• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.4
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• pp.341-348
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• 2019

This paper reports the microstructure and electrochemical properties of Si-Al-Fe ternary amorphous alloys prepared by rapid solidification as an anode for lithium secondary batteries. The microstructure was analyzed using XRD and HR-TEM with EDS mapping. In accordance with DSC analysis, annealing was performed to crystallize the active nano-Si in the amorphous alloy. Thus, nano-Si forms (~80 nm) embedded in the matrix alloy, such as $Fe_2Al_3Si_3$, $FeSi_2$, and $Fe_{0.42}Si_{2.67}$, were successfully synthesized. The electrode based on the Si-Al-Fe ternary alloy delivered an initial discharge capacity of approximately $700mAh^{g-1}$, and exhibited a high Coulombic efficiency of 99.0~99.6% from the $2^{nd}$ to $70^{th}$ cycles.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.3
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• pp.179-186
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• 2019

This work investigated the effects of different conductive agents on the electrochemical properties of anodes. SiOx possesses high theoretical capacity and shows excellent cycle performance; however, the low initial coulombic efficiency and poor electrical conductivity limit its applications in real batteries. In this study, electrodes were fabricated using two different conductive agents, and the resulting physical and electrochemical properties were analyzed. SEM observations confirmed the formation of a CNT conductive network throughout the electrodes, while the electrical conductivity contributed to the electrode was confirmed by impedance measurements. Thus, the electrode fabricated with the CNT conductive agent showed greater capacity and superior cycle performance than did the electrode fabricated using the DB conductive agent.

• Journal of Electrochemical Science and Technology
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• v.12 no.1
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• pp.74-81
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• 2021

Silicon (Si) is recognized as a promising anode material for high-energy-density lithium-ion batteries. However, under a condition of electrode comparable to commercial graphite anodes with low binder content and a high electrode density, the practical use of Si is limited due to the huge volume change associated with Si-Li alloying/de-alloying. Here, we report a novel core-shell composite, having a reversible capacity of ~ 500 mAh g-1, by forming a shell composed of a mixture of nano-Si, graphite nanosheets and a pitch carbon on a spherical natural graphite particle. The electrochemical measurements are performed using electrodes with 2 wt % styrene butadiene rubber (SBR) and 2 wt.% carboxymethyl cellulose (CMC) binder in an electrode density of ~ 1.6 g cm-3. The core-shell composites having the reversible capacity of 478 mAh g-1 shows the outstanding capacity retention of 99% after 100 cycles with the initial coulombic efficiency of 90%. The heterostructure of core-shell composites appears to be very effective in buffering the volume change of Si during cycling.

• Journal of Electrochemical Science and Technology
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• v.13 no.1
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• pp.159-166
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• 2022

The assembly of the micron-sized Si/CNT/carbon composite wrapped with graphene (SCG composite) is designed and synthesized via a spray drying process. The spherical SCG composite exhibits a high discharge capacity of 1789 mAh g^-1 with an initial coulombic efficiency of 84 %. Moreover, the porous architecture of SCG composite is beneficial for enhancing cycling stability and rate capability. In practice, a blended electrode consisting of spherical SCG composite and natural graphite with a reversible capacity of ~500 mAh g^-1, shows a stable cycle performance with high cycling efficiencies (> 99.5%) during 100 cycles. These superior electrochemical performance are mainly attributed to the robust design and structural stability of the SCG composite during charge and discharge process. It appears that despite the fracture of micro-sized Si particles during repeated cycling, the electrical contact of Si particles can be maintained within the SCG composite by suppressing the direct contact of Si particles with electrolytes.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.1
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• pp.78-85
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• 2019

The effect of various lithium sources such as LiCl, LiOH, and Li-metal on the microstructure and electrochemical properties of granulated $SiO_x$ powders were investigated. Various lithium sources were metallurgically added for a passive pre-lithiation of $SiO_x$ to improve its low initial coulombic efficiency. In spite of using the same amount of Li in various sources, as well as the same process conditions, different lithium silicates were obtained. Moreover, irreversible phases were formed without reduction of $SiO_x$, which might be from additional oxygen incorporation during the process. Accordingly, there were no noticeable electrochemical enhancements. Nevertheless, the $Li_4SiO_4$ phase changes the initial electrochemical reaction, and consequently the relationship between the microstructure and electrochemical properties of metallurgically pre-lithiated $SiO_x$ could provide a guideline for the optimization of the performance of lithium ion batteries.

