• 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 the Korean Electrochemical Society
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• v.9 no.4
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• pp.158-169
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• 2006

The present article is concerned with the overview of the chemically/surface modified cubic spinel $LiMn_2O_4$ as a cathode electrode far lithium ion secondary batteries. Firstly, this article presented a comprehensive survey of the cubic spinel structure and its correlated electrochemical behaviour of $LiMn_2O_4$. Subsequently, the various kinds of the chemically/surface modified $LiMn_2O_4$ and their electrochemical characteristics were discussed in detail. Finally, this article reviewed our recent research works published on the mechanism of lithium transport through the chemically/surface modified $Li_{1-\delta}Mn_2O_4$ electrode from the kinetic view point by the analyses of the experimental potentiostatic current transients and ac-impedance spectra.

• Electrical & Electronic Materials
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• v.14 no.12
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• pp.7-10
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• 2001

Orthorhombic type LiCo$_{x}$Mn$_{1-x}$ O$_2$(0$\leq$x$\leq$0.14) oxides have been synthesized by hydrothermal treatment of (Co$_{x}$Mn$_{1-x}$ )$_3$O$_4$precursors and LiOH aqueous solution at 17$0^{\circ}C$. As-synthesized powders showed well-ordered $\beta$-MaMnO$_2$structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic LiCo$_{0.1}$Mn$_{0.9}$O$_2$, comparing to orthorhombic LiMnO$_2$./TEX>.EX>.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.64-65
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• 2008

3D microbattery에 사용할 수 있는 $LiMn_2O_4$ 3차원 박막전극을 제조하여 그 전기화학적 특성을 관찰하였다. 3차원 구조의 형성을 위하여 먼저 polystyrene(PS) microsphere를 platinum이 증착된 Si/$SiO_2$ 기판위에 dip-coating 방식으로 코팅시켜 template로 사용하였다. 그 위에 sol-gel법을 이용, 박막을 형성시킨 후 template 를 제거하는 방식으로 $LiMn_2O_4$ 3차원 박막전극을 형성하였는데 이때 solution은 Lithium acetylacetonate[$LiCH_3CO-CHCOCH_3$], Manganese(III) acetylacetonate [Mn$(CH_3COCHCOCH_3)_3$]를 source 물질로 1-butanol과 acetic acid를 solvent로 활용하여 제조하였다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1997.11a
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• pp.275-278
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• 1997

We investigated effectness of sort and volume of conductive agent to charge/discharge capacity of LiMn$_2$O$_4$. LiMn$_2$O$_4$is prepared by reacting stoichiometric mixture of LiOH . $H_2O$ and MnO$_2$(mole ratio 1 : 2) and heating at 80$0^{\circ}C$ for 24h, 36h, 48h, 60h and 72h. All LiMn$_2$O$_4$cathode active materials show spinel structure. Cathode active materials calcined at 80$0^{\circ}C$ for 36h, charge/discharge characteristics and cycle stability have remarkable advantages. Used that super-s-black and 20wt% as conductive agent in LiMn$_2$O$_4$, it is excellent than property of cathode used Acetylene black or mixture of Super-s-black and acetylene black at charge/discharge capacity and cycle stability. Also, specific efficiency of cathode is excellent as over 98% and that of first cycle is excellent as 92%.

• 한국전기화학회:학술대회논문집
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• 2003.11a
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• pp.1-18
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• 2003

• Journal of the Korean Chemical Society
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• v.66 no.6
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• pp.451-458
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• 2022

Through the crystal alignment research based on the magnetic properties of LiNi_xMn_yCo_1-(x+y)O₂ such as magnetic susceptibility and related anisotropy, a crystal aligned LiNi_0.6Mn_0.2Co_0.2O₂ electrode is obtained, in which the (00l) plane is frequently oriented perpendicular to the surface of a current collector. The crystal aligned LiNi_0.6Mn_0.2Co_0.2O₂ electrode steadily exhibits low electrode polarization properties during the charge/discharge process in a lithium-ion battery, thus affording an improved capacity compared to a pristine LiNi_0.6Mn_0.2Co_0.2O₂ electrode. The aligned LiNi_0.6Mn_0.2Co_0.2O₂ electrode may have an appropriate structural nature for fast lithium-ion transport due to the oriented (00l) plane, and thus it contributes to enhancing the battery performance. This enhancement is analyzed in terms of various electrochemical theories and experiment results; thus, it is verified to occur because of the considerably fast lithium-ion transport in the aligned LiNi_0.6Mn_0.2Co_0.2O₂ electrode.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_{2}$(0 ${\times}$ 0.14) oxides have been synthesized by hydrothermal treatment of $(Co_{x}Mn_{1-x})_{3}O_{4}$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}-NaMnO_{2}$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_{2}$, comparing to orthorhombic $LiMnO_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_2$ (0 x 0.14) oxides have been synthesized by hydrothermal treatment of ($Co_{x}Mn_{1-x}$)$_3O_4$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}$-$NaMnO_2$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_2$, comparing to orthorhombic $LiMnO_2$.

• Journal of the Korean Electrochemical Society
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• v.14 no.3
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• pp.184-190
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• 2011

$LiMn_2O_4$ with mesoporous hollow sphere shape was synthesized by precipitation method with silica template. The synthesized $LiMn_2O_4$ has nanosized first particle and mesoporous hollow sphere shape. Silica template was removed by chemical etching method using NaOH solution. When the concentration of NaOH solution was increased, first particle size of manganese oxide was decrease and confirmed mesoporous hollow shpere shape. X-ray diffraction(XRD) patterns revealed that the synthesized samples has spinel structure with Fd3m space group. In case the ratio of silica and maganese salt increased, the size of first particles was decreased. The tetragoanal $LiMn_2O_4$ with micron size was synthesized at ratio of silica and manganese salt over 1 : 9. The prepared samples were assembled as cathode materials of Li-ion battery with 2032 type coin cell and their electrochemical properties are examined by charge-discharge and cyclic performance. Electrochemical measurements show that the nano-size particles had lower capacity than micron-size particles. But, cyclic performance of nano-size particles had better than that of micron-size particles.