• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.21 no.11
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• pp.1029-1035
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• 2008

$LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ cathode materials prepared from different precursors in lithium rechargeable batteries were characterized by various analytical methods. $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ powders were synthesized by using solid-state reaction method and their physical and chemical properties were analyzed by XRD, SEM, particle size analyzer and TCP-AES. These materials showed different crystallinity, particle size, surface morphology and chemical composition. Also, the charge/discharge cycling of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ electrodes was carried out under various cut-off voltages and it showed different behaviors. It was found that the electrochemical cyclability of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was strongly related to its crystallinity.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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• pp.318-319
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• 2005

본 연구에서는 $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ 혼합 정극활물질로 사용하여 전극을 제작하고 성능을 평가하였다. $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$와 $LiCoO_2$의 혼합비에 따른 충방전 거동 및 임피던스 변화를 측정하였다. 각 조성에서의 초기용량은 160 ~ 170 mAh/g 정도였으며, $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$의 첨가 비율이 증가함에 따라 비용량이 증가하였으나 고율에서의 방전용량은 낮았다.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.1
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• pp.64-70
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• 2006

In this study, the $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the content of $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ increased in a mixed cathode, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability was deteriorated. On the contrary the rate capability of the cathode enhanced, but the reversible specific capacity and cycleability were deteriorated, increasing the content of $LiCoO_2$ in the mixed cathode. The cell of $LiCoO_2/LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ ($50:50 wt\%$) mixed cathode delivered a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell showed very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.29 no.5
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• pp.298-302
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• 2016

In this work, $LiMn_2O_4$ and $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode materials are mixed by some specific ratios to enhance the practical capacity, energy density and cycle performance of battery. At present, the most used cathode material in lithium ion batteries for EVs is spinel structure-type $LiMn_2O_4$. $LiMn_2O_4$ has advantages of high average voltage, excellent safety, environmental friendliness, and low cost. However, due to the low rechargeable capacity (120 mAh/g), it can not meet the requirement of high energy density for the EVs, resulting in limiting its development. The battery of $LiMn_2O_4-LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ (50:50 wt%) mixed cathode delivers a energy density of 483.5 mWh/g at a current rate of 1.0 C. The accumulated capacity from $1^{st}$ to 150th cycles was 18.1 Ah/g when the battery is cycled at a current rate of 1.0 C in voltage range of 3.2~4.3 V.

• Journal of Electrochemical Science and Technology
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• v.3 no.1
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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.

• Journal of the Korean Electrochemical Society
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• v.11 no.3
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• pp.197-210
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• 2008

The cathode materials for lithium ion battery have been developed in accordance with the battery performance. $LiCoO_2$ initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of $LiCoO_2$. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are $LiNi_{1-x}{M_xO_2}$, $Li[Ni_{x}Mn_{y}Co_{z}]O_{2}$, $Li[{Ni}_{1/2}{Mn}_{1/2}]O_{2}$. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. ${LiMn}_{2}{O}_{4}$ and $LiFePO_4$ are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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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.

• Journal of Powder Materials
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• v.25 no.4
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• pp.296-301
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• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.2
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• pp.139-144
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• 2006

A fabrication condition of the cathode electrode was optimized in a lithium secondary battery. The $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ powders were used as a cathode material. The $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$/Li cells were prepared with a certain formulation and their cycleability and rate-capability were evaluated. Optimum electrode composition simulated from the evaluated value was 86.3: 5.6: 8.1 in mass $\%$ of active material: binder: conducting material. Discharge capacity decreased markedly as the press ratio exceeded $30\%$ during preparation of the electrode. Discharge performance at a high current rate deteriorated abruptly as the electrode thickness was over $120{\mu}m$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.06a
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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.