• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.1995-2000
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• 2013

Layered $Li_{1.2}(Fe_{0.16}Mn_{0.32}Ni_{0.32})O_2$ was prepared by the mixed hydroxide method at various temperatures. Xray diffraction (XRD) pattern shows that this material has a ${\alpha}-NaFeO_2$ layered structure with $R{\bar{3}}m$ space group and that cation mixing is reduced with increasing synthesis temperature. Scanning electron microscopy (SEM) reveals that nano-sized $Li_{1.2}(Fe_{0.16}Mn_{0.32}Ni_{0.32})O_2$ powder has uniform particle size distribution. X-ray absorption near edge structure (XANES) analysis is used to study the local electronic structure changes around the Mn, Fe, and Ni atoms in this material. The sample prepared at $700^{\circ}C$ delivers the highest discharge capacity of 207 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ with good capacity retention of 80% after 20 cycles.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.622-628
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• 2013

Nanocrystalline spinel lithium manganese oxide ($LiMn_2O_4$) powders with narrow-size-distribution, pure-phase particles, and high crystallinity with an average crystallite size of about 70 nm were synthesized at $600^{\circ}C$ for 6 h in air by freeze drying method. Spinel $LiMn_2O_4$ is also prepared by sol-gel using citric acid as a chelating agent. The influence of different parameters such as pH conditions, solvent, molar ratio of citric acid to total metal ions, calcination temperature, starting material on the structure, morphology and purity of this oxide was investigated. The results of sol-gel method show that pure $LiMn_2O_4$ with average crystallite size of about 130 nm can be produced from nitrate salts as starting materials at $800^{\circ}C$ for 6 h in air. The optimum pH and molar ratio of chelating agent to total metal ions are $4{\leq}pH{\leq}6$ and 1.0, respectively. A possible mechanism on the formation of the nanocrystallines synthesized by sol-gel was also discussed. At the end a comparison of the differences between two methods was made on the basis of x-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA) tests.

• Journal of Powder Materials
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• v.19 no.3
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• pp.210-214
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• 2012

Mass production-capable $Li_2MnSiO_4$ powder was synthesized for use as cathode material in state-of-the-art lithium-ion batteries. These batteries are main powder sources for high tech-end digital electronic equipments and electric vehicles in the near future and they must possess high specific capacity and durable charge-discharge characteristics. Amorphous silicone was quite superior to crystalline one as starting material to fabricate silicone oxide with high reactivity between precursors of sol-gel type reaction intermediates. The amorphous silicone starting material also has beneficial effect of efficiently controlling secondary phases, most notably $Li_xSiO_x$. Lastly, carbon was coated on $Li_2MnSiO_4$ powders by using sucrose to afford some improved electrical conductivity. The carbon-coated $Li_2MnSiO_4$ cathode material was further characterized using SEM, XRD, and galvanostatic charge/discharge test method for morphological and electrochemical examinations. Coin cell was subject to 1.5-4.8 V at C/20, where 74 mAh/g was observed during primary discharge cycle.

• Journal of the Korean Electrochemical Society
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• v.15 no.2
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• pp.67-73
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• 2012

Spherical lithium manganese oxide spinel, $LiMn_{2-x}M_xO_4$ (M = Al, Mg, B) prepared by wet-milling, spray-drying, and sintering process has been investigated as a cathode material for lithium ion batteries. As-prepared powders exhibit various surface morphologies and internal density in terms of boron (B) doping level. It is found that the dopant B drives the growth of the primary particle and minimizes the surface area of the powder. As a result, the dopant enhances the internal density of the particles. Electrochemical tests demonstrated that the capacity of the synthesized material at 5 C could be maintained up to 90% of that at 0.2 C. The cycle performance of the material showed that the initial capacity was retained up to 80% even after 500 cycles under the high temperature of $60^{\circ}C$.

• Korean Journal of Crystallography
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• v.15 no.1
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• pp.44-50
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• 2004

Spinel structured lithium managanese oxide $(LiMn_2O_4)$ powder with well defined facetted morphology was prepared by precipitation-evaporation method. {111}, {110}, and {100} planes are mainly observed in the $LiMn_2O_4$ powder. And powder shape of tetradecahedron and octahedron was observed depending on the calcinations temperature. The observed powder morphology observed seemed to be related to the nonstoichiometry of the oxygen in the $LiMn_2O_4$ spinel structure. Oxygen nonstoichiometry might be responsible for the Jahn-teller effect and structure transition which in turn affects the surface energy of the {111}, {110}, and {100} planes. Powder shape transition from tetradecahedron to octahedron seemed to be related to the surface energy of the {111}, {110}, and {100} planes with oxygen nonstoichiometry.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.12 no.10
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• pp.4660-4665
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• 2011

New precursors as a Li adsorbent, $Li_{1.6}(MnM)_{1.6}O_4$ (M=Cu, Ni, Co, Fe), were synthesized by hydrothermal method and their physicochemical properties were discussed. XRD and HRTEM results revealed that the original spinel structure was stabilized by cobalt-doping while Cu-, Ni- and Fe-doping led to structural changes. Such a structural stabilization by Cobalt-doping was maintained after lithium leaching by acid treatment. Li absorption efficiency from seawater was significantly enhanced by using the Cobalt-doped spinel manganese oxide, $Li_{1.6}[MnCo]_{1.6}O_4$, compared to the commercially available $Li_{1.33}Mn_{1.67}O_4$; the adsorbed amount of Li from 1g-adsorbent was 35 and 16 mg by $Li_{1.6}[MnCo]_{1.6}O_4$, and $Li_{1.33}Mn_{1.67}O_4$, respectively.

