• 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.

• 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.

• Journal of the Korean Electrochemical Society
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• v.8 no.2
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• pp.82-87
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• 2005

The cathode material, $LiNi_{0.5}Mn_{1.5}O_4$, for high voltage applications of Li-ion batteries exhibits impurity phases due to oxygen deficiency during the high temperature heat treatment. The impurity phase reduces the electrochemical properties of the electrode since the deficiency spinel structure disturbs the lithium ion intercalation and deintercalation. In this study, Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$ powders are synthesized by a sol-gel method in order to reduce the amount of the impurity phases in the $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$. Thermal analysis of the cathode material shows that the $LiNi_{0.5}Mn_{1.5}O_4$ without Cr substitution looses $2\%$ of its weight due to oxygen deficiency but the amount of weight loss is diminished when Cr is substituted. XRD analysis also supports the reduction of the impurity phases in the cathode after chromium substitution, suggesting that the improvement of the electrochemical properties such as the capacity retention and electrochemical stability are attributed to the low content of impurity phases in the Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4.$

• Journal of the Korean Electrochemical Society
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• v.7 no.1
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• pp.1-8
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• 2004

This paper deals with the recent development of high-voltage cathode materials of mono- and di- metal ions substituted spinel $LiMn_2O_4$ for lithium batteries. $LiCu_xMn_{2-x}O_4(0{\leq}x{\leq}0.5)$ shows reversible intercalation/deintercalation in two potential regions, $3.9\~43\;and\;4.8-5.0V$ and stable electrochemical cycling behavior but with low capacity. $LiNi_{0.5}Mn_{1.5}O_4$ obtained by a sol-gel process delivers a capacity of 127mAh $g^{-1}$ on the first cycle and sustains a value of 124 mAh $g^{-1}$ even after the 60th cycle. The $Li_xCr_yMn_{2-y}O_4(0{\leq}x{\leq}0.5)$ solid-solutions exhibit enhanced specific capacity, larger average voltage, and improved cycling behaviors for low Cr content. $LiCr_yMn_{2-y}O_4$ presents a reversible Li deintercalation process at 4.9V, whose capacity is proportional to the Cr content in the range of $0.25{\leq}x{\leq}0.5$ and delivers higher capacities. $LiM_yCr_{0.5-y}Mn_{1.5}O_4(M=Fe\;or\;Al)$ shows that the capacity retention is lowered compared with lithium manganate. The cumulative capacities obtainable with Al-substitutted materials are less than those with Fe-substituted materials. $LiCr_xNi_{0.5-x}Mn_{1.5}O_4(x=0.1)$ delivers a high initial capacity of 1$152mAh\;g^{-1}$ with excellent cycleability.

• 한국전기화학회:학술대회논문집
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• 1999.10a
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• pp.63-63
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• 1999

• Bulletin of the Korean Chemical Society
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• v.20 no.1
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• pp.53-58
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• 1999

We synthesize the spinel lithium manganese oxides of the LiCrxMn2-xO4 from x=0.00 to 0.70 at 750 ℃ in air and identifiy them with X-ray crystallography.

• Journal of the Mineralogical Society of Korea
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• v.16 no.3
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• pp.223-232
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• 2003

The co-precipitation method is applied to synthesize the cathode material Li[L $i_{x}$M $n_{1-x-y}$C $r_{y}$ ] $O_2$ for lithium rechargeable batteries at $650^{\circ}C$ (CR650) and 8$50^{\circ}C$ (CR850), respectively. Rietveld indices indicate that $R_{wp}$ with respect to $R_{exp}$ ( $R_{wp}$/ $R_{exp}$) are 9.2%/10.1% for CR650 and 15.9%/9.76% for CR850, respectively. $R_{B}$ and S (GofF) shows 10.9%, 8.54% and 1.9, 1.6, respectively. Rietveld structure refinement reveals that layer structure of LiMn $O_2$ (R3m) coexists with lower symmetry of Li[L $i_{1}$3/M $n_{2}$3/] $O_2$ (C2/c) due to superlattice ordering of Li and Mn in metal-transition containing layers. Unit-cell parameters are calculated as a=2.8520(2)$\AA$, c=14.248(2)$\AA$, V=100.40(l)$\AA^3$ for CR650, and a=2.8504(1)$\AA$, c=14.2371(7)$\AA$, V=100.179(8)$\AA^3$ for CR850. Final chemistry is obtained as Li[L $i_{0.35}$M $n_{0.56}$C $r_{0.09}$] $O_2$ (CR650) and Li[L $i_{0.27}$M $n_{0.61}$C $r_{0.13}$] $O_2$ (CR850), respectively.y...y..vely.y...y..

• 한국전기화학회:학술대회논문집
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• 2003.04a
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• pp.22-22
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• 2003

• 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.

• Proceedings of the KIEE Conference
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• 2001.11b
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• pp.106-108
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• 2001

As 3V cathode material, a new doping spinel material, LiMn1.6Se0.4O4 powder with a phase-pure polycrystalline was synthesized by a sol-gel method. In spite of Jahn-teller distortion in 3V region($2.4{\sim}3.5V$), the LiMn1.6Se0.4O4 electrode shows no capacity loss. The material in the 3V region initially delivers a discharge capacity of 100mAh/g which increase with cycling to reach 105mAh/g after 90cycles. And 5V cathode material LiNi0.5-xMxMn1.5O4(M=Cr, V, Fe) compounds have been synthesized by sol-gel method. a series of electroactive spinel compounds, LiNi0.5-xMxMn1.5O4(M=Cr, V, Fe) has been studied by crystallographic and electrochemical methods. The material presents only one plateau at around 4.5 V vs. Li/Li+ with a large discharge capacity of 152mAh/g and fairly good cyclability.