• Korean Journal of Materials Research
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• v.22 no.8
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• pp.385-389
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• 2012

Significant improvements in the switching voltage distribution are required for the development of unipolar resistive memory devices using $MnO_x$ thin films. The $V_{set}$ of the as-grown $MnO_x$ film ranged from 1 to 6.2 V, whereas the $V_{set}$ of the oxygen-annealed film ranged from 2.3 to 3 V. An excess of oxygen in an $MnO_x$ film leads to an increase in $Mn^{4+}$ content at the $MnO_x$ film surface with a subsequent change in the $Mn^{4+}/Mn^{3+}$ ratio at the surface. This was attributed to the change in $Mn^{4+}/Mn^{3+}$ ratios at the $MnO_x$ surface and to grain growth. Oxygen annealing is a possible solution for improving the switching voltage distribution of $MnO_x$ thin films. In addition, crystalline $MnO_x$ can help stabilize the $V_{set}$ and $V_{reset}$ distribution in memory switching in a Ti/$MnO_x$/Pt structure. The improved uniformity was attributed not only to the change of the crystallinity but also to the redox reaction at the interface between Ti and $MnO_x$.

• Journal of the Korean Electrochemical Society
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• v.10 no.4
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• pp.239-244
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• 2007

In order to investigate the effect of fluorine ion in the $Li_{1-x}FeO_2Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8) cathode material, it was synthesized $Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8, $0.05{\le}y{\le}0.15$) cathode materials at $350^{\circ}C$ for 10hrs using solid-state method. $Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8, $0.0{\le}y{\le}0.1$ was composed many large needle-like particles of about $1-1.5\;{\mu}m$ and small particles of about 50-100 nm, which were distributed among the larger particles. However, $Li_{1-x}FeO_{1.85}F_{0.15}-Li_xMnO_2$ material showed slightly different particle morphology. The particles of $Li_{1-x}FeO_{1.85}F_{0.15}-Li_xMnO_2$ were suddenly increased and started to be a spherical type of particle shape. $Li/Li_{1-x}FeO_{1.9}F_{0.1}-Li_xMnO_2$ cell showed a high initial discharge capacity of 163 mAh/g and a high cycle retention rate of 95% after 50 cycles. The initial discharge capacity of $Li/Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ ($0.05{\le}y{\le}0.15$) cells increased according to the increase of F content. However, the cycleability of this cell was very rapidly decreased when the substituted fluorine content is over 0.1. We suggested that too large amount of F ion fail to substitute into the $Li_{1-x}FeO_2-Li_xMnO_2$ structure, which resulted in the severe decline of battery performance.

• Journal of the Korean Chemical Society
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• v.38 no.11
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• pp.785-791
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• 1994

The $Sr_1-_xY_xMnO_3$ (x = 0.0∼1.0) system was synthesized using amorphous citrate process. The stability of various structures and the electronic transport properties of this system were investigated. X-ray diffraction study indicated that the $Sr_1-_xY_xMnO_3$ system has three different structures depending on composition, namely, 4L-hexagonal perovskite (when x is less than 0.3), pseudocubic perovskite (when x is 0.3∼0.7), and hexagonal nonperovskite (when x is larger than 0.7) structures. The structural changes and electronic properties were interpreted based on two factors, i.e., the size of cations and the oxidation state of manganese ion. When the concentration of Y substitution exceeds 30%, the Mn-Mn repulsive interaction dominates over intermetallic attraction, and thus structure changes to pseudocubic perovskite. In perovskite phase the unit cell dimensions increases with increasing $Mn^{3+}$ ions due to yttrium substitution. The band gap of $Sr_{0.9}Y_{0.1}MnO_3$ is greater than that of $Sr_{0.5}Y_{0.5}MnO_3$. The greater band gap of $Sr_{0.9}Y_{0.1}MnO_3$ indicates that the 4L-hexagonal structure is more stabilized than cubic perovskite due to the Mn-Mn bond.

• Applied Chemistry for Engineering
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• v.10 no.6
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• pp.832-837
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• 1999

Stability of a cathode material was determined by Tafel plot in 1 M LiOH solution. The stabilized $LiM_xMn_{2-x}O_4$ (x=0.05~0.1) electrode resulted in overpotential of 0.13~0.15 mV at 100 mA. This overpotential was 0.05 mV lower than that of the spinel structured $LiMn_2O_4$ electrode. Conductivity test at various potentials showed that the conductivity of $LiM_xMn_{2-x}O_4$ was higher than that of the spinel structured $LiMn_2O_4$ and the bulk resistance of $LiM_xMn_{2-x}O_4$ due to the dissolution of $Mn^{2+}$ was lowered.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.23 no.4
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• pp.323-326
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• 2010

