• Bulletin of the Korean Chemical Society
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• 제30권10호
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• pp.2429-2432
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• 2009

• Bulletin of the Korean Chemical Society
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• 제32권9호
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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.

• 전기화학회지
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• 제7권1호
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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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• 제27권9호
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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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• 제47권1호
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• pp.84-88
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• 2009

Al이 치환된 $LiMn_2O_4$ 미세 분말을 구연산과 에틸렌 글리콜이 첨가된 분무용액으로부터 분무열분해 공정에 의해 합성하였다. 구형의 형상, 다공성의 구조 및 마이크론 크기를 가지는 전구체 분말들은 $800^{\circ}C$ 이상의 후열처리 온도에서 마이크론 크기 및 균일한 형태를 가지는 $LiMn_{11/6}Al_{1/6}O_4$ 분말들로 전환되었다. 후열처리 온도가 $700^{\circ}C$ 일 때 $LiMn_{11/6}Al_{1/6}O_4$ 분말은 94 mAh/g의 낮은 초기 방전 용량을 가졌다. 후열처리 온도가 $750^{\circ}C$에서 $1,000^{\circ}C$로 증가함에 따라 $LiMn_{11/6}Al_{1/6}O_2$ 분말의 초기 방전 용량은 103 mAh/g에서 117 mAh/g로 변화하였으며, 후열처리 온도 $750^{\circ}C$에서 최대 초기 방전용량을 가졌다. 반면에 후열처리 온도 $900^{\circ}C$에서 얻어진 $LiMn_{11/6}Al_{1/6}O_2$ 분말들이 좋은 사이클 특성을 가졌다. 전류밀도 0.1 C에서 70 사이클 충방전 후에 $LiMn_{11/6}Al_{1/6}O_4$ 분말들의 방전 용량은 107 mAh/g에서 100 mAh/g으로 감소하였고 93%의 사이클 효율을 유지하였다.