• Bulletin of the Korean Chemical Society
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• v.19 no.4
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• pp.462-466
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• 1998

The homobimetallic anion, $({\eta}^5-MeCp)Mn(CO)_2Mn(CO)_5-M^+\; (M^+=Na^+, PPN^+$) was disrupted by $PR_3\;(R=C_6H_5,\;C_2H_5,\;OCH_3)$ in THF at various temperatures (r.t. ∼65℃) under the pseudo first order reaction conditions where excess of $PR_3$ was employed under a nitrogen atmosphere. For the reaction involving $PPN^+$ analog, Mn-Mn heterolytic cleavage occurred, leading to $PPN^+Mn(CO)_5^-\; and \;({\eta}^5-MeCp)Mn(CO)_2PR_3$ as products; however, in case of $Na^+\; analog,\; Na^+$ seems to play a novel counter ion effect on the disruption reaction by transferring one terminal CO from the $Mn(CO)_5$ moiety on to the $({\eta}^5-MeCp)Mn(CO)_2$ of the corresponding homobimetallic complex, eventually resulting in $Na^+Mn(CO)_4PR_3^-\;and\;({\eta}^5-MeCp)Mn(CO)_3$. This reaction is of overall first order with respect to [homobimetallic complex] with the activation parameters (ΔH≠=23.0±0.7 kcal/mol, ΔS≠= - 8.7±0.8 e.u. for $Na^+$ analog; ΔH≠=28.8±0.4 kcal/mol, ΔS≠=15.7±0.6 e.u. for $PPN^+$ analog reaction).

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.18 no.8
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• pp.702-707
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• 2005

Spinel $LiMn_2O_4$ has become appealing because manganese is inexpensive and environmentally benign. In general, cathodes for lithium ion batteries include carbon as a conductive agent that provides electron transfer between the active material and the current collector. In this work, we selected Acetylene Black and Super P Black as conductive agents, and then carried out their comparative investigation for the performances of the $Li/LiMn_2O_4$ cells using different conductive agents with different particle size. In addition, their electrochemical impedance characteristic of $Li/Mn_2O_4$ cells using different conductive agents is effectively identified through a.c. impedance technique. As a consequence, $Li/LiMn_2O_4$ cells with Super P Black show better electrochemical performances ascribed to the significant contribution of feasible ionic conduction due to larger particle size than those with Acetylene Black.

• Korean Chemical Engineering Research
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• v.49 no.5
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• pp.541-547
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• 2011

Nanorod-clustered $MnO_2$ precursors with ${\alpha}$-, ${\beta}$-, and ${\gamma}$-phases are synthesized by hydrothermal reaction of $MnSO_45H_2O$ and $(NH_4)S_2O_8$. The formation of nanorod-clustered ${\beta}-MnO_2$ is particularly confirmed under the conditions of high reactant concentration and hydrothermal reaction at $150^{\circ}C$. The spinel $LiMn_2O_4$ nanorod-clusters are also prepared by lithiating the $MnO_2$ precursors, varying the concentration of lithiating agent ($LiC_3H_3O_2{\cdot}2H_2O$) and heat treatment temperature, and characterized for use as cathode material of lithium-ion batteries. As a result, the nanorod-clustered $LiMn_2O_4$ prepared from the ${\beta}-MnO_2$ at higher $LiC_3H_3O_2{\cdot}2H_2O$ concentration and the annealing at $800^{\circ}C$ is proven to show the cubic spinel structure and to achieve the high initial discharge capacity of 120 mAh/g.

• Journal of the Korean Ceramic Society
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• v.48 no.5
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• pp.379-383
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• 2011

This paper presents the synthesis of one-dimensional spinel $LiMn_2O_4$ nanostructures using a facile and scalable two-step process. $LiMn_2O_4$ nanorods with average diameter of 100 nm and length of 1.5 ${\mu}m$ have been prepared by solid-state lithiation of hydrothermally synthesized ${\beta}$-$MnO_2$ nanorods. $LiMn_2O_4$ nanowires with diameter of 10 nm and length of several micrometers have been fabricated via solid-state lithiation of ${\beta}$-$MnO_2$ nanowires. The precursors have been lithiated with LiOH and reaction temperature and pressure have been controlled. The complete structural transformation to cubic phase and the maintenance of 1-D nanostructure morphology have been evaluated by XRD, SEM, and TEM analysis. The size distribution of the spinel $LiMn_2O_4$ nanorods/wires has been similar to the $MnO_2$ precursors. By control of reaction pressure, cubic 1-D spinel $LiMn_2O_4$ nanostructures have been fabricated from tetragonal $MnO_2$ precursors even below $500^{\circ}C$.