$(Zn_{1-x}Ca_x)_2SiO_4$:Mn phosphors doped with Ca were synthesized by solid state reaction method. $(Zn_{1-x}Ca_x)_2SiO_4$:Mn phosphors showed XRD patterns of Willemite structure. Also, $CaSiO_3$ structure and new peak near 610 nm in $(Zn_{1-x}Ca_x)_2SiO_4$:Mn with increasing value of x were observed from XRD and PL. The new peak near 610 nm in $(Zn_{1-x}Ca_x)_2SiO_4$:Mn with doping Ca was attributed to formation of $CaSiO_3$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2005.07a
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• pp.418-419
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• 2005

$\o-LiMnO_2$ is known to have poor cycle performance causing the irreversible phase transformation on cycling. In this paper, the effect of chemical substitution on improving cycle performance of $o-LiMnO_2$ was studied at the compositions of $LiCr_xMn_{1-x}O_2$(x=0, 0.1, 0.2, 0.4). XRD is showed that structure of $LiCr_xMn_{1-x}O_2$ transformed from orthorhombic to spinel according to the increase of substitute degree. For lithium ion battery applications, $LiCr_xMn_{1-x}O_2$/Li cell were characterized electrochemically by charge/discharge cycling.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.6 no.4
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• pp.600-608
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• 1996

Specific structural properties of Li intercalation reaction into the spinel relatedmanganese dioxide, $Li_{x}Mn_{2}O_{4}(0.2{\leq}x{\leq}2.0)$, are investigated by X-ray diffractional and electrochemical studies of Li/1M $LiClO_{4}$-propylene carbonate solution/$Li_{x}Mn_{2}O_{4}$ cell. The effect of the chemical composition and the reaction temperature on electrochemical parameter of $Li_{x}Mn_{2}O_{4}$ are studied by the phenomena of phase-transition, analysis of crystal lattice, fine structure, and thermal analysis. Treatment of the spinel $Li_{x}Mn_{2}O_{4}$ with aqueous acid was found to result in conversiton of $Li_{x}Mn_{2}O_{4}$ to nearly pure $MnO_{2}$, as evidenced by a reduction in the lattice constant $a_{c}$ from 8.255 to $8.031\;{\AA}$. At a composition range of $0.2{\leq}x{\leq}0.6$ in $Li_{x}Mn_{2}O_{4}$ the reduction proceeded in a homogeneous phase, which was characterized by a constant voltage of 3.9~3.7 V together with a lattice constant of $8.255\;{\AA}$.

• Journal of the Korean Ceramic Society
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• v.36 no.2
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• pp.145-150
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• 1999

Gd1-xSrxMnO3(0$\leq$X$\leq$0.6) as the cathode for solid oxide fuel cell was synthesized by citrate process and studied for its crystal structure, electrical conductivity, thermal expansion coefficient (TEC), and investigated reactivity with 8 mol% yttria stabilized zirconia(8YSZ) or Ce0.8Gd0.2O1.9 (CGO). The crystal structure of Gd1-xSrxMnO3 changed from orthorhombic (0$\leq$X$\leq$0.3) through cubic (0.4$\leq$X$\leq$0.5) to tetragonal structure (X=0.6). When Sr contents was increased, the electrical conductivity of Gd1-xSrxMnO3 was inthose of La1-xSrxMnO3, 8YSZ and CGO if Sr content was above 30mol%. TEC of Gd1-xSrxMnO3 was increased with Sr content. After heat treatment at 1300$^{\circ}C$ for 48 hours, reaction product of Gd1-xSrxMnO3 and 8YSZ was SrZrO3. However CGO had no reaction product with Gd1-xSrxMnO3.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.774-780
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• 1998

For the stabilization of the spinel structured $LiMn_2O_4$, a fraction of manganese was substituted with various metals such as Mg, Fe, V, W, Cr, Mo with Mn that had a similar ionic radii ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$). The $LiM_xMn_{2-x}O_4$ showed a substantial improvement as lower capacity loss than that of the spinel structured $LiMn_2O_4$ when it was used as a cathode material. And with the partial substitution, the chemical diffusion coefficient for $LiMg_{0.05}Mn_{1.9}O_4$ and $LiCr_{0.1}Mn_{1.9}O_4$ was increased by and order of magnitude compared to that of the $LiMn_2O_4$ with spinel structure. The results showed that significant improvement can be made on the electrochemical characteristics as the structure of the $LiMn_2O_4$ electrode material was stabilized by the partial substitution.

• Proceedings of the Korea Crystallographic Association Conference
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• 2002.11a
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• pp.16-16
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• 2002

The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).