• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2000.04b
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• pp.117-120
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• 2000

The relation of crystal phase and charge/discharge capacity of $Li[Li_yMn_{2-y}]O_4$ were studied for different degrees of Li substitution (y). All cathode material showed spinel phase based on cubic phase in X-ray diffraction. Other peaks didn't show in spite of the increase of y value in $Li[Li_yMn_{2-y}]O_4$. Ununiform of $Li[Li_yMn_{2-y}]O_4$ which calcinated by (111) face and (222) face was more stable than that of pure $LiMn_2O_4$. In addition, At TG analysis, calcined $Li[Li_{0.1}Mn_{1.9}]O_4$ exhibited much mass loss at $800{\mu}m$. The cycle performance of the $Li(Li_yMn_{2-y}]O_4$ was improved by the substitution of $Li^{1+}$ for $Mn^{3+}$ in the octahedral sites. Specially, $Li[Li_{0.08}Mn_{1.92}]O_4$ and $Li[Li_{0.1}Mn_{1.9}]O_4$ cathode materials showed the charge and discharge capacity of about 125mAh/g at first cycle, and about 95mAh/g after 70th cycle. It is excellent than that of pure $LiMn_2O_4$, which 125mAh/g at first cycle, 65mAh/g at 70th.

• 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.

• Journal of the Korean Vacuum Society
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• v.20 no.3
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• pp.205-210
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• 2011

Structural and electrochemical properties of spinel oxide $LiMn_2O_4$ thin films prepared by using a sol-gel method on Pt/Ti/$SiO_2$/Si substrates were investigated. When Li/Mn molar ratio of the film was smaller than 0.5, $Mn_2O_3$hase was found to coexist with $LiMn_2O_4$. Half-cell batteries fabricated using the $LiMn_2O_4$ films as the cathode were put into chargedischarge (C-D) cycles and the change in structural properties of the cathode after the cycles was examined by X-ray diffraction and Raman spectroscopy. As the C-D cycle number increases, the discharge capacity of pure $LiMn_2O_4$ battery gradually decreases, being reduced to 72% of the initial capacity at 300 cycles. Such capacity fading is attributable to the decrease in the number of $Li^+$ ions that return to the tetrahedral sites of the spinel structure during the discharge step and the resultant increase in $Mn^{4+}$ density in the film. Also, $Mn_2O_3$ phase gradually appeared in the film as the cycle number increases.

• Journal of the Korean Ceramic Society
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• v.36 no.9
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• pp.930-936
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• 1999

For LiMn2O4 based spinel structures the stoichiometric reaction conditions need be considered carefully because the electrical properties depend on the structural stability. In order to obtain the homogeneous compound the Pechini process was chosen which could obtain a stoichiometry phase even low temperature and dependency of the synthetic condition on structural stability and electrochemical performance was investigated. X-ray diffraction studies showed that the compounds doped with transition metal have smaller lattice constants than those un doped. The dc conductivity was evaluated by a four probe method in the low and high temperature region respectively. The variations of basal spacings for the cathode were detected to be dependent on the extent of current flows (under dc)

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1153-1158
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• 1997

The powder characteristics of LiMn2O4 prepared by the citrate sol-gel method have been investigated. The optimum pH for the preparation of homogeneous citrate gel was calculated by the theoretical consideration of thermodynamic equilibrium constants for metal-citrate complexes and metal salts. The obtained citrate gel was prefired at 300 ℃ and calcined at 300-700 ℃ for 1 h. The obtained powders were characterized by TG/DSC, FT-IR spectrometer, X-ray diffractometer, SQUID magnetometer, SEM, and particle size analyzer. It was observed that the mixed phases of spinel LiMn2O4 and Mn3O4 were transformed into spinel LiMn2O4 phase and the vibrational bands due to the carbonate and nitrate were also disappeared over 400 ℃. At temperatures below 150 K, inverse molar susceptibilities of every sample began to show an antiferromagnetic ordering of Mn magnetic moments.

• Korean Journal of Crystallography
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• v.15 no.1
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• pp.44-50
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• 2004

Spinel structured lithium managanese oxide $(LiMn_2O_4)$ powder with well defined facetted morphology was prepared by precipitation-evaporation method. {111}, {110}, and {100} planes are mainly observed in the $LiMn_2O_4$ powder. And powder shape of tetradecahedron and octahedron was observed depending on the calcinations temperature. The observed powder morphology observed seemed to be related to the nonstoichiometry of the oxygen in the $LiMn_2O_4$ spinel structure. Oxygen nonstoichiometry might be responsible for the Jahn-teller effect and structure transition which in turn affects the surface energy of the {111}, {110}, and {100} planes. Powder shape transition from tetradecahedron to octahedron seemed to be related to the surface energy of the {111}, {110}, and {100} planes with oxygen nonstoichiometry.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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• pp.418-419
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• 2005

$\o-LiMnO_2$ is known to have poor cycle performance causing the irreversible phase transformation on cycling. In this paper, the effect of chemical substitution on improving cycle performance of $o-LiMnO_2$ was studied at the compositions of $LiCr_xMn_{1-x}O_2$(x=0, 0.1, 0.2, 0.4). XRD is showed that structure of $LiCr_xMn_{1-x}O_2$ transformed from orthorhombic to spinel according to the increase of substitute degree. For lithium ion battery applications, $LiCr_xMn_{1-x}O_2$/Li cell were characterized electrochemically by charge/discharge cycling.

• 한국신재생에너지학회:학술대회논문집
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• 2007.11a
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• pp.125-128
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• 2007

In these recent years, low cost and stable battery electrode materials have been studied for HV/HEV application. Spinel cathode material $LiMn_2O_4$ is widely studied as a promising cathode material of lithium ion secondary batteries because of it is low cost, easily to be prepared and capable to be operated in high voltage range. In this study, $LiMn_2O_4$ was undergoing surface modification with spinel lithium titanium oxide by sol-gel method in order to enhance its capacity retention. Properties of both unmodified and surface-modified $LiMn_2O_4$ were characterized by XRD, SEM, particle size analyzer while their cycling performance was tested with charge and discharge tester.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.18 no.8
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• pp.702-707
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• 2005

Spinel $LiMn_2O_4$ has become appealing because manganese is inexpensive and environmentally benign. In general, cathodes for lithium ion batteries include carbon as a conductive agent that provides electron transfer between the active material and the current collector. In this work, we selected Acetylene Black and Super P Black as conductive agents, and then carried out their comparative investigation for the performances of the $Li/LiMn_2O_4$ cells using different conductive agents with different particle size. In addition, their electrochemical impedance characteristic of $Li/Mn_2O_4$ cells using different conductive agents is effectively identified through a.c. impedance technique. As a consequence, $Li/LiMn_2O_4$ cells with Super P Black show better electrochemical performances ascribed to the significant contribution of feasible ionic conduction due to larger particle size than those with Acetylene Black.

• 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.