).

• 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.

• Journal of Electrochemical Science and Technology
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• 제3권1호
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• pp.29-34
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• 2012

The structural changes of $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material for lithium ion battery during the first charge was investigated in comparison with $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$ using a synchrotron based in situ X-ray diffraction technique. The structural changes of these two cathode materials show similar trend during first charge: an expansion along the c-axis of the unit cell with contractions along the a- and b-axis during the early stage of charge and a major contraction along the c-axis with slight expansions along the a- and b-axis near the end of charge at high voltage limit. In $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode, however, the initial unit cell volume of H2 phase is bigger than that of H1 phase since the c-axis undergo large expansion while a- and b- axis shrink slightly. The change in the unit cell volume for $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ during charge is smaller than that of $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$. This smaller change in unit cell volume may give the $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material a better structural reversibility for a long cycling life.

• 전기화학회지
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• 제16권4호
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• pp.191-197
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• 2013

리튬2차전지용 양극소재인 $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$를 공침법을 이용해 $Ni_{0.5}Co_{0.2}Mn_{0.3}(OH)_2$ 전구체로부터 합성하였고, 공침조건을 조절하여 전구체의 1차 입자 형상을 Flake형상과 Needle형상으로 제어하였다. 동일한 공정으로 리튬과 혼합하고 열처리하여, 입도, 탭밀도, 화학적 성분 등이 동일한 분체물성의 양극 소재를 합성하였다. 전구체의 1차입자 형상에 따른 $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$의 전기화학적 특성을 평가하고, 이 특성의 변화를 SEM, XRD, EELS로 이용하여 분석하여 연관성을 고찰하였다. Needle형상 전구체로 합성한 $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$ 양극의 1차입자는 Flake형상 전구체로 합성한 경우보다 작고, EELS결과로는 입자표면의 Li농도가 내부보다 상대적으로 높았다. 전기화학적인 수명과 출력특성에서 Needle형상 전구체로 합성한 양극이 Flake형상 전구체의 경우보다 우수한 특성을 보였는데, 임피던스 측정으로부터 낮은 전하이동저항에 연관되어 있을 것으로 생각된다.

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

• 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.

• 한국전기전자재료학회논문지
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• 제20권5호
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• pp.443-449
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• 2007

The structural and thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ electrode during cycling process was studied. The sample was prepared by simple combustion method. Although there were irreversible changes on the initial cycle, O3 stacking for $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ structure was retained during the first and subsequent cycling process. Impedance of the test cell was decreased after the first charge-discharge process, which would be of benefit to intercalation and deintercalation of lithium ion on subsequent cycling. As expected, cycling test for 75 times increased impedance of the cell a little, instead, thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ was improved. Moreover, based on DSC analysis, the initial exothermic peak was shifted to high temperature range and the amount of heat was also decreased after cycling test, which displayed that thermal stability was not deteriorated during cycling.

• 전기화학회지
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• 제16권2호
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• pp.59-64
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• 2013

$Na_2CO_3$와 [M($SO_4$)(M = Ni, Co, Mn)]을 사용함으로써, Carbonate 공침 합성법에 의해 $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ 전구체를 합성하였다. 합성된 전구체는 공기분위기에서 $Li_2CO_3$와 혼합하여 각각, 750, 850 그리고 $950^{\circ}C$에서 소성되었고, 이로 인한 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ 양극활 물질의 소성온도가 미치는 영향을 조사하였다. $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$의 구조와 특성은 X-선 회절 분석(XRD), 시차주사현미경(SEM) 그리고 전기화학적 측정으로 분석되었는데, X-선 회절 결과 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 소성온도가 증가함에 따라서 $I_{(003)}/I_{(104)}$는 증가하고 R-factor 는 감소하였으며, 시차주사현미경 결과에서는 1차 입자의 크기가 증가하는 경향을 보였다. 특히, $950^{\circ}C$에서 24시간 동안 소성된 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 가역 용량이 $165.3mAhg^{-1}$[cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] 그리고 50번째 충 방전 사이클 [cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)]까지 95.4%의 우수한 용량 보존율을 가지면서 가장 우수한 전기화학적 특성을 보여주었다.

• Journal of Electrochemical Science and Technology
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• 제5권1호
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• pp.32-36
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• 2014

The $0.3Li_2MnO_3{\cdot}0.7LiMn_{0.55}Ni_{0.30}Co_{0.15}O_2$ cathode material was prepared via a co-precipitation method. The vapor grown carbon fiber (VGCF) was used as a conductive material and its effects on electrochemical properties of the $0.3Li_2MnO_3{\cdot}0.7LiMn_{0.55}Ni_{0.30}Co_{0.15}O_2$ cathode material were investigated. From the XRD pattern, the typical complex layered structure was confirmed and a solid solution between $Li_2MnO_3$ and $LiMO_2$ (M = Ni, Co and Mn) was formed without any secondary phases. The VGCF was properly distributed between cathode materials and conductive sources by a FE-SEM. In voltage profiles, the electrode with VGCF showed higher discharge capacity than the pristine electrode. At a 5C rate, 146 mAh/g was obtained compared with 232 mAh/g at initial discharge in the electrode with VGCF. Furthermore, the impedance of the electrode with VGCF did not changed much around $9-10{\Omega}$ while the pristine electrode increased from 21.5${\Omega}$ to $46.3{\Omega}$ after the $30^{th}$ charge/discharge cycling.

• 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.