• Journal of the Korean Electrochemical Society
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• v.25 no.4
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• pp.184-190
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• 2022

Spinel LiMn₂O₄ (LMO) and layered LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) are widely used as positive electrode materials for lithium-ion batteries. LMO and NCM positive electrode materials have a complementary properties. LMO has low cost and high safety and NCM materials show a relatively high specific capacity and better cycle life even at elevated temperature. Therefore, the LMO and NCM active materials are blended and used as a positive electrode in large-size batteries for electric vehicles (xEV). In this study, the cycle performance of a blended electrode prepared by simply mixing LMO and NCM and a bi-layer electrode in which two electrode layers aree sequentially coated are compared. The bi-layer electrode prepared by composing the same ratio of both active materials has similar capacity and cycle performance to the blend electrode. However, the LN electrode coated with LMO first and then NCM is the best in the full cell cycle performance at elevated temperature, and the NL electrode, in which NCM is first coated with LMO has a faster capacity degradation than the blended electrode because LMO is mainly located on the top of the electrode adjacent to electrolyte and graphite negative electrode. Also, the LSTA (linear sweep thermmametry) analysis results show that the LN bi-layer electrode in which the LMO is located inside the electrode has good thermal stability.

• Korean Journal of Materials Research
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• v.29 no.12
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• pp.774-780
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• 2019

The performance of Li-ion hybrid supercapacitors (asymmetric-type) depends on many factors such as the capacity ratio, material properties, cell designs and operating conditions. Among these, in consideration of balanced electrochemical reactions, the capacity ratio of the negative (anode) to positive (cathode) electrode is one of the most important factors to design the Li-ion hybrid supercapacitors for high energy storing performance. We assemble Li-ion hybrid supercapacitors using activated carbon (AC) as anode material, lithium manganese oxide as cathode material, and organic electrolyte (1 mol L^-1 LiPF₆ in acetonitrile). At this point, the thickness of the anode electrode is controlled at 160, 200, and 240 ㎛. Also, thickness of cathode electrode is fixed at 60 ㎛. Then, the effect of negative and positive electrode ratio on the electrochemical performance of AC/LiMn₂O₄ Li-ion hybrid supercapacitors is investigated, especially in the terms of capacity and cyclability at high current density. In this study, we demonstrate the relationship of capacity ratio between anode and cathode electrode, and the excellent electrochemical performance of AC/LiMn₂O₄ Li-ion hybrid supercapacitors. The remarkable capability of these materials proves that manipulation of the capacity ratio is a promising technology for high-performance Li-ion hybrid supercapacitors.

• Korean Journal of Materials Research
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• v.32 no.4
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• pp.210-215
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• 2022

Extensive research is being carried out on Ni-rich Li(Ni_xCo_yMn_1-x-y)O₂ (NCM) due to the growing demand for electric vehicles and reduced cost. In particular, Ni-rich Li(Ni_xCo_yMn_1-x-y-zAl_z)O₂ (NCMA) is attracting great attention as a promising candidate for the rapid development of Co-free but electrochemically more stable cathodes. Al, an inactive element in the structure, helps to improve structural stability and is also used as a doping element to improve cycle capability in Ni-rich NCM. In this study, NCMA was successfully synthesized with the desired composition by direct coprecipitation. Boron and tin were also used as dopants to improve the battery performance. Macro- and microstructures in the cathodes were examined by microscopy and X-ray diffraction. While Sn was not successfully doped into NCMA, boron could be doped into NCMA, leading to changes in its physicochemical properties. NCMA doped with boron revealed substantially improved electrochemical properties in terms of capacity retention and rate capability compared to the undoped NCMA.

• Applied Chemistry for Engineering
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• v.35 no.3
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• pp.182-191
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• 2024

Li(Ni_xCo_yMn_1-x-y)O₂ (NCM) is the intensively developed cathode material for expanding the electric vehicle market and developing lithium-ion batteries that meet higher capacity, longer life, and lower cost. High-nickel NCM increases the nickel content to 80% or more, securing price competitiveness by improving performance with high energy density and reducing the cost of cobalt. However, the high-nickel NCM materials have a residual lithium problem, leading to issues in battery performance degradation and stability. While various methods exist for removing residual lithium, such as washing, doping, and coating, this paper focuses on recent research trends in coatings aimed at enhancing NCM performance and stability by removing residual lithium.

• Journal of Powder Materials
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• v.23 no.2
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• pp.136-142
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• 2016

As precursors of cathode materials for lithium ion batteries, $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders are prepared in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH in the presence of $NH_4OH$ in air or nitrogen ambient. Calcination of the precursors with $Li_2CO_3$ for 8 h at $1,000^{\circ}C$ in air produces dense spherical cathode materials. The precursors and final powders are characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analysis, tap density measurement, and thermal gravimetric analysis. The precursor powders obtained in air or nitrogen ambient show XRD patterns identified as $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$. Regardless of the atmosphere, the final powders exhibit the XRD patterns of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (NCM). The precursor powders obtained in air have larger particle size and lower tap density than those obtained in nitrogen ambient. NCM powders show similar tendencies in terms of particle size and tap density. Electrochemical characterization is performed after fabricating a coin cell using NCM as the cathode and Li metal as the anode. The NCM powders from the precursors obtained in air and those from the precursors obtained in nitrogen have similar initial charge/discharge capacities and cycle life. In conclusion, the powders co-precipitated in air can be utilized as precursor materials, replacing those synthesized in the presence of nitrogen injection, which is the usual industrial practice.

