• Title/Summary/Keyword: $Mn^{2+}$ ion

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Electrochemical Properties of LiMnO2-organic Composite Cathodes with High Capacity for Lithium Ion Polymer Battery (리튬 이온 폴리머 전지용 고용량 LiMnO2-organic Composite 정극의 전기화학적 특성)

  • 김종욱;조영재;구할본
    • 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.

A Study on the Cathodoluminescence and Structure of Thin Film $ZnGa_2O_4:Mn$ Oxide Phosphor (박막형 $ZnGa_2O_4:Mn$ 산화물 형광체의 음극선루미느센스와 구조적 특성에 관한 연구)

  • Kim, Joo-Han;Holloway Paul H.
    • Journal of the Korean Vacuum Society
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    • v.15 no.5
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    • pp.541-546
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    • 2006
  • In this study we have investigated cathodoluminescence (CL) and structural properties of thin film $ZnGa_2O_4:Mn$ oxide phosphor by using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), photoluminescence (PL), and cathodoluminescence. PL emission peaked at 506 nm was observed from the $ZnGa_2O_4:Mn$ phosphor target and it was attributed to the $^4T_1-^6A_1$ transition in $Mn^{2+}$ ion. The color coordinates of the emission were x = 0.09 and y = 0.67. The $ZnGa_2O_4:Mn$ films showed the excitation spectrum peaked at 294 nm by $Mn^{2+}$ ion absorption. It was found that the higher intensity of CL emission at 505 nm appears to result from the denser and closely-packed structure in $ZnGa_2O_4:Mn$ phosphor films deposited at lower pressures. The CL intensity did not show any systematic dependence on film surface roughness.

Photoluminescence Properties of Novel $Mg_{2}SnO_{4}:Mn$ Phosphor (새로운 $Mg_{2}SnO_{4}:Mn$ 형광체의 광 발광 특성)

  • Kim, Kyung-Nam;Jung, Ha-Kyun;Park, Hee-Dong;Kim, Do-Jin
    • Journal of the Korean Ceramic Society
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    • v.38 no.9
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    • pp.817-821
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    • 2001
  • A new $Mg_{2-x}MN_xSnO_4$ phosphor with an inverse spinel structure was synthesized by the solid-state reaction technique. The photoluminescence properties of the $Mg_2SnO_4$:Mn phosphors were investigated under 147nm -vacuum ultraviolet ray excitation. The Mn-doped $Mg_2SnO_4$ phosphor exhibited high emission intensity with the spectrum centered at 500nm wavelength. It was explained that the green emission in $Mg_2SnO_4$:Mn phosphor has originated from energy transfer from $^4T_1$ to $^6A_1$ of $Mn^{2+}$ ion at tetrahedral site of the spinel structure. The $Mn^{2+}$ ion concentration exhibiting the maximum emission intensity under the excitation of 147nm-vacuum ultraviolet ray was 0.25mol%. And the decay time of the phosphor was shorter than 10ms.

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A Study on Electronic Structures of Spinel-Type Manganese Oxides for Lithium Ion Adsorbent using DV-Xα Molecular Orbital Method (DV-Xα 분자궤도법을 이용한 리튬이온 흡착제용 스피넬형 망간산화물의 전자상태에 관한 연구)

  • Kim, Yang-Su;Jeong, Gang-Seop;Lee, Jae-Cheon
    • Korean Journal of Materials Research
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    • v.12 no.4
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    • pp.274-278
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    • 2002
  • Discrete-variational(DV)-$X{\alpha}$ method was applied to investigate the electronic structures of spinel- type manganese oxide which is well known to the high performance adsorbent or cathode material for lithium ion. The results of DOS(density of states) and Mulliken population analysis showed that Li was nearly fully ionized and interactions between Mn and O were strong covalent bond. The effective charge of Li and Mn was +0.77 and +1.44 respectively and the overlap population between Mn and O was 0.252 in $LiMn_2O_4$. These results from DV-X$\alpha$ method were well coincided with the experimental result by XPS analysis and supported the feasibility of theoretical interpretation for the $LiMn_2O_4$ compound.

The Research and Development Trend of Cathode Materials in Lithium Ion Battery (리튬이차전지용 양극재 개발 동향)

  • Park, Hong-Kyu
    • Journal of the Korean Electrochemical Society
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    • v.11 no.3
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    • pp.197-210
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    • 2008
  • The cathode materials for lithium ion battery have been developed in accordance with the battery performance. $LiCoO_2$ initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of $LiCoO_2$. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are $LiNi_{1-x}{M_xO_2}$, $Li[Ni_{x}Mn_{y}Co_{z}]O_{2}$, $Li[{Ni}_{1/2}{Mn}_{1/2}]O_{2}$. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. ${LiMn}_{2}{O}_{4}$ and $LiFePO_4$ are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite.

