• 한국전기전자재료학회논문지
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• 제14권8호
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• pp.663-669
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• 2001

Spinel LiM $n_2$ $O_4$ and LiM $n_{1.9}$M $g_{0.1}$ $O_4$ power was synthesized with solid-state method by calcining the mixture of LiOH.$H_2O$, Mn $O_2$ and MgO at 80$0^{\circ}C$ for 36 h in an air atmosphere. To investigate the effect of temperature on he cycle performance of cathode material during cycling, charge-discharge experiments and ac impedance measurement were performed. Initial discharge capacity was gradually increased with the increase of charge-discharge temperature. Discharge capacity at high temperature was suddenly decreased during cycling. On the other hand, discharge capacity at low temperature was almost constant during cycling. It confirmed that Mn dissolution is serious at high temperature than at low temperature. LiM $n_2$ $O_4$ and LiM $n_{1.9}$M $g_{0.1}$ $O_4$ showed the best capacity and stability at room temperature.ure.ure.

• 전기화학회지
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• 제3권3호
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• pp.131-135
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• 2000

[ $LiMn_2O_4$ ]박막전지의 충방전 사이클에 따른 용량 감소의 원인을 파악하기 위하여, $LiMn_2O_4/1M\;LiClO_4-PC/Li$전지를 구성하여 충방전 사이클에 따른 AC impedance분석을 수행하였다. 적절한 등가회로를 이용하여 비선형 최소자승 맞춤에서 얻은 값이 Impedance측정 결과와 잘 일치하였다. 충방전에 따른 정전용량은 초기의 급격한 감소를 보인 이후 완만한 감소를 보였다. 충방전 사이클이 초기 70-100사이클까지는 저항 성분 중 양극전해질 계면의 전하 전달저항 성분이 급격히 증가하다가 이후 안정된 값을 보임으로 초기 급격한 용량변화의 원인으로 파악되었다. 전하전달 저항이 안정된 이후에는 Warburg저항이 충방전에 따라 조금씩 증가하였으며, LiMn2O4박막의 화학확산 계수가 사이클에 따라 초기 $5.15\times10^{-11}cm^2/sec$에서 800사이클이 지난 후 $6.3\times10^{-12}cm^2/sec$로 점차 감소하는 것이 관찰되어 100사이클이 후의 용량감소의 지배적 원인으로 파악하였다. Warburg저항의 증가는 Jahn-Teller변형 또는 Mn용해에 의한 것으로 추정하였다.

• 한국전기전자재료학회논문지
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• 제15권4호
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• pp.361-366
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• 2002

Spinel $LiMn_{2-y}M_yO_4$ and $LiMn_{2-y}M_yO_4$ (M=Mg, Zn) powders were synthesized by solid-state method at $800^{\circ}C$ for 37h. Crystal structure and electrochemical properties were analyzed by X-ray diffraction, charge-discharge test, cyclic voltammetry and ac impedance to $LiMn_{2-y}M_yO_4$. All cathode material showed spinel structure in X-ray diffraction. Ununiform distortion which calculated by (111) face and (222) face was almost constant in spite of the change of the kind and the substituting ratio of the metal cation in $LiMn_{2-y}M_yO_4$ (M=Mg, Zn). $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cell substituted $Mg^{+2}$ and $Zn^{+2}$ showed excellent discharge capacities than other cells, which it presented about 120mAh/g at the 1st cycle and about 73mAh/g at the 250th cycle, respectively. AC impedance of $LiMn_{2-y}M_yO_4/Li$ cells showed the similar resistance of about 65~110$\Omega$ before cycling.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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• pp.455-458
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• 2001

Spinel $LiMn_{2-y}$$M_{y}$ $O_4$powder was prepared solid-state method by calcining the mixture of LiOH - $H_2O$, Mn $O_2$, ZnO and MgO at 80$0^{\circ}C$ for 36h. To investigate the effect of substitution with Mg, Zn cation, charge-discharge experiments and initial impedance spectroscopy performed. The structure of $LiMn_{2-y}$$M_{y}$ $O_4$crystallites was analyzed from powder X-ray diffraction data as a cubic spinel, space group Fd3m. all cathode material showed spinel phase based on cubic phase in X-ray diffraction. Ununiform which calculated by (111) face and (222) face was constant in spite of the change of y value, except PUf\ulcorner LiM $n_2$ $O_4$. The discharge capacities of the cathode for the cation subbstitUtes $LiMn_{2-y}$$M_{y}$ $O_4$/Li cell at the 1st cycle and at the 40th cycle were about 120~124 and 108~112mAh/g except LiM $n_{1.9}$Z $n_{0.1}$ $O_4$/Li cell, respectively. This cell capacity is retained by 93% after 40th cycle. AC impedance of $LiMn_{2-y}$$M_{y}$ $O_4$/Li cells revealed the similar resistance of about 65~110$\Omega$ before cycling. before cycling.g.g.

