• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.14 no.4
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• pp.316-322
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• 2001

Cathode materials $LiMn_{2-y}$$M_{y}$ $O_4$(M=Zn and Mg) were obtained by reacting the mixture of LiOH.$H_2O$, Mn $O_2$ and MgO ar ZnO at 80$0^{\circ}C$ for 36h in an air atmosphere. These materials showed an extended cycle life in lithium-anode cells working at room temperatue in a 3.0 to 4.3V potential window. Among these materials, LiM $n_{1.9}$M $g_{0.1}$ $O_4$ showed the best cycle performance in terms of the capacity and cycle life. The discharge capacities of the cathode for the Li/LiM $n_{1.9}$ $M_{0.1}$ $O_4$ cell at the 1st cycle and at the 70th cycle were about 120 and 105mAh/g, respectively. This cell capacity is retained by 88% after 70th cycle. In cyclic voltammetry measurement, all cells revealed tow oxidation peaks and reduction peaks. However, Li/$LiMn_{2-y}$$M_{y}$ $O_4$ cell substituted with Zn and Mg showed new reaction peak during reduction reaction.eaction.ion.ion.

• Journal of Environmental Science International
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• v.15 no.4
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• pp.333-340
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• 2006

A (5 wt.%)Mn-(1 wt.%)$V_{2}O_{5}/TiO_{2}$ catalyst were prepared by co-precipitation method and used for low-temperature selective catalytic reduction (SCR) of $NO_x$ with ammonia in the presence of oxygen. The properties of the catalysts were studied by X-ray diffraction (XRD), temperature programmed reduction (TPR) and scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDS). The experimental results showed that (5 wt.%)Mn-(1 wt.%)$V_{2}O_{5}/TiO_{2}$ catalyst yielded 81% NO conversion at temperature as low as $150^{\circ}C$ and a space velocity of $2,400\;h^{-1}$. Crystalline phase of $Mn_{2}O_3$ was present at ${\ge}\;15%$ Mn on $V_{2}O_{5}/TiO_{2}$. XRD confirmed the presence of manganese oxide ($Mn_{2}O_{3}$) at $2{\theta}=32.978^{\circ}(222)$. The XRD patterns presented of (5 wt.%)Mn-(1 wt.%)$V_{2}O_{5}/TiO_{2}$ did not show intense or sharp peaks for manganese oxides and vanadia oxides. The TPR profiles of (5 wt.%)Mn-(1 wt.%)$V_{2}O_{5}/TiO_{2}$ catalyst showed main reduction peat of a maximum at $595^{\circ}C$.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.11
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• pp.878-885
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• 2012

In this study we aims to examine the co-doping effects of 1/3 mol% $Mn_3O_4+Co_3O_4$ (1:1) on the reaction, microstructure, and electrical properties such as the bulk defects and grain boundary properties of $ZnO-Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Co-doped ZBS, ZBS(MCo) varistors were controlled by Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$) was decomposed and promoted densification at lower temperature on heating in Sb/Bi=1.0 by Mn rather than Co. Pyrochlore on cooling was reproduced in all systems however, spinel (${\alpha}$- or ${\beta}$-polymorph) did not formed in Sb/Bi=0.5. More homogeneous microstructure was obtained in $Sb/Bi{\geq}1.0$ In ZBS(MCo), the varistor characteristics were improved drastically (non-linear coefficient, ${\alpha}$=30~49), and seemed to form $Zn_i^{..}$(0.17 eV) and $V_o^{\bullet}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy (IS & MS), the grain boundaries have divided into two types, i.e. the one is tentatively assign to $ZnO/Bi_2O_3(Mn,Co)/ZnO$ (0.47 eV) and the other ZnO/ZnO (0.80~0.89 eV) homojunctions.

• 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.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.48 no.3
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• pp.179-184
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• 1999

In the past ten years, $LiMn_2O_4$-based spinels have been extensively studied as positive electrode materials for lithium-ion batteries. To improve the cycle performance of spinel $LiMn_2O_4$ as the cathode of 4V class lithium secondary batteries, spinel phases $LiMn_2O_4$ were prepared at various temperatures ranging form 600-900$^{\cire}C$ in air. The results showed that charge.dischare capacity of $LiMn_2O_4$ varied at 1st temperature from $200^{\circ}C to 600^{\circ}C$ increase with increasing temperature. $LiMn_2O_4$ synthesized at 2nd temperature $750^{\circ}C$excellent charge.discharge capacity, efficiency and cyclability compared to the samplesynthesized different temperatures. The value of lst charge.discharge capacity was 121mAh/g, 118mAh/g, Also, the efficiency value was about 97%.

• Transactions of the Korean hydrogen and new energy society
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• v.17 no.4
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• pp.353-361
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• 2006

As one of the thermochemical water splitting hydrogen production cycles, which could be operated at the lower temperature below 1200 K, we investigated the feasibility of the cyclic operation of Ispra Mark 2 cycle with the addition of $ZrO_2$. The cycle is theoretically composed of three reaction steps; (1) 1st step($2MnO_2{\rightarrow}Mn_2O_3+0.5O_2$), (2) 2nd step($Mn_2O_3+4NaOH{\rightarrow}2Na_2O{\cdot}MnO_2+H_2+H_2O$) and (3) 3rd step($2Na_2O{\cdot}MnO_2H_2O{\rightarrow}4NaOH+2MnO_2$). From the TPR tests, the temperature ranges for $O_2$ production in 1st step and $H_2$ production in 2nd step were $550{\sim}750^{\circ}C$ and $650{\sim}750^{\circ}C$, respectively. In $MnO_2/Mn_2O_3/NaOH$ system, the formation of molten products due to the reaction between manganese oxides and NaOH were greatly decreased with the addition of $ZrO_2$. In addition, the results of a cyclic test were discussed with the viewpoint of $H_2$ production amounts and the feasibility of the process improvement.

