• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2000년도 하계학술대회 논문집
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• pp.548-551
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• 2000

Spinel phase LiF $e_{y}$M $n_{2-y}$ $O_4$samples are synthesized by calcining a LiOH.$H_2O$, Mn $O_2$and F $e_2$ $O_3$mixture at 80$0^{\circ}C$ for 36h in air. Preparing LiF $e_{y}$M $n_{2-y}$ $O_4$showed spinel phase with cubic phase. The ununiform distortion of the crystallite of the spinel LiF $e_{y}$M $n_{2-y}$ $O_4$was more stable than that of the pure. The discharge capacity of the cathode for the Li/LiF $e_{0.1}$M $n_{1.9}$ $O_4$cell at the first than that of the pure. The discharge capacity of the cathode for the Li/LiF $e_{0.1}$M $n_{1.9}$ $O_4$cell at the first cycle and at the 70th cycle was about 113 and 90mAh/g, respectively. This cell capacity was retained about 82% of the first cycle after 70th cycle. Impedance profile of this cell was more stable than that pure. The resistance, the capacitance and chemical diffusion coefficients of lithium ion showed approximately 80$\Omega$, 36133.87$\mu$F ; 1.4$\times$10$^{-8}$ c $m^2$ $s^{-1}$ , respectively. , respectively.ely.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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• pp.455-458
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• 2001

Spinel $LiMn_{2-y}$$M_{y}$ $O_4$powder was prepared solid-state method by calcining the mixture of LiOH - $H_2O$, Mn $O_2$, ZnO and MgO at 80$0^{\circ}C$ for 36h. To investigate the effect of substitution with Mg, Zn cation, charge-discharge experiments and initial impedance spectroscopy performed. The structure of $LiMn_{2-y}$$M_{y}$ $O_4$crystallites was analyzed from powder X-ray diffraction data as a cubic spinel, space group Fd3m. all cathode material showed spinel phase based on cubic phase in X-ray diffraction. Ununiform which calculated by (111) face and (222) face was constant in spite of the change of y value, except PUf\ulcorner LiM $n_2$ $O_4$. The discharge capacities of the cathode for the cation subbstitUtes $LiMn_{2-y}$$M_{y}$ $O_4$/Li cell at the 1st cycle and at the 40th cycle were about 120~124 and 108~112mAh/g except LiM $n_{1.9}$Z $n_{0.1}$ $O_4$/Li cell, respectively. This cell capacity is retained by 93% after 40th cycle. AC impedance of $LiMn_{2-y}$$M_{y}$ $O_4$/Li cells revealed the similar resistance of about 65~110$\Omega$ before cycling. before cycling.g.g.

• 한국전기전자재료학회논문지
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• 제19권7호
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• pp.650-654
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• 2006

[ $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ ] cathode material was synthesized by a mixed hydroxide method. Structural characterization was carried out using X-ray diffraction studies. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. DSC (Differential scanning calorimetry) data showed that exothermic reactions of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ charged to 4.3 V versus Li started at high temperatures$(280\sim390^{\circ}C)$. The cell of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ mixed cathode delivered a discharge capacity of 150 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of 134 mAh/g was obtained at a 2 C rate. The reversible capacity after 100th cycles was 126 mAh/g when a cell was cycled at a current rate of 0.5 C in $2.8\sim4.3V$.

• 전기화학회지
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• 제16권3호
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• pp.162-168
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• 2013

$Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) 나노 복합체는 높은 이론 용량을 가지고 있어 전기 자동차용 2차 전지 활물질 재료로 많은 연구가 진행되고 있다. 하지만 $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)로부터 250 mAh/g 이상의 용량을 구현하기 위해서는 4.4 V 이상의 구동전압이 필요하며, 이러한 높은 구동 전압은 전지의 수명 및 고온 방치 특성의 저해 요소로 작용하고 있다. 본 연구에서는 이러한 문제점을 개선하기 위해서 FEC (Fluoroethylene carbonate), 플루오로알킬 에테르, $LiPF_6$가 주성분인 신규 전해액(F-based EL)을 설계하였다. F-based EL은 1.3 M $LiPF_6$ EC/EMC/DMC (3/4/3, v/v/v) (STD) 대비 안정한 SEI를 형성하며, 산화 안정성이 뛰어나 $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)/graphite 셀의 수명 및 방치 중 가스 저감에 효과가 있음을 확인할 수 있었다.