• 한국응용과학기술학회지
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• 제20권1호
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• pp.33-43
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• 2003

$LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

• 한국전기전자재료학회논문지
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• 제15권2호
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• pp.162-168
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• 2002

The purpose of this study is to research and develop LiMnO$_2$-organic and Li$_{0.3}$MnO$_{2}$-organic composite with high energy density for Lithium ion polymer battery. This paper describes cyclic voltammetry, impedance sepctroscopy, electrochemical properties of LiMnO$_2$-organic and Li$_{0.3}$MnO$_{2}$-organic composite with polymer electrolyte as a function of a mixed ratio. The first discharge capacity of LiMnO$_2$-PAn with 3 wt.% PAn was 83mHA/g, while that of Li$_{0.3}$MnO$_{2}$-PPy composite was 136 mAh/g. The Ah efficiency was above 98% after the 2nd cycle. The LiMnO$_2$-PAn with DMcT 2 wt.% and Li$_{0.3}$MnO$_{2}$-PPy composites cathode with 5wt. PPy in PVDF-PC-EC-LiClO$_4$ electrolyte showed good capaity with cycling. The discharge capacity of LiMnO$_2$-PAn with wt.% DMcT was 80 and 130 mAh/g at 1st and 12th cycle, respectively. The capacity of LiMnO$_2$-PAn composite with 2 wt.% DMcT was higher than that of LiMnO$_2$-PAn composite.mposite.

• 전기화학회지
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• 제9권4호
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• pp.158-169
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• 2006

The present article is concerned with the overview of the chemically/surface modified cubic spinel $LiMn_2O_4$ as a cathode electrode far lithium ion secondary batteries. Firstly, this article presented a comprehensive survey of the cubic spinel structure and its correlated electrochemical behaviour of $LiMn_2O_4$. Subsequently, the various kinds of the chemically/surface modified $LiMn_2O_4$ and their electrochemical characteristics were discussed in detail. Finally, this article reviewed our recent research works published on the mechanism of lithium transport through the chemically/surface modified $Li_{1-\delta}Mn_2O_4$ electrode from the kinetic view point by the analyses of the experimental potentiostatic current transients and ac-impedance spectra.

• 전기화학회지
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• 제10권4호
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• pp.239-244
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• 2007

산소자리에 치환된 불소가 $Li_{1-x}FeO_2Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8) 양극 활물질에 미치는 영향을 고찰하기 위해 다양한 양의 불소를 치환시킨 $Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8, $0.05{\le}y{\le}0.15$) 양극 활물질을 고상법을 이용하여 합성하였다. 불소 미치환 시료 및 치환양이 0.05와 0.1의 시료의 경우, $1-1.5\;{\mu}m$ 크기의 막대 형상 분말 형태에 50-100 nm정도의 작은 구형 입자들이 주위에 분포되어 있는 형태이었다. 반면, 불소 치환양이 0.15인 시료의 경우, 그 모양이 구형으로 변화되어지며 입자가 급격하게 성장하였다. 합성된 시료를 이용하여 제작된 셀들의 충 방전 수행 결과, $Li/Li_{1-x}FeO_{1.9}F_{0.1}-Li_xMnO_2$ 셀이 163 mAh/g의 가장 높은 초기용량을 보였으며 50 싸이클 후에도 95%의 높은 가역 특성을 보였다. 특히, 활물질내의 불소 치환양이 증가할수록 초기 방전용량도 같이 증가하였으나, 불소이온의 치환양이 일정량을 (y>0.1) 넘는 경우에는 산소 자리에 불소이온이 완전하게 치환되지 못하고 불순물로 존재함으로써 전지의 가역특성을 현저하게 저하시키는 요인으로 작용함을 확인하였다.

• 전기화학회지
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• 제16권3호
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• pp.162-168
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• 2013

$Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) 나노 복합체는 높은 이론 용량을 가지고 있어 전기 자동차용 2차 전지 활물질 재료로 많은 연구가 진행되고 있다. 하지만 $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)로부터 250 mAh/g 이상의 용량을 구현하기 위해서는 4.4 V 이상의 구동전압이 필요하며, 이러한 높은 구동 전압은 전지의 수명 및 고온 방치 특성의 저해 요소로 작용하고 있다. 본 연구에서는 이러한 문제점을 개선하기 위해서 FEC (Fluoroethylene carbonate), 플루오로알킬 에테르, $LiPF_6$가 주성분인 신규 전해액(F-based EL)을 설계하였다. F-based EL은 1.3 M $LiPF_6$ EC/EMC/DMC (3/4/3, v/v/v) (STD) 대비 안정한 SEI를 형성하며, 산화 안정성이 뛰어나 $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)/graphite 셀의 수명 및 방치 중 가스 저감에 효과가 있음을 확인할 수 있었다.

• Journal of Electrochemical Science and Technology
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• 제7권2호
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• pp.139-145
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• 2016

The electrochemical performance of carbon-coated LiMn₂O₄ nanoparticles was reported. The polydopamine layer was introduced as a new organic carbon source. The carbon layer was homogeneously coated onto the surface of the LiMn₂O₄ nanoparticles because the polymerization process from the dopamine solution (in a buffer solution, pH 8.5) easily and uniformly formed a polydopamine layer. The phase integrity of LiMn₂O₄ deteriorated during the carbon-coating process due to oxygen loss, although the main structure was maintained. The carbon-coated sample led to improved rate capability because of the effect of the conductive carbon layer. Moreover, the carbon coating also enhanced the cyclic performance. This indicates that the carbon layer may suppress unwanted side reactions with the electrolytes and compensate for the low electronic conductivity of the pristine LiMn₂O₄.