• Journal of Powder Materials
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• v.23 no.4
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• pp.287-296
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• 2016

$Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders have been synthesized in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH using $NH_4OH$ as a chelating agent. The co-precipitation temperature is varied in the range of $30-80^{\circ}C$. Calcination of the prepared precursors with $Li_2CO_3$ for 8 h at $1000^{\circ}C$ in air results in Li $Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ powders. Two kinds of obtained powders have been characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analyzer, and tap density measurements. The co-precipitation temperature does not differentiate the XRD patterns of precursors as well as their final powders. Precursor powders are spherical and dense, consisting of numerous acicular or flaky primary particles. The precursors obtained at 70 and $80^{\circ}C$ possess bigger primary particles having more irregular shapes than those at lower temperatures. This is related to the lower tap density measured for the former. The final powders show a similar tendency in terms of primary particle shape and tap density. Electrochemical characterization shows that the initial charge/discharge capacities and cycle life of final powders from the precursors obtained at 70 and $80^{\circ}C$ are inferior to those at $50^{\circ}C$. It is concluded that the optimum co-precipitation temperature is around $50^{\circ}C$.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.10 no.3
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• pp.219-225
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• 2000

The spinel structured $LiMn_2O_4$was obtained by two consecutive heat treatment on xerogel; the first heat treatment was at $150^{\circ}C$ and the second at $350^{\circ}C$ was obtained by sol-gel process using an aqueous solution of lithium hydroxide and manganese acetate. The synthesized $LiMn_2O_4$ by the sol-gel process showed a discharge capacity of 88~56 mAh/g after 15 cycles in Li/lM $LiClO_4$(in PC)/$LiMn_2O_4$at a current density of 0.25 mA/$\textrm{cm}^2$ and the voltage ranged 3.5 V to 4.3 V. For the second heat treatment above $350^{\circ}C$, $Mn_2O_3$was formed as a by-product during the synthesis of $LiMn_2O_4$. The heat treatment at $500^{\circ}C$, for example, showed a lower discharge capacity 81~47 mAh/g, after the 15 charge/discharge cycles. The lower capacity was due to the increment of $Mn^{3+}$ ion and this phenomenon was in agreement with the Jahn-Teller distortion.

• Journal of the Korean Electrochemical Society
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• v.13 no.3
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• pp.211-216
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• 2010

Boron trifluoride lithium methacrylate ($BF_3$LiMA)-based gel polymer electrolytes (GPEs) were synthesized with various $BF_3$LiMA concentration to elucidate the effect on ionic conductivity and electrochemical stability by a AC impedance and linear sweep voltammetry (LSV). As a result, the highest ionic conductivity reached $5.3{\times}10^{-4}Scm^{-1}$ at $25^{\circ}C$ was obtained for 4 wt% of $BF_3$LiMA. Furthermore, high electrochemical stability up to 4.3 V of the $BF_3$LiMA-based GPE was observed in LSV measurement since the counter anion was immobilized in this self-doped system. On the other hand, it was assumed that there was a rapid decomposition of electrolytes on a lithium metal electrode which results in a high solid electrolyte interface (SEI) resistance. However, a high stability toward graphite or lithium cobalt oxide (LCO) electrode thereby a low SEI resistance was observed from the AC impedance measurement as a function of storage time at $25^{\circ}C$. Consequently, the high ionic conductivity, good electrochemical stability and the good interfacial compatibility with graphite and LCO were achieved in $BF_3$LiMA-based GPE.

• Environmental Engineering Research
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• v.25 no.1
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• pp.88-95
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• 2020

An investigation of rare metals recovery from LiNi_xCo_yMn_zO₂ cathode material of the end-of-life lithium-ion batteries is presented. To determine the influence of reductant on the leach process, the cathode material (containing Li 7.6%, Co 20.4%, Mn 19.4%, and Ni 19.3%) was leached in H₂SO₄ solutions either with or without H₂O₂. The optimal process parameters with respect to acid concentration, addition dosage of H₂O₂, temperature, and the leaching time were found to be 2.0 M H₂SO₄, 4 vol.% H₂O₂, 70℃, and 150 min, respectively. The yield of metal values in the leach liquor was > 99%. The leach liquor was subsequently treated by precipitation techniques to recover nickel as Ni(C₄H₇N₂O₂)₂ and lithium as Li₂CO₃ with stoichiometric ratios of 2:1 and 1.2:1 of dimethylglyoxime:Ni and Na₂CO₃:Li, respectively. Cobalt was recovered by solvent extraction following a 3-stage process using Na-Cyanex 272 at pH_eq ~5.0 with an organic-to-aqueous phase ratio (O/A) of 2/3. The loaded organic phase was stripped with 2.0 M H₂SO₄ at an O/A ratio of 8/1 to yield a solution of 114 g/L CoSO₄; finally recovered CoSO₄.xH₂O by crystallization. The process economics were analyzed and found to be viable with a margin of $476 per ton of the cathode material.

