• Title/Summary/Keyword: MnO2

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Oxidation State of Manganese in LiMn2O4 Powders and its Effect on Electrochemcal Properties

  • Kim, Seon-Hye;Lee, Kook-Jae;Shim, Kwang-Bo;Kim, Chang-Sam
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2006.09b
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    • pp.1220-1221
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    • 2006
  • [ $LiMn_2O_4$ ] powders for lithium ion batteries were synthesized from two separate raw material pairs of LiOH/MnO and $LiOH/MnO_2$. The powders prepared at 780 and $850^{\circ}C$ and their difference of electrochemical properties were investigated. Both powders calcined at 780 and $850^{\circ}C$ were composed of a single-phase spinel structure but those treated at $850^{\circ}C$ showed a lower intensity ratio of $I_{311}$ to $I_{400}$, a slightly larger lattice parameter, and an increased discharge capacity by 10% under $3.0{\sim}4.3V$ voltage range. The XPS study on the oxidation states of manganese repealed that powders made from LiOH/MnO had less $Mn^{3+}$ ion and gave better battery performances than those from $LiOH/MnO_2$.

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A Study on the Charateristics for Ozone Decomposition over Recovered Mn from Spent Betteries (폐건전지에서 회수된 Mn을 이용한 오존분해 특성 연구)

  • Kim, Geo Jong;Hong, Sung Chang
    • Applied Chemistry for Engineering
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    • v.24 no.2
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    • pp.161-164
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    • 2013
  • In this study, the application of recovered metals from spent batteries by extraction was investigated for ozone decomposition as a catalyst. Among the recovered metals, Mn contents was the most important factor for ozone decomposition. It was also found that the deactivation rate of the catalyst was dependent on the Zn contents, while K contents and activities were not perfectly correlated for ozone decomposition. In addition, the catalytic activity the $TiO_2$ added catalyst was decreased, due to the reduction of Mn contents. The structural characteristics of maganase oxide was not associated with the catalytic activity for ozone decomposition.

Janggunite, a New Mineral from the Janggun Mine, Bonghwa, Korea (경북(慶北) 봉화군(奉化郡) 장군광산산(將軍鑛山産) 신종광물(新種鑛物) 장군석(將軍石)에 대(對)한 광물학적(鑛物學的) 연구(硏究))

  • Kim, Soo Jin
    • Economic and Environmental Geology
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    • v.8 no.3
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    • pp.117-124
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    • 1975
  • Wet chemical analysis (for $MnO_2$, MnO, and $H_2O$(+)) and electron microprobe analysis (for $Fe_2O_3$ and PbO) give $MnO_2$ 74.91, MnO 11.33, $Fe_2O_3$ (total Fe) 4.19, PbO 0.03, $H_2O$ (+) 9.46, sum 99.92%. 'Available oxygen determined by oxalate titration method is allotted to $MnO_2$ from total Mn, and the remaining Mn is calculated as MnO. Traces of Ba, Ca, Mg, K, Cu, Zn, and Al were found. Li and Na were not found. The existence of (OH) is verified from the infrared absorption spectra. The analysis corresponds to the formula $Mn^{4+}{_{4.85}}(Mn^{2+}{_{0.90}}Fe^{3+}{_{0.30}})_{1.20}O_{8.09}(OH)_{5.91}$, on the basis of O=14, 'or ideally $Mn^{4+}{_{5-x}}(Mn^{2+},Fe^{3+})_{1+x}O_{8}(OH)_{6}$ ($x{\approx}0.2$). X-ray single crystal study could not be made because of the distortion of single crystals. But the x-ray powder pattern is satisfactorily indexed by an orthorhombic cell with a 9.324, b 14.05, c $7.956{\AA}$., Z=4. The indexed powder diffraction lines are 9.34(s) (100), 7.09(s) (020), 4.62(m) (200, 121), 4.17(m) (130), 3.547(s) (112), 3.212(vw) (041), 3.101(s) (300), 2.597(w) (013), 2.469(m) (331), 2.214(vw)(420), 2.098(vw) (260), 2.014 (vw) (402), 1.863(w) (500), 1.664(w) (314), 1.554(vw) (600), 1.525(m) (601), 1.405(m) (0.10.0). DTA curve shows the endothermic peaks at $250-370^{\circ}C$ and $955^{\circ}C$. The former is due to the dehydration: and oxidation forming$(Mn,\;Fe)_2O_3$(cubic, a $9.417{\AA}$), and the latter is interpreted as the formation of a hausmannite-type oxide (tetragonal, a 5.76, c $9.51{\AA}$) from $(Mn,\;Fe)_2O_3$. Infrared absorption spectral curve shows Mn-O stretching vibrations at $515cm^{-1}$ and $545cm^{-1}$, O-H bending vibration at $1025cm^{-1}$ and O-H stretching vibration at $3225cm^{-1}$. Opaque. Reflectance 13-15%. Bireflectance distinct in air and strong in oil. Reflection pleochroism changes from whitish to light grey. Between crossed nicols, color changes from yellowish brown with bluish tint to grey in air and yellowish brown to grey through bluish brown in oil. No internal reflections. Etching reactions: HCl(conc.) and $H_2SO_4+H_2O_2$-grey tarnish; $SnCl_2$(sat.)-dark color; $HNO_3$(conc.)-grey color; $H_2O_2$-tarnish with effervescence. It is black in color. Luster dull. Cleavage one direction perfect. Streak brownish black to dark brown. H. (Mohs) 2-3, very fragile. Specific gravity 3.59(obs.), 3.57(calc.). It occurs as radiating groups of flakes, flower-like aggregates, colloform bands, dendritic or arborescent masses composed of fine grains in the cementation zone of the supergene manganese oxide deposits of the Janggun mine, Bonghwa-gun, southeastern Korea. Associated minerals are calcite, nsutite, todorokite, and some undetermined manganese dioxide minerals. The name is for the mine, the first locality. The mineral and name were approved before publication by the Commission on New Minerals and Mineral Names, I.M.A.

