• Journal of Electrochemical Science and Technology
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• v.15 no.1
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• pp.161-167
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• 2024

Despite the important role of manganese (Mn) in cobalt-free, Ni-rich cathode materials, existing reports on the effects of Mn as a substitute for cobalt are not consistent. In this work, we analyzed the performance of cathodes comprised of Li(Ni_1-xMn_x)O₂ (LNMO). Both beneficial and detrimental results occurred as a result of the Mn substitution. We found that a complex interplay of effects (Li/Ni mixing driven by magnetic frustration, grain growth suppression, and retarded lithium insertion/extraction kinetics) influenced the performance and was intimately related to calcination temperature. This indicates the importance of establishing an optimal reaction temperature for the development of high-performance LNMO.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1310-1314
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• 2006

Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

• 한국전기화학회:학술대회논문집
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• 2002.11a
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• pp.57-65
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• 2002

The presence of tetragonal phase at the surface of $LiMn_2O_4$ pinicle due to a Jahn-Teller offset was previously reported to be one of the causes for capacity fading observed during cycling of $Li//Li_xMn_2O_4$ in 4V range. Further, it is reported that a Jahn-Teller effect in 4V range may be suppressed by substitution of Mn ions with Li ions or other transition metal ions. However, the direct evidence of the suppression of a Jahn-Teller effect in 4V range by substitution of Mn ions with other metal ions has not been reported. The dissolution and formation of surface film at the surface of $LiMn_2O_4$ electrodes also reportedly affect the capacity fading or rate capability. This study reports on the evidence of the onset and suppression of a Jahn-Teller effect in 4V range and the dissolution and formation of surface film at the surface of $LiMn_2O_4$ thin film electrodes using in situ bending beam method (BBM) in situ electrochemical quartz crystal microbalance (EQCM).

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.2
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• pp.245-250
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• 1999

The effect of cation substitution on the inonic conductivity was studied in $(Li_{0.5}La_{0.5})_{1-y}Sr_yTi_{1-x}Mn_xO_3$ system. In case of Sr substitution, the ionic conductivity abrubtly decreased over y=0.05. This may be caused by the decrease of lithium contents which contribute to lithium inonic conductivity. Jahn-Teller distortion as well as lattice parameter variation influenced the inonic conductivity in case of Mn substitution. A and B-site cations effects on the conductivities were found to be independent, and the ionic conductivity as high as $2.8{\times}10^{-2}$S/cm was obtained in x=0.0006 and y=0.05.

• Journal of Environmental Science International
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• v.13 no.7
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• pp.619-626
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• 2004

We have studied the catalytic combustion of soot particulates over perovskite-type oxides prepared by malic acid method, The catalysts were modified to enhance the activity by substitution of metal into A or B site of perovskite oxide. In addition, the reaction conditions such as temperature and $O_2$ concentration were investigated. The partial substitution of alkali metals into A site in the $LaMnO_3$ catalyst, enhanced the catalytic activity in the combustion of carbon particulate and the activity was shown in the order: Cs > K > Na. For the $La_{1-x}Cs_{x}MnO_{3}$ catalysts, the catalytic activity showed the maximum value with x=0.3 but no more increase on the catalytic activity was shown with x > 0.3. For the $La_{0.8}Cs_{0.2}MnO_{3}$ catalyst, the substitution of Fe or Ni increased the ignition temperature. The ignition temperature decreased with an increase of $O_2$ concentration, however, no more increase in the catalytic activity was shown with $O_2$ concentration > 0.2. The introduction of NO into reactants showed no effect on the catalytic activity.

• Proceedings of the Korean Magnestics Society Conference
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• 1995.05a
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• pp.60-61
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• 1995

• Journal of the Korean Ceramic Society
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• v.37 no.5
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• pp.466-472
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• 2000

As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

• Korean Journal of Materials Research
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• v.29 no.3
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• pp.150-154
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• 2019

This study investigates the effect of MnO2 and CuO as acceptor additives on the microstructure and piezoelectric properties of $0.96(K_{0.5}Na_{0.5})_{0.95}Li_{0.05}Nb_{0.93}Sb_{0.07}O_3-0.04BaZrO_3$, which has a rhombohedral-tetragonal phase boundary composition. $MnO_2$ and CuO-added $0.96(K_{0.5}Na_{0.5})_{0.95}Li_{0.05}Nb_{0.93}Sb_{0.07}O_3-0.04BaZrO_3$ ceramics sintered at a relatively low temperature of $1020^{\circ}C$ show a pure perovskite phase with no secondary phase. As the addition of $MnO_2$ and CuO increases, the sintered density and grain size of the resulting ceramics increases. Due to the difference in the amount of oxygen vacancies produced by B-site substitution, Cu ion doping is more effective for uniform grain growth than Mn ion doping. The formation of oxygen vacancies due to B-site substitution of Cu or Mn ions results in a hardening effect via ferroelectric domain pinning, leading to a reduction in the piezoelectric charge coefficient and improvement of the mechanical quality factor. For the same amount of additive, the addition of CuO is more advantageous for obtaining a high mechanical quality factor than the addition of $MnO_2$.

• Journal of Magnetics
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• v.9 no.4
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• pp.113-115
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• 2004

The magnetization properties have been measured for amorphous $Fe_{82}Mn_{8-x}B_xZr_{10}$ (x = 0-8) alloys. The temperature dependence of magnetization for these alloys shows the existence of antiferromagnetic couplings between Fe atoms in low fields at low temperatures. The magnetic parameters, obtained from the magnetization behavior are consistent with the presence of mixed magnetic state. The Curie temperature and magnetic moment increased with an increase of the concentration of B and spin glass like transition observed at low temperature decreases and finally vanishes at x = 8 at %. Our result suggests that the substitution of B for Mn seems to cause an increase of magnetic order.

• Journal of the Korean Ceramic Society
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• v.28 no.4
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• pp.297-304
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• 1991

Dielectric hysteresis characteristics of Pb(Zr0.52Ti0.48)O3 ceramics have been investigated as a function of the amount of MnO2 addition ranged from 0.0 wt% in Pb(Zr0.52Ti0.48)O3 ceramics enhanced the dielectric strength, aging effect and remanent polarization, while reduced the coercive field. These results could be explained by the effect of Mn-Vo association due to the substitution of Mn for the (Zr, Ti) site in PZT.