• 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.

• Applied Chemistry for Engineering
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• v.10 no.3
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• pp.445-449
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• 1999

Hydrophilic polyphosphazenes were synthesized from hydrophobic polyphosphazenes by adding methoxyethylenoxy side chains and cast by dip-coating method into membranes supported on porous polypropylene mesh filter sheet for metal separation testing. A solution of $Cr^{3+},\;Co^{2+},\;Mn^{2+}$ nitrates was used in diffusion experiments which were conducted from $25^{\circ}C$ to $60^{\circ}C$. lt was found that the ion transport properties were increased as the repeating number of ethylenoxy side chain increased. Membrane from trifluoroethoxy methoxyethoxyethoxyethoxy co-substituted polyphosphazenes was found to separate $Cr^{3+}$ ion from $Mn^{2-}$ and $Co^{2+}$ ions with separation factor of 4.5 at $60^{\circ}C$.

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.245-250
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• 2016

The layered $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composite with well crystalized and high specific capacity is prepared by molten-salt method and using the substitution of Na for Li-ion battery. The effects of annealing temperature, time, Na contents, and electrochemical performance are investigated. In XRD analysis, the substitution of Na-ion resulted in the P2-$Na_{2/3}MO_2$ structure ($Na_{0.70}MO_{2.05}$), which co-exists in the $Na_{0.6}Li_{0.6}[Mn_{0.72}Ni_{0.18}Co_{0.10}]O_2$ composites. The discharge capacities of cathode materials exhibited $284mAhg^{-1}$ with higher initial coulombic efficiency.

• 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 Electrochemical Science and Technology
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• v.15 no.1
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• pp.168-177
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• 2024

Ni-rich cathode is one of the promising candidates for high-energy lithium-ion battery applications. Due to its specific capacity, easy industrialization, and good circulation ability, Ni-rich cathode materials have been widely used for lithium-ion batteries. However, due to the limitation of the co-precipitation method, including sewage pollution, and the instability of the long production cycles, developing a new efficient and environmentally friendly synthetic approach is critical. In this study, the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder was successfully synthesized by an efficient spray-drying method using carbonate compounds as a raw material. This Ni_0.91Co_0.06Mn_0.03CO₃ precursor was calcined by mixing with LiOH·H₂O (5 wt% excess) at 480℃ for 5 hours and then sintered at two different temperatures (780℃/800℃) for 15 hours under an oxygen atmosphere to complete the cathode active material preparation, which is a key component of lithium-ion batteries. As a result, LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were obtained successfully via a simple sintering process on the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder. Furthermore, the obtained LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were characterized. Overall, the material sintered at 780℃ shows superior electrochemical performance by delivering a discharge capacity of 190.76 mAh/g at 1^st cycle (0.1 C) and excellent capacity retention of 66.80% even after 50 cycles.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.07a
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• pp.713-716
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• 2001

In many papers, the electrochemical analysis of LiMn$_2$O$_4$shows the transition results of Mn$^{3+}$ ion. Charge ordering is accompanied by simultaneous orbital ordering due to the Jahn-Teller effect in Mnl$^{3+}$ ions. To analyze the cycle performance of LiMn$_{2-x}$Cu$_{x}$ O$_4$as the cathode of 4 V class lithium secondary batteries, XRD, TGA analysis were conducted. Although the cycle performance of the LiMn$_{2-x}$Cu$_{x}$ O$_4$was improved from pure LiMn$_2$O$_4$, the discharge capacity was significantly lower than LiCoO$_2$. In this paper, We study the Electrochemical characterization and enhanced stability of Cu-doped spinels in the LiMn$_{2-x}$Cu$_{x}$ O$_4$upon initial cycling.l cycling.