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Structural Behavior of Mixed $LiMn_2O_4-LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ Cathode in Li-ion Cells during Electrochemical Cycling

  • Yun, Won-Seop;Lee, Sang-U
    • 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.

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Dielectric and Piezoelectric Characteristics of PMW-PNN-PT-PZ Ceramics with addiction of MnO$_2$ (MnO$_2$가 첨가된 PMW-PNN-PT-PZ계 세라믹스의 유전 및 압전 특성)

  • 박석환;윤광희;박정흠;김현재;박창엽
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1996.05a
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    • pp.63-67
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    • 1996
  • In this paper, effect of MnO$_2$ addition(0, 0.1, 0.2, 0.3, 0.5wt%) on the microstructure, dielectric and piezoelectric properties of [xPMW - (0.15-x) PNN] - [yPT-(0.85-y)PZ] (x=0, 0.01, 0.02, 0.03, 0.05, y = 0.35, 0.40, ().425, 0.45, 0.5) were investigated. When Ti/Zr ratio was 1.0, dielectric and piezoelectric properties were highest value. With PMW 2mol%, dielectric constant, dielectric constant (d$\_$33/, d$\_$31/) and electromechanical coupling factor (kp, k$\_$31/) were highest values of 1995, 479, 186(x10$\^$-12/C/N), 0.61, 0.36, respectively. With the addition of MnO$_2$, dielectric constant, electromechanical coupling factor (kp, k$\_$31/) were decreased, but with 0.3wt% MnO$_2$, eletromechanical coupling factor was highest value of 0.63. With the addition of MnO$_2$, mechanical quality(Q$\_$m/ was increased.

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Thermodynamic Behavior of Si in Mn-Si Melts (Mn-Si 용탕내 Si의 열역학적 거동)

  • Paek, Min-Kyu;Jang, Jung-Mock;Kang, Youn-Bae;Pak, Jong-Jin
    • Korean Journal of Metals and Materials
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    • v.50 no.2
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    • pp.116-121
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    • 2012
  • Equilibria between Mn-Si melts and $MnO-SiO_2$ slags were studied at 1673 K and 1773 K in MnO crucibles to accurately determine the thermodynamic property of the Mn-Si melts. The Unified Interaction Parameter Formalism (UIPF) was used to describe the thermodynamic property of the Mn-Si liquid. Using the UIPF, the experimental results obtained in the present study were thermodynamically analyzed to determine the activity coefficient of Si at infinite dilution and the 1st- and 2nd-order self-interaction parameters of Si in the Mn-Si melts.

