• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1516-1522
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• 2014

A series of 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ surface treatments were applied to $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates. The $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates were synthesized using a co-precipitation method. Sample (a) was left pristine and variations of the 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ were applied to samples (b), (c) and (d). XRD was used to verify the space group of the samples as R$\bar{3}$m. Additional morphology and particle size data were obtained using SEM imagery. The $Al_2O_3$ coating layers of sample (b) and (d) were confirmed by TEM images and EDS mapping of the SEM images. 2032-type coin cells were fabricated in a glove box in order to investigate their electrochemical properties. The cells were charged and discharged at room temperature ($25^{\circ}C$) between 2.0V and 4.8V during the first cycle. The cells were then charged and discharged between 2.0V and 4.6V in subsequent cycles. Sample (d) exhibited lower irreversible capacity loss (ICL) in the first charge-discharge cycle as compared to sample (c). Sample (d) also had a higher discharge capacity of ~250 mAh/g during the first and second charge-discharge cycles when compared with sample (c). The rate capability of the $Al_2O_3$-coated sample (b) and (d) was lower when compared with sample (a) and (c). Sample (d), coated with $Al_2O_3$ after the surface treatment with $(NH_4)_2SO_4$, showed an improvement in cycle performance as well as an enhancement of discharge capacity. The thermal stability of sample (d) was higher than that of the sample (c) as the result of DSC.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1675-1680
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• 2012

Three new cyanide-bridged $Cr^{III}Mn^{II}$ binuclear complexes, $[Mn(phen)_2Cl][Cr(bpmb)(CN)_2]{\cdot}H_2O$ ($\mathbf{1}$) (phen = 1,10-phenanthroline, $bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-methyl-benzenate), $[Mn(phen)_2Cl][Cr(bpmb)-(CN)_2]{\cdot}H_2O$ ($\mathbf{2}$) ($bpdmb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4,5-dimethyl-benzenate), and $[Mn(phen)_2Cl]-[Cr(bpClb)(CN)_2]{\cdot}CH_3OH{\cdot}H_2O$ ($\mathbf{3}$) ($bpClb^{2-}$ = 1,2-bis(pyridine-2-carboxamido)-4-chloro-benzenate) were obtained based on $Mn(phen)_2Cl_2$ and a series of dicyanidechromate(III) building blocks. Single crystal X-ray diffraction analysis shows the structures of the three complexes are dimeric type with two different metal centers linked by a cyanide group from corresponding dicyanidechromate(III) building block. Magnetic investigations indicate the existence of relatively weak antiferromagnetic coupling between Cr(III) and Mn(II) ions with best-fit constants $J_{CrMn}=-2.78(5)cm^{-1}$ for $\mathbf{1}$, $J_{CrMn}=-3.02(2)cm^{-1}$ for $\mathbf{2}$ and $J_{CrMn}=-2.27(3)cm^{-1}$ for $\mathbf{3}$ based on the spin exchange Hamiltonian = $-2J_{CrMn}\hat{S}_{Cr}\hat{S}_{Mn}$. The magneto-structural correlation of cyanide-bridged $Cr^{III}Mn^{II}$ complexes has been discussed at last.

• Journal of Industrial and Engineering Chemistry
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• v.68
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• pp.180-186
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• 2018

We report the discovery of Li-rich $Li_{1+x}[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y]O_2$ as a cathode material for rechargeable lithium-ion batteries in which a small amount of tetravalent vanadium ($V^{4+}$) is selectively and completely incorporated into the manganese sites in the lattice structure. The unwanted oxidation of vanadium to form a $V_2O_5-like$ secondary phase during high-temperature crystallization is prevented by uniformly dispersing the vanadium ions in coprecipitated $[(Ni_{0.225}Co_{0.15}Mn_{0.625})_{1-y}V_y](OH)_2$ particles. Upon doping with $V^{4+}$ ions, the initial discharge capacity (>$275mA\;h\;g^{-1}$), capacity retention, and voltage decay characteristics of the Li-rich layered oxides are improved significantly in comparison with those of the conventional undoped counterpart.

• Journal of the Korean Electrochemical Society
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• v.21 no.3
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• pp.47-54
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• 2018

To maximize the areal capacity($mAh\;cm^{-2}$) of $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$(NCM523) electrode with the same loading level of $15mg\;cm^{-2}$, three NCM523 electrodes with 4, 2, and 1 wt% poly(vinylidene fluoride)(PVdF) binder content are fabricated. Due to the delamination issue of electrode composite at the edge during punching process, the 1 wt% electrode is excluded for further evaluation. When the PVdF binder content decreases from 4 to 2 wt%, both adhesion strength and shear stress decrease from 0.4846 to $0.2627kN\;m^{-1}$ by -46% and from 3.847 to 2.013 MPa by -48%, respectively. Regardless of these substantial decline of mechanical properties, their initial electrochemical properties such as initial coulombic efficiency and voltage profile are almost the same. However, owing to high loading level, the 2 wt% electrode not only exhibits worse cycle performance than the 4 wt% electrode, but also cannot maintain its mechanical integrity only after 80 cycles. Therefore, if the binder content is reduced to increase the area capacity, the mechanical properties as well as the cycle performance must be carefully evaluated.

• Proceedings of the Korean Vacuum Society Conference
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• 2006.02a
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• pp.189-189
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• 2006

• 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.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.