• Journal of the Korean Ceramic Society
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• v.37 no.10
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• pp.968-974
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• 2000

Nb$_2$O$_{5}$와 MnO 첨가에 따른 Pb$_{0.6}$Sr$_{0.4}$TiO$_3$반도체 세라믹의 미세구조와 전기적 특성은 유전특성, I(current)-V(voltage) 측정, 그리고 복소 임피던스 측정 등을 이용하여 고찰하였다. Nb 도핑량이 0.4 mol% 이하인 경우 Nb 도핑량에 따라 전도성과 입성장은 증가되었으나 그 이상의 도핑량에서는 Sr이나 Pb 공공의 생성으로 인하여 전도성이 감소되고 입성장도 억제되는 것을 관찰할 수 있었다. 0.4 mol% Nb-doped Pb$_{0.6}$Sr$_{0.4}$TiO$_3$에 0.01 mol% MnO를 첨가한 경우 비저항비($ ho$$_{max}$/$\rho$/min/)가 $10^2$에서 $10^4$으로 크게 향상되었다. 그리고 전이 온도 주변에서 여러 개의 변곡점을 지니는 비옴성 거동이 발견되었다. 이와 같은 현상은 입계에 존재하는 Mn 이온이 부분적으로 편석되어 표면 전하의 보상 효과에 영향을 미치는 것이라고 사료된다.

• Bulletin of the Korean Chemical Society
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• v.32 no.8
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• pp.2683-2688
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• 2011

Silica-manganese oxides with a core-shell structure were synthesized via precipitation of manganese oxides on the $SiO_2$ core while varying the concentration of a precipitation agent. Elemental analysis, crystalline property investigation, and morphology observations using low- and high-resolution electron microscopes were applied to the synthesized silica-manganese oxides with the core-shell structure. As the concentration of the precipitating agent increased, the manganese oxide shells around the $SiO_2$ core sequentially appeared as $Mn_3O_4$ particles, $Mn_2O_3+Mn_3O_4$ thin layers, and ${\alpha}-MnO_2$ urchin-like phases. The prepared samples were assembled as electrodes in a supercapacitor with 0.1 M $Na_2SO_4$ electrolyte, and their electrochemical properties were examined using cyclic voltammetry and charge-discharge cycling. The maximum specific capacitance obtained was 197 F $g^{-1}$ for the $SiO_2-MnO_2$ electrode due to the higher electronic conductivity of the $MnO_2$ shell compared to those of the $Mn_2O_3$ and $Mn_3O_4$ phases.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.15 no.2
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• pp.162-168
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• 2002

The purpose of this study is to research and develop LiMnO$_2$-organic and Li$_{0.3}$MnO$_{2}$-organic composite with high energy density for Lithium ion polymer battery. This paper describes cyclic voltammetry, impedance sepctroscopy, electrochemical properties of LiMnO$_2$-organic and Li$_{0.3}$MnO$_{2}$-organic composite with polymer electrolyte as a function of a mixed ratio. The first discharge capacity of LiMnO$_2$-PAn with 3 wt.% PAn was 83mHA/g, while that of Li$_{0.3}$MnO$_{2}$-PPy composite was 136 mAh/g. The Ah efficiency was above 98% after the 2nd cycle. The LiMnO$_2$-PAn with DMcT 2 wt.% and Li$_{0.3}$MnO$_{2}$-PPy composites cathode with 5wt. PPy in PVDF-PC-EC-LiClO$_4$ electrolyte showed good capaity with cycling. The discharge capacity of LiMnO$_2$-PAn with wt.% DMcT was 80 and 130 mAh/g at 1st and 12th cycle, respectively. The capacity of LiMnO$_2$-PAn composite with 2 wt.% DMcT was higher than that of LiMnO$_2$-PAn composite.mposite.

• Journal of the Korean Ceramic Society
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• v.29 no.11
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• pp.900-904
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• 1992

High temperature electrical conductivity was measured for perovskite La0.98Sr0.02MnO3 at 200~130$0^{\circ}C$ as a function of Po2 and 1/T. Perovskite La1-xSrxMnO3 system is the typical oxygen electrode in solid oxide fuel cell (SOFC). Acetate precursors were used for the preparation of mixed water solution and the calcined powders were reacted with Na2CO3 flux in order to obtain highly reactive powders of perovskite La0.98Sr0.02MnO3. The relative density was greatly increased above 90% because of the homogeneous sintering. From the conductivity ($\sigma$)-temperature and conductivity-Po2 at constant temperature, the defect structure of La0.98Sr0.02MnO3 was discussed. From the slope of 1n($\sigma$) vs 1/T, the activation energy of 0.069 and 0.108eV were evaluated for above 40$0^{\circ}C$, respectively. From the relationship between $\sigma$ and Po2, it was found that the decomposition of La0.98Sr0.02MnO3 was occurred at 10-15.5 atm(97$0^{\circ}C$) and 10-11 atm(125$0^{\circ}C$). It is supposed that the improvement of p-type conductivity may be leaded by the increase of Mn4+ concentration through the substitution of divalent/monovalent cations for La site in LaMnO3.