• Journal of the Korean Electrochemical Society
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• v.7 no.3
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• pp.131-137
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• 2004

Sol-gel method which provides better electrochemical and physiochemical properties compared to the solid-state method was used to synthesize the material of $LiFe_yMn_{2-y}O_4$. Fe was substituted to increase the structural stability so that the effects of the substitution amount and sintering temperature were analyzed. XRD was used for the structural analysis of produced material, which in turn, showed the same cubic spinel structure as $LiMn_2O_4$ despite the substitution of $Fe^{3+}$. During the synthesis of $LiFe_yMn_{2-y}O_4$, as the sintering temperature and the doping amount of Fe(y=0.05, 0.1, 0.2)were increased, grain growth proceeded which in turn, showed a high crystalline and a large grain size, certain morphology with narrow specific surface area and large pore volume distribution was observed. In order to examine the ability for the practical use of the battery, charge-discharge tests were undertaken. When the substitution amount of $Fe^{3+}\;into\;LiMn_2O_4$ increased, the initial discharge capacity showed a tendency to decrease within the region of $3.0\~4.2V$ but when charge-discharge processes were repeated, other capacity maintenance properties turned out to be outstanding. In addition, when the sintering temperature was $800\~850^{\circ}C$, the initial capacity was small but showed very stable cycle performance. According to EVS(electrochemical voltage spectroscopy) test, $LiFe_yMn_{2-y}O_4(y=0,\;0.05,\;0.1,\;0.2)$ showed two plateau region and the typical peaks of manganese spinel structure when the substitution amount of $Fe^{3+}$ increased, the peak value at about 4.15V during the charge-discharge process showed a tendency to decrease. From the previous results, the local distortion due to the biphase within the region near 4.15V during the lithium extraction gave a phase transition to a more suitable single phase. When the transition was derived, the discharge capacity decreased. However the cycle performance showed an outstanding result.

• Journal of the Korean Electrochemical Society
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• v.4 no.1
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• pp.1-5
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• 2001

Composite ratio of $LiMn_2O_4$ in cathode was optimized as function of specific surface area. Binder has to be used as possible as little, and it should maintain adhesive property between cathode composite and current collector even though in electrolytes. For this purpose, We used 'Hot Roll Pressing' method, and it was effective. To prevent separation of cathode composite from current collector, PVDF(Polyvinylidenefluoride) has to be mixed more than $1.1\%$ in weight ratio to sum of surface area of lithium manganese oxide and conducting agents. Specific internal resistance was reduced as by increasing electrical conductivity of cathode. And Ratio of 2C rate discharge capacity to 0.2C rate discharge capacity was increased by $17\%$, as increasing electrical conductivity from 0.019 mS/cm to 0.036 mS/cm.

• Korean Journal of Materials Research
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• v.31 no.2
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• pp.68-74
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• 2021

Zinc-ion Batteris (ZIBs) are recently being considered as energy storage devices due to their high specific capacity and high safety, and the abundance of zinc sources. Especially, ZIBs can overcome the drawbacks of conventional lithium ion batteris (LIBs), such as cost and safety issues. However, in spite of their advantages, the cathode materials under development are required to improve performance of ZIBs, because the capacity and cycling stability of ZIBs are mainly influenced by the cathode materials. To design optimized cathode materials for high performance ZIBs, a novel manganese oxide (MnO2) coated graphite sheet is suggested herein with improved zinc-ion diffusion capability thanks to the uniformly decorated MnO2 on the graphite sheet surface. Especially, to optimize MnO2 on the graphite sheet surface, amounts of percursors are regulated. The optimized MnO2 coated graphite sheet shows a superior zinc-ion diffusion ability and good electrochemical performance, including high specific capacity of 330.8 mAh g-1 at current density of 0.1 A g-1, high-rate performance with 109.4 mAh g-1 at a current density of 2.0 A g-1, and remarkable cycling stability (82.2 % after 200 cycles at a current density of 1.0 A g-1). The excellent electrochemical performance is due to the uniformly decorated MnO2 on the graphite sheet surface, which leads to excellent zinc-ion diffusion ability. Thus, our study can provide a promising strategy for high performance next-generation ZIBs in the near future.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3553-3558
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• 2014

The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.