• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2429-2432
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• 2009

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3333-3337
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• 2011

$ZnMn_2O_4$ has been prepared by a mechanochemical process using a mixture of $Mn_2O_3$ and ZnO as starting materials, and investigated as a possible anode material for lithium-ion batteries. The phase evolution and morphologies of the ball-milled and annealed powders are characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) with energy dispersive microanalysis (EDX), respectively. The solid-state reaction for the formation of $ZnMn_2O_4$, under the given experimental conditions, is achieved in a short time (30 min), and the prepared samples exhibit excellent electrochemical performances including an enhanced initial coulombic efficiency, high reversible capacity, and stable capacity retention with cycling.

• 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.

• 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.

• Korean Chemical Engineering Research
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• v.47 no.1
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• pp.84-88
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• 2009

Al doped $LiMn_2O_4$ cathode powders with fine size were synthesized by an ultrasonic spray pyrolysis method from the spray solution with citric acid and ethylene glycol. The as-prepared powders with spherical shape, porous structure and micron size turned into $LiMn_{11/6}Al_{1/6}O_4$ powders with micron size and regular morphology after post-treatment above $800^{\circ}C$. The $LiMn_{11/6}Al_{1/6}O_4$ powders had low initial discharge capacity of 94 mAh/g at a post-treatment temperature of $700^{\circ}C$. As the post-temperature increased from $750^{\circ}C$ to $1,000^{\circ}C$, the initial discharge capacities of the $LiMn_{11/6}Al_{1/6}O_4$ powders changed from 103 to 117 mAh/g. The $LiMn_{11/6}Al_{1/6}O_4$ powders had the maximum discharge capacity at a post-treatment temperature of $750^{\circ}C$. However, the $LiMn_{11/6}Al_{1/6}O_4$ powders post-treated at a temperature of $900^{\circ}C$ had the good cycle properties. The discharge capacities of the $LiMn_{11/6}Al_{1/6}O_4$ powders dropped from 107 to 100 mAh/g (93% capacity retention) by the 70th cycle at a current density of 0.1 C.