• Electrical & Electronic Materials
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• v.7 no.4
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• pp.317-324
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• 1994

In this study, new preparation method of LiCoO$_{2}$ was applied to develop cathode active material for Li rechargeable cell, and followed by X-ray diffraction analysis, electrochemical properties and initial charge/discharge characteristics as function of current density. HC8A72- and CC9A24-LiCoO$_{2}$ were prepared by heating treatment of the mixture of LiOH H$_{2}$O/CoCO$_{3}$(1:1 mole ratio) and the mixture of Li$_{2}$CO$_{3}$/CoCO$_{3}$(1:2 mole ratio) at 850 and 900.deg. C, respectively. Two prepared LiCoO$_{2}$s were identified as same structure by X-ray diffraction analysis. a and c lattice constant were 2.816.angs. and 14.046.angs., respectively. The electrochemical potential of CFM-LiCoO$_{2}$(Cyprus Foote Mineral Co.'s product), HC8A72-LiCoO$_{2}$ and CC9A24 LiCoO$_{2}$ electrode were approximately between 3.32V and 3.42V vs. Li/Li reference electrode. Stable cycling behavior was obtained during the cyclic voltammetry of LiCoO$_{2}$ electrode. According as scan rate increases, cathodic capacity decreases, but redox coulombic efficiency was about 100% at potential range between 3.6V and 4.2V vs. Li/Li reference electrode. Cathodic capacity of HC8A72-LiCoO$_{2}$ was 32% higher than that of CFM-LiCoO$_{2}$ and that of CC9A24-LiCoO$_{2}$ was 47% lower than that of CFM-LiCoO$_{2}$ at 130th cycle in the condition of lmV/sec scan rate. Constant cur-rent charge/discharge characteristics of LiCoO$_{2}$/Li cell showed increasing Ah efficiency with initial charge/discharge cycle. Specific discharge capacities of CFM and HC8A72-LiCoO$_{2}$ cathode active materials were about 93mAh/g correspondent to 34% of theretical value, 110mAh/g correspondent to 40% of theretical value, respectively. In the view of reversibility, HC8A72-LiCoO$_{2}$ was also more excellent than CFM- and CC9A24-LiCoO$_{2}$.

• Journal of the Korean institute of surface engineering
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• v.51 no.4
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• pp.243-248
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• 2018

All solid state thin film batteries with two types of cell structure, Pt / $LiCoO_2$ / LiPON / Cu and Pt / $LiCoO_2$ / LiPON / $LiCoO_2$ / Cu, are prepared and their electrochemical performances are investigated to evaluate the effect of $LiCoO_2$ interlayer at the interface of LiPON / Cu. The crystallinity of the deposited $LiCoO_2$ thin films is confirmed by XRD and Raman analysis. The crystalline $LiCoO_2$ cathode thin film is obtained and $LiCoO_2$ as the interlayer appears to be amorphous. The surface morphology of Cu current collector after cycling of the batteries is observed by AFM. The presence of a 10 nm-thick layer of $LiCoO_2$ at the interface of LiPON / Cu enhances the interfacial adhesion and reduces the interfacial resistance. As a result, Li plating / stripping at the interface of LiPON / Cu during charge/discharge reaction takes place more uniformly on Cu current collector, while without the interlayer of $LiCoO_2$ at the interface of LiPON / Cu, the Li plating / stripping is localized on current collector. The thin film batteries with the interlayer of $LiCoO_2$ at the interface of LiPON / Cu exhibits enhanced initial coulombic efficiency, reversible capacity and cycling stability. The thickness of the anode current collector Cu also appears to be crucial for electrochemical performances of all solid state thin film batteries.

• Korean Chemical Engineering Research
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• v.57 no.1
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• pp.5-10
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• 2019

In this study, electrochemical characteristics of artificial graphite coated with petroleum pitch using solvent method as anode material of lithium ion battery were investigated. As the solvent, n-hexane, toluene, tetrahydrofuran and quinoline were used. The surface of the prepared anode material was analyzed by SEM and TEM. Also the electrochemical performances of the prepared anode materials were performed by constant current first charge/discharge, cycle, cyclic voltammetry and impedance tests in the electrolyte of $LiPF_6$ dissolved inorganic solvents (EC:DEC=1:1 vol%). The coating thickness of the prepared graphite was about 100-500 nm and the graphite coated with THF solvent had a smoother surface than that using other solvents. It was found that pitch-coated graphite (THF) show the low initial irreversible capacity (51 mAh/g), the high discharge capacity (360 mAh/g) and coulombic efficiency (99%).

• Clean Technology
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• v.27 no.3
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• pp.223-231
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• 2021

In order to address many issues associated with large volume changes of silicon, which has very low electrical conductivity but offers about 10 times higher theoretical capacity than graphite (Gr), a silicon nanoparticles/hollow carbon (SiNP/HC) composite having bimodal-mesopores was prepared using silica nanoparticles as a template. A control SiNP/C composite without a hollow structure was also prepared for comparison. The physico-chemical and electrochemical properties of SiNP/HC were analyzed by X-ray diffractometry, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements for surface area and pore size distribution, scanning electron microscopy, transmission electron microscopy, galvanostatic cycling, and cyclic voltammetry tests to compare them with those of the SiNP/C composite. The SiNP/HC composite showed significantly better cycle life and efficiency than the SiNP/C, with minimal increase in electrode thickness after long cycles. A hybrid composite, SiNP/HC@Gr, prepared by physical mixing of the SiNP/HC and Gr at a 50:50 weight ratio, exhibited even better cycle life and efficiency than the SiNP/HC at low capacity. Thus, silicon/carbon composites designed to have hollow spaces capable of accommodating volume expansion were found to be highly effective for long cycle life of silicon-based composites. However, further study is required to improve the low initial coulombic efficiency of SiNP/HC and SiNP/HC@Gr, which is possibly because of their high surface area causing excessive electrolyte decomposition for the formation of solid-electrolyte-interface layers.

• 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.