Analysis of $Cr_2O_7^{-2}/MnO_4^{-}$ Mixtures by an Absorption Spectrometry Coupled with Flow Injection Analysis(FIA) (흐름주입분석기법에 접목된 흡수분광분석법에 의한 $Cr_2O_7^{-2}/MnO_4^{-}$혼합물의 분석)

  • Hwang, Hoon
    • Journal of the Korean Chemical Society
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    • v.44 no.3
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    • pp.212-219
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    • 2000
  • An absorption spectrometry coupled with flow injection analysis has been developed and tested for the analysis of the Cr$_2O_7^{2-}$/Nn$O_4^-$ mixtures. Even though one has to inject the sample twice into the FIA system and the process of the sample treatment is required to completely destroy the Mn$O_4^-$ ion for the analysis of the Cr$_2O_7^{2-}$ ion, the new method has definite advantages over the current method. It utilizes only a single analytical wavelength (570 nm) and enables one to construct calibration curves which accurately follow the Beer's law over wide ranges of analytical concentrations of both ions ($2.0{\times}10^{-6}$M∼$8.0{\times}10^{-3}$M for Cr$_2O_7^{2-}$ ion, $2.0{\times}10^{-6}$M∼$4.0{\times}10^{-3}$M for MnO4- ion).

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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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A Microscopic Study on Treatment Mechanism of Acid Mine Drainage by Porous Zeolite-slag Ceramics Packed in a Column Reactor System (컬럼반응조 내 충진된 다공성 zeolite-slag 세라믹에 의한 산성광산배수의 처리기작에 대한 미세분석 연구)

  • Yim, Soo-Bin
    • Journal of Korean Society of Water Science and Technology
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    • v.26 no.6
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    • pp.13-26
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    • 2018
  • This research was conducted to elucidate the removal mechanism of heavy metals and sulfate ion from acid mine drainage(AMD) by porous zeolite-slag ceramics (ZS ceramics) packed in a column reactor system. The average removal efficiencies of heavy metals and sulfate ion from AMD by the 1:3(Z:S) porous ZS ceramics in the column reactor under the HRT condition of 24 hours were Al 97.5%, As 98.8%, Cd 86.1%, Cu 96.2%, Fe 99.7%, Mn 64.1%, Pb 97.2%, Zn 66.7%, and $SO_4{^{2-}}$ 76.0% during 121 days of operation time. The XRD analysis showed that the ferric iron from AMD could be removed by adsorption and/or ion-exchange on the porous ZS ceramics. In addition it was known that Al, As, Cu, Mn, and Zn could adsorb or coprecipitate on the surface of Fe precipitates such as schwertmannite, ferrihydrite, or goethite. The EDS analysis revealed that Al, Fe, and Mn, which were of relatively high concentration in the AMD, would be adsorbed and/or ion-exchanged on the porous ZS ceramics and also exhibited that Al, Cu, Fe, Mn, and Zn could be precipitated as the form of metal hydroxide or sulfate and adsorbed or coprecipitated on the surface of Fe precipitates. The microscopic results on the porous ZS ceramics and precipitated sludge in a column reactor system suggested that the heavy metals and sulfate ion from AMD would be eliminated by the multiple mechanisms of coprecipitation, adsorption, ion-exchange as well as precipitation.

Defect Chemistry of BaTiO_3$ Codoped with Mn and Nb

  • Han, Young-Ho;Shin, Dong-Jin
    • The Korean Journal of Ceramics
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    • v.4 no.2
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    • pp.68-71
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    • 1998
  • The effect of Mn and Nb additions on the electrical properties of BaTiO$_3$ has been studied by means of equilibrium electrical conductivity as a function of temperature, oxygen partial pressure(Po$_2$) and composition. If the manganese ion is added to the normal Ti site, i.e. BaTi$_{1-x}Mn_xO_{\delta-6}$, the equilibrium conductivity shows strong evidence of acceptor-doped behavior. The conductivity minimum, corresponding to the transition from oxygen excess, p-type behavior to oxygen deficient, n-type behavior with decreasing Po$_2$, is displaced to lower Po$_2$ and is broadened and flattened. The partial replacement of Mn ion with Nb decreases the acceptor-doped effect and the total replacement exhibits a typical donor-doped behavior. It was confirmed that unlike undoped or other acceptor-doped behavior. It was confirmed that unlike undoped or other acceptor-doped samples, for the p-type region, the electrical conductivity follows the 1/6th power dependence of oxygen partial pressure.

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