• Journal of the Korean Electrochemical Society
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• v.23 no.4
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• pp.105-112
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• 2020

Transition metal oxide, which undergoes a conversion reaction in the negative electrode material for a lithium-ion batteries, has a high specific capacity, but still has several critical problems. In this study, manganese pyrophosphate (Mn₂P₂O₇), nickel pyrophosphate (Ni₂P₂O₇), and carbon composite materials with pyrophosphates as novel negative electrode materials instead of transition metal oxide, are synthesized through simple solid-state reaction. The initial reversible capacity of Mn₂P₂O₇ and Ni₂P₂O₇ are 333 and 340 mAh g^-1, and when the composite materials are composed with carbon, the reversible capacity increases to 433 and 387 mAh g^-1, respectively. The initial Coulombic efficiency is also improved by about 10%. The Mn₂P₂O₇ and carbon composite material has the highest initial capacity and efficiency, and has the best cycle performance. Mn₂P₂O₇ containing polyanion, has a lower specific capacity due to the large mass of polyanion compared to MnO (manganese oxide). However, since Mn₂P₂O₇ shows a voltage curve with a slope, the charging (lithiation) voltage increases from 0.51 to 0.57 V (vs. Li/Li⁺), and the discharge (delithiation) voltage decreases from 1.15 to 1.01 V (vs. Li/Li⁺). Therefore, the voltage efficiency of the cell is improved because the voltage difference between charging and discharging is greatly reduced from 0.64 to 0.44 V, and the operating voltage of the full cell increases because the negative electrode potential is lowered during the discharging process.

• Resources Recycling
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• v.23 no.4
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• pp.21-29
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• 2014

Nickel, cobalt and manganese-based(NCM, $Li(Ni_xCo_yMn_z)O_2$) cathode active materials of spent lithium-ion batteries contained valuable metals such as cobalt(15 ~ 20%), nickel(25 ~ 30%), manganese(10 ~ 15%) and lithium(5 ~ 10%). It was investigated the eco-friendly leaching process for the recovery of valuable metal from spent lithium-ion battery NCM cathode active materials by DL-malic acid($C_4H_5O_6$) as an organic leachant in this research. The experiments were carried out to optimize the process parameters for the recovery of cobalt, nickel and lithium by varying the concentration of lixivant, reductant concentration, solid/liquid ratio and temperature. The leaching solution was analyzed using ICP-OES(Inductively Coupled Plasma Optic Emission Spectrometer). Cathode active materials of 5 wt. % were introduced into the leaching solution which was 2 M DL-malic acid in addition of 5 vol. % $H_2O_2$ at $80^{\circ}C$ and it resulted in the recovery of 99.10% cobalt, 99.80% nickel and 99.75% lithium in 120 min. $H_2O_2$ in DL-malic acid solution acts as an effective reducing agents, which enhance the leaching of metals.

• Journal of the Korean earth science society
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• v.27 no.1
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• pp.49-60
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• 2006

The purpose of this study is to investigate geochemical characteristics for stream sediments in the Naju area. We collected 139 stream sediments samples from primary channels. Samples were dried slowly in the laboratory and chemical analysis was carried out using XRF. ICP-AES and NAA. In order to investigate geochemical characteristics, the geological groups categorized into granitic gneiss area, schist area, granite area, arenaceous rock area, tuff area, andesite area, and rhyolite area. Average contents of major elements for geological groups are $SiO_2\;58.37{\sim}66.06wt.%,\;Al_2O_3\;13.98{\sim}18.41wt.%,\;Fe_2O_3\;4.09{\sim}6.10wt.%,\;CaO\;0.54{\sim}1.33wt.%,\;MgO\;0.86{\sim}1.34wt.%,\;K_2O\;2.38{\sim}4.01wt.%,\;Na_2O\;0.90{\sim}1.32wt.%,\;TiO_2\;0.82{\sim}1.03wt.%,\;MnO\;0.09{\sim}0.15wt.%,\;P_2O_5\;0.11{\sim}0.18wt.%$. According to the comparison of average contents of major elements, $Al_2O_3\;and\;K_2O$ are higher in granitic gneiss area, $Fe_2O_3,\;CaO,\;P_2O_5$ are higher in tuff area, MgO and $TiO_2$ are higher in andesite area, $Na_2O_$ is higher in rhyolite area, $SiO_2$, and MnO are higher in arenaceous rock area. Average contents of minor and rare earth elements for geological groups are $Ba\;1278{\sim}1469ppm,\;Be\;1.1{\sim}1.5ppm,\;Cu\;18{\sim}25ppm,\;Nb\;25{\sim}37ppm,\;Ni\;16{\sim}25ppm,\;Pb\;21{\sim}28ppm,\;Sr\;83{\sim}155ppm,\;V\;64{\sim}98ppm,\;Zr\;83{\sim}146ppm,\;Li\;32{\sim}45ppm,\;Co\;7.2{\sim}12.7ppm,\;Cr\;37{\sim}76ppm,\;Cs\;4.8{\sim}9.1ppm,\;Hf\;7.5{\sim}25ppm,\;Rb\;88{\sim}178ppm,\;Sc\;7.7{\sim}12.6ppm,\;Zn\;83{\sim}143ppm,\;Pa\;11.3{\sim}37ppm,\;Ce\;69{\sim}206ppm,\;Eu\;1.1{\sim}1.5ppm,\;Yb\;1.8{\sim}4.4ppm$. According to the comparison of average contents of minor and rare earth elements for geological groups, Pb, Li, Cs, Hf, Rb, Sb, Pa, Ce, Eu, and Yb are higher in granitic gneiss area; Ba, Co, and Cr in schist area; Nb, Ni, and Zr in arenaceous rock area; Sr in tuff area: and Be, Cu, V, Sc, and Zn are such in andesite area.