• Resources Recycling
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• v.33 no.1
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• pp.58-68
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• 2024

Critical minerals such as nickel, cobalt and lithium, are known as materials for cathodic active materials of lithium ion batteries. The consumption of the minerals is expected to grow with increasing the demands of electric vehicles, resulting from carbon neutrality. Especially, the demand for LIB (lithium ion battery) recycling is expected to increase to meet the supply of nickel, cobalt and lithium for LIB. The recycling of EOL (end-of-life) LIB can be achieved by leaching EOL LIB using inorganic acid such as HCl, HNO₃ and H₂SO₄, which are regarded as hazardous materials. In the present study, the potential use of MSA (Methanesulfonic acid), as an alternative lixiviant replacing sulfuric acid was investigated. In addition, leaching behaviors of NCM black mass leaching with MSA was also investigated by studying various leaching factors such as chemical concentration, leaching time, pulp density (P/D) and temperatures. The leaching efficiency of nickel (Ni), cobalt (Co), lithium (Li), and manganese (Mn) from LIB was enhanced by increasing concentration of lixiviant and reductant, leaching time and temperature. The maximum leaching of the metals was above 99% at 80℃. In addition, MSA can replace sulfuric acid to recover Ni, Co, Li, Mn from NCM black mass.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4205-4209
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• 2011

The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ silicate was prepared by blending of $Li_2MnSiO_4$ and $Li_2FeSiO_4$ precursors with same molar ratio. The one of the silicates of $Li_2FeSiO_4$ is known as high capacitive up to ~330 mAh/g due to 2 mole electron exchange, and the other of $Li_2FeSiO_4$ has identical structure with $Li_2MnSiO_4$ and shows stable cycle with less capacity of ~170 mAh/g. The major drawback of silicate family is low electronic conductivity (3 orders of magnitude lower than $LiFePO_4$). To overcome this disadvantage, carbon composite of the silicate compound was prepared by sucrose mixing with silicate precursors and heat-treated in reducing atmosphere. The crystal structure and physical morphology of $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ was investigated by X-ray diffraction, scanning electron microscopy, and high resolution transmission electron microscopy. The $Li_2Mn_{0.5}Fe_{0.5}SiO_4$/C nanocomposite has a maximum discharge capacity of 200 mAh/g, and 63% of its discharge capacity is retained after the tenth cycles. We have realized that more than 1 mole of electrons are exchanged in $Li_2Mn_{0.5}Fe_{0.5}SiO_4$. We have observed that $Li_2Mn_{0.5}Fe_{0.5}SiO_4$ is unstable structure upon first delithiation with structural collapse. High temperature cell performance result shows high capacity of discharge capacity (244 mAh/g) but it had poor capacity retention (50%) due to the accelerated structural degradation and related reaction.

• 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 IKEEE
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• v.26 no.3
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• pp.515-519
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• 2022

In this paper, we propose the development of a high-sensitivity entry-level nuclide analysis module. The proposed measurement sensor module consists of an electronic driving circuit for nuclide analysis resolution, prototype production with nuclide analysis function, and GUI development applied to prototypes. The electronic part driving circuit for nuclide analysis resolution is divided into nuclide analysis resolution process by the electronic part driving circuit block diagram, MCU circuit design used for radiation measurement, and PC program design for Spectrum acquisition. Prototyping with nuclide analysis function is made by adding a 128×128 pixel OLED display, three buttons for operation, a Li-ion battery, and a USB-C type port for charging the battery. The GUI development department applied to the prototype develops the screen composition such as the current time, elapsed measurement time, total count, and nuclide Spectrum. To evaluate the performance of the proposed measurement sensor module, an expert witness test was conducted. As a result of the test, it was confirmed that the calculated result by applying the resolution formula to the Spectrum (FWHM@662keV) obtained using the Cs-137 standard source in the nuclide analysis device had a resolution of 17.77%. Therefore, it was confirmed that the nuclide analysis resolution method proposed in this paper produces improved performance while being cheaper than the existing commercial nuclide analysis module.

• Korean Chemical Engineering Research
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• v.57 no.6
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• pp.861-867
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• 2019

$Li_4Ti_5O_{12}$ is a promising next-generation anode material for lithium-ion batteries due to excellent cycle life, low irreversible capacity, and little volume expansion during charge-discharge process. However, it has poor charge capacity at high current density due to its low electrical conductivity. To improve this weakness, porous $Li_4Ti_5O_{12}$ was synthesized by sol-gel method with P123 as chelating agent. The physical characteristics of as-prepared sample was investigated by XRD, SEM, and BET analysis, and electrochemical properties were characterized by cycle performance test, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS). $Li_4Ti_5O_{12}$ synthesized by 0.01mol ratio of P123/Ti showed most unified particle size, high specific surface area, and relatively high porosity. EIS analysis showed that depressed semicircle size was remarkably reduced, which suggested resistance value in electrode was decreased. Capacity in rate performance showed 178 mAh/g at 0.2C, 170 mAh/g at 0.5C, 110 mA/h at 5C, and 90 mAh/g at 10C. Capacity retention also showed 99% after rate performance.

• Journal of Electrochemical Science and Technology
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• v.15 no.2
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• pp.291-298
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• 2024

Due to its high theoretical capacity, Silicon (Si) has shown great potential as an anode material for lithium-ion batteries (LIBs). However, the large volume change of Si during cycling leads to poor cycling stability and low Coulombic efficiency. In this study, we synthesized Si/Carbon C45:Graphene composites using a ball-milling method with a fixed Si content (20%) and investigated the influence of the C45/Gr ratio on the electrochemical performance of the composites. The results showed that carbon C45 networks can provide good conductivity, but tend to break at Si locations, resulting in poor conductivity. However, the addition of graphene helps to reconnect the broken C45 networks, improving the conductivity of the composite. Moreover, the C45 can also act as a protective coating around Si particles, reducing the volume expansion of Si during charging/discharging cycles. The Si/C45:Gr (70:10 wt%) composite exhibits improved electrochemical performance with high capacity (~1660 mAh g^-1 at 0.1 C) and cycling stability (~1370 mAh g^-1 after 100 cycles). This work highlights the effective role of carbon C45 and graphene in Si/C composites for enhancing the performance of Si-based anode materials for LIBs.