• 한국결정성장학회지
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• 제10권3호
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• pp.219-225
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• 2000

스피넬형의 $LiMn_2$O$_4$는 출발물질로 LiOH와 Mn($CH_3$COO)$_2$.$4H_2$O를 사용하여 졸-겔법으로 합성한 xerogel을 $150^{\circ}C$로 1차 열처리한 후 $350^{\circ}C$로 2차 열처리하여 합성하였다. 그러나 $350^{\circ}C$ 이상으로 열처리할 경우 $Mn_2O_3$가 생겼으며, 이로 인해서 Li/lM $LiClO_4$(in PC)$LiMn_2O_4$cell을 구성하여 0.25 mA/$\textrm{cm}^2$의 전류밀도로 충.방전 실험을 한 결과 $350^{\circ}C$에서 열처리한 것은 15 cycle후에 88 mAh/g에서 56 mAh/g으로 35.7%의 용량감소가 나타났으나 $500^{\circ}C$에서 열처리한 것은 89 mAh/g에 51 mAh/g으로 42.5%의 용량감소가 나타났으며 이는 $Mn^{3+}$ 의 증가로 인한 Jahn-Teller distortion의 결과로 볼 수 있다.

• 한국세라믹학회지
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• 제42권7호
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• pp.503-508
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• 2005

A simple and effective method for the synthesis of LiMn$_{2}$O$_{4}$ powder as a cathode material for lithium secondary battery is reported. Micrometer size LiMn$_{2}$O$_{4}$ was prepared by combustion synthesis technique employing initial mixture of l.l LiNO$_{3}$ -1.3Mn-0.7MnO$_{2}$-1NaCl composition. Parametric study of the combustion process including molar ratio of Mn/MnO$_{2}$ and NaCl concentration were carried out under air atmosphere. The combustion products obtained were additionally heat treated at the temperature 900$^{\circ}C$ and the washed by distilled water. The results of charging-discharging characteristics revealed that LiMn$_{2}$O$_{4}$ cell synthesized in the presence of NaCl had a high capacity and much better reversibility than one formed without NaCl An approximate chemical mechanism for LiMn$_{2}$O$_{4}$ formation is proposed.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2002년도 하계학술대회 논문집 Vol.3 No.2
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• pp.707-710
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• 2002

Spinel $LiMn_2O_4$ and $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4$ powders were synthesized by solid-state method at $800^{\circ}C$ for 36h. Crystal structure and electrochemical properties were analyzed by X-ray diffraction, charge-discharge test, cyclic voltammetry and ac impedance to $LiMn_2O_4$ and $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$. All cathode material showed spinel structure in X-ray diffraction. $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cell substituted $Mg^{2+}$ and $Zn^{2+}$ showed excellent discharge capacities than other cells, which it presented about 120mAh/g at the 1st cycle and about 73mAh/g at the 250th cycle, respectively. AC impedance of $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cells showed the similar resistance of about $65{\sim}110{\Omega}$ before cycling.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 춘계학술대회 논문집 센서 박막재료 반도체 세라믹
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• pp.299-305
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• 2003

The battery industries have been developed to the implementation of lithium ion secondary cell from the cell of Ni/Cd and Ni/MH in the past to be asked of an age of high technology from low technology. Also in resent the polymeric cell to get a good high function with an age of new advanced information system is changed from the 21 century to the secondary batteries society. The properties of lithium secondary batteries have the high energy density, the long cycle time, the low self discharge area and the high active voltage. The wanted properties of secondary batteries for the motion of an apparatuses of industries of an high skill age have a small type trend of the energy density and it is become with a strong asking of the industrial society market about the storable medium of the convenience and new power energy. The electrochemical properties is researched for the cell to be synthesised and crystallized the positive active material LiMnO2 of the secondary cell at 9250C to get a new improved data of the electric discharge for that the capacitance of the LiMnO2 thin film that is improving and researching with the properties and a merit and demerit in the this kind of asking.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1598-1602
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• 2009

The particle size of Li[$Ni_{0.2}Li_{0.2}Mn_{0.6}]O_2$ cathode powder was controlled effectively by dispersion using lauric acid as a surfactant. The samples treated by lauric acid showed smaller particles of approximately half the original size compared to the particles of a pristine sample. A structural change due to the dispersion of Li[$Ni_{0.2}Li_{0.2}Mn_{0.6}]O_2$ powder was not detected. The rate performance of the Li[$Ni_{0.2}Li_{0.2}Mn_{0.6}]O_2$ cathode was improved by dispersion using lauric acid, which was likely due to the decrease of the particle size. In particular, a sample dispersed pristine powder using lauric acid (L2) presented a greatly enhanced discharge capacity and capacity retention at a high C rate. The discharge capacity of a pristine sample was only 133 m$Ahg^{-1}$ (3C rate) and 96 m$Ahg^{-1}$ (12C rate) at the tenth cycle. In contrast, the L2 electrode delivered higher discharge capacities of 160 m$Ahg^{-1}$ (3C rate) and 129 m$Ahg^{-1}$ (12C rate) at the tenth cycle. The capacity retention at a rate of 12C/2C was also enhanced from ~ 45% (pristine sample) to 57% (L2) by treatment with lauric acid.

• 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.