Development of Continuous Galvanization-compatible Martensitic Steel

  • Gong, Y.F.;Song, T.J.;Kim, Han S.;Kwak, J.H.;De Cooman, B.C.
    • Corrosion Science and Technology
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    • v.11 no.1
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    • pp.1-8
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    • 2012
  • The development of martensitic grades which can be processed in continuous galvanizing lines requires the reduction of the oxides formed on the steel during the hot dip process. This reduction mechanism was investigated in detail by means of High Resolution Transmission Electron Microscopy (HR-TEM) of cross-sectional samples. Annealing of a martensitic steel in a 10% $H_2+N_2$ atmosphere with the dew point of $-35^{\circ}C$ resulted in the formation of a thin $_{C-X}MnO.SiO_{2}$ (x>1) oxide film and amorphous $_{a-X}MnO.SiO_{2}$ oxide particles on the surface. During the hot dip galvanizing in Zn-0.13%Al, the thin $_{C-X}MnO.SiO_{2}$ (x>1) oxide film was reduced by the Al. The $_{a-X}MnO.SiO_{2}$ (x<0.9) and $a-SiO_{2}$ oxides however remained embedded in the Zn coating close to the steel/coating interface. No $Fe_{2}Al_{5-X}Zn_{X}$ inhibition layer formation was observed. During hot dip galvanizing in Zn-0.20%Al, the $_{C-X}MnO.SiO_{2}$ (x>1) oxide film was also reduced and the amorphous $_{a-X}MnO.SiO_{2}$ and $a-SiO_{2}$ particles were embedded in the $Fe_{2}Al_{5-X}Zn_{X}$ inhibition layer formed at the steel/coating interface during hot dipping. The results clearly show that Al in the liquid Zn bath can reduce the crystalline $_{C-X}MnO.SiO_{2}$ (x>1) oxides but not the amorphous $_{a-X}MnO.SiO_{2}$ (x<0.9) and $a-SiO_{2}$ oxides. These oxides remain embedded in the Zn layer or in the inhibition layer, making it possible to apply a Zn or Zn-alloy coating on martensitic steel by hot dipping. The hot dipping process was also found to deteriorate the mechanical properties, independently of the Zn bath composition.

Effects of $TiO_2$Addition on the Electromagnetic Properties of Mn-Zn Ferrites ($TiO_2$첨가와 Mn-Zn ferrites의 전자기적 특성)

  • 정원희;송병무;한영호
    • Journal of the Korean Ceramic Society
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    • v.37 no.11
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    • pp.1065-1070
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    • 2000
  • TiO$_2$의 첨가가 Mn-Zn ferrites의 전자기적 물성에 미치는 효과에 대해 연구하였다. TiO$_2$의 첨가량이 증가함에 따라 밀도와 전기비저항이 증가된 반면 초기투자율은 감소하였다. TiO$_2$의 첨가에 따라 Fe$^{2+}$ ion의 증가에 기인하여 전력손실의 최소 값을 나타내는 온도가 저온으로 이동하였다. TiO$_2$를 0.12wt% 첨가한 시편의 경우, 100 kHz, 200 mT, 8$0^{\circ}C$ 측정 조건에서는 소결온도가 증가함에 따라 전력손실이 감소하였으며 125$0^{\circ}C$ 소결한 시편이 340 mW/㎤으로 가장 낮은 값을 보였다. 500 kHz, 50 mT, 8$0^{\circ}C$의 측정 조건에서는 소결 온도가 감소함에 따라 전력손실이 감소하였으며 115$0^{\circ}C$ 소결한 시편이 105 mW/㎤으로 가장 낮은 전력손실 값이 관찰되었다.

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Structure and Electrochemical Characterization of LiNi0.5Mn0.3Co0.2O2 as the Cathode Material Synthesized by Simple-combustion Method (단순 연소법으로 합성한 LiNi0.5Mn0.3Co0.2O2 양극 활물질의 구조 분석 및 전기화학적 특성 연구)

  • Cho, Sung-Woo;Ju, Jeong-Hun;Ryu, Seong-Hyeon;Ryu, Kawng-Sun
    • Journal of the Korean Electrochemical Society
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    • v.13 no.4
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    • pp.264-269
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    • 2010
  • $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ active material was prepared by simple-combustion method and investigated as the cathode material for li-ion battery. The structural characterization was analyzed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), respectively. The XRD patterns of $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ sample was indicated a phase of layered hexagonal structure. The size of particles has not uniform diameters ranging from 100 to 300 nm. The electrochemical performance of the $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ was measured by Cyclic Voltammetry and galvanostatics. The $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ shows the discharge capacity of ~162 mAh/g in the range of 2.8 to 4.3 V at the first cycle.