• Journal of the Korean Electrochemical Society
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• v.17 no.3
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• pp.149-155
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• 2014

In this study, a positive-electrode material in a lithium secondary battery $Li[Ni_{0.575}Co_{0.1}Mn_{0.325}]O_2$ was synthesized as precursor by co-precipitation. Cathode material was synthesized by adding iron. The synthesized cathode material was analyzed by scanning electron microscope and x-ray diffraction. The analysis of x-ray diffraction showed that the a-axis and c-axis is increased by doping iron. And $I_{(003)}/I_{(104)}$ is increased and $I_{(006)}+I_{(102)}/I_{(101)}$ is decreased. Through this result, it was confirmed that the structural stability is improved. And impedance measurements show that the charge transfer resistance ($R_{ct}$) is lowered by doping iron. Consequently, electrochemical properties are improved by doping iron. In particular, the cycle characteristics are improved at a high temperature condition (328 K). Structural stabilities are contributing to the cycle properties.

• Journal of the Korean Electrochemical Society
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• v.6 no.4
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• pp.229-235
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• 2003

A precursor of lithium manganese oxide was synthesized by mixing $(CH_3)_2CHOLi\;with\;Mn(CH_3COO)_2{\cdot}4H_2O$ in ethanol using a sol-gel method, then heat-treated at $400^{\circ}C\;and\;800^{\circ}C$ in air atmosphere. The condition of heat treatment was determined by thermogravimetric analysis/differential thermogravimetric analysis (TGA/DTA). The characterization of the lithium manganese oxide was done by X-ray diffraction (XRD) spectra and scanning electron microscopy (SEM). The electrochemical characteristics of lithium manganese oxide electrode for lithium ion battery were measured by cyclic voltammetry (CV), chronoamperometry and AC impedance method using constant charge/discharge process. The electrochemical behaviors of the electrode have been investigated in a 1.0M $LiClO_4/propylene$ carbonate electrolyte solution. The diffusivity of lithium ions, $D^+\;_{Li}\;^+$, as determined by AC impedance technique was $6.2\times10^{-10}cm^2s^{-1}$.

• Journal of the Korean Electrochemical Society
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• v.9 no.1
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• pp.34-39
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• 2006

Electrochemical properties of Cu foil current collector with a $Li_{0.5}La_{0.5}TiO_3$ Cu a Si thin film deposited by r.f sputtering as an anode for Li free battery were evaluated. The Cu foil current collectors were lied in and out of plasma during sputtering process. The X-ray diffraction results indicated that the as-deposited Si and $Li_{0.5}La_{0.5}TiO_3$ thin films in and out of plasma did not show any crystalline difference. The $Li_{0.5}La_{0.5}TiO_3$ film in plasma and Si film out of plasma showed better cyclability since crystalline $Li_{0.5}La_{0.5}TiO_3$ has much higher ionic conductivity and crystalline Si film is much sensitive far volume change during charge-discharge process. These results suggested that the deposition of amorphous Si on Cu foil current collector is much better for fabrication of Li free battery and it can be useful for the unique battery with a cycling number constraint of below 10.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.51-57
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• 2015

We report the effect of the impurities including water and bromide in the propylmethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PMPyr-TFSI) on the electrochemical performance of lithium ion batteries. The several kinds of PMPyr-TFSI electrolytes with different amount of impurities are applied as the electrolyte to the cell with the high potential electrode, $LiNi_{0.5}Mn_{1.5}O_4$ spinel. It is found that the impurities in the electrolytes cause the detrimental effect on the cell performance by tracing the cycleability, voltage profile and Coulombic efficiency. Especially, the polarization and Coulombic efficiency go to worse by both impurities of water and bromide, but the cycleability was not highly influenced by bromide impurity unlike the water impurity.

• Economic and Environmental Geology
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• v.46 no.5
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• pp.375-390
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• 2013

The Kenticha rare-element (Ta-Li-Nb-Be) mineralized zone is located in ophiolitic fold and thrust complex of southern Ethiopia and was firstly discovered by joint exploration program of Ethiopia-Soviet in 1980s. It includes Dermidama, Kilkele, Shuni Hill, Kenticha, and Bupo pegmatites from south to north. The Kenticha pegmatite intruded parallel to NS-striking serpentinite and talc-chlorite schist, and is exposed approximately 2 km length and 400-700 m width. The Kenticha pegmatite is internally zoned and subdivided into lower quartz-muscovite-albite granite, intermediate muscovite-quartz-albite-microcline pegmatite, and upper spodumene-quartz-albite pegmatite, based on their mineral assemblage. The major, trace elements (e.g., Rb, Li, Nb, Ta, and Ga), and element ratios (e.g., K/Rb, Nb/Ta, Mg/Li, and Al/Ga) suggest that the fractionation and solidification of pegmatite have progressed from the lower towards upper pegmatite. In contrast, unlike general magmatic fractionation, Mg/Li ratios of the Kenticha pegmatite tend to be increased towards the upper pegmatite. It may result from post-magmatic hydrothermal alteration and/or interaction with upper ultramafic rock. Rare-element mineralization in Kenticha pegmatite concentrates on the upper pegmatite, which contains up to 3.0 wt % $Li_2O$, 3,780 ppm Rb, 111 ppm Cs, 1,320 ppm Ta, and 332 ppm Nb. Ore minerals in Kenticha pegmatite mostly include tantalite, spodumene, and lepidolite, and tantalite has an association with coarser quartz-spodumene and relatively fine sacchroidal albite. The tantalite is classified into Mn-tantalite as a function of $Mn^*[Mn/(Mn+Fe)]$ and $Ta^*[Ta/(Ta+Nb)]$ values. Its compositions ($Mn^*$, $Ta^*$, and Nb/Ta) between coarse and fine tantalites are different and the former is strongly enriched in Ta and depleted in Nb compared to latter one. In conclusion, rare-element mineralization in the Kenticha pegmatite may has occurred in the latest stage of magmatic fractionation.