• Korean Chemical Engineering Research
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• v.62 no.1
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• pp.19-26
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• 2024

In this study, the electrochemical properties of SiOx@C composite materials were prepared to alleviate volume expansion and cycle stability of silicon and to increase the capacity of anode material for LIBs. SiO₂ particles of 100, 200, and 500 nm were synthesized by the Stӧber method, and reduced to SiOx (0≤x≤2) through the magnesiothermic reduction method. Then, SiOx@C anode materials were synthesized by carbonization of PVC on SiOx. The physical properties of prepared SiOx and SiOx@C anode materials were analyzed by XRD, SEM, TGA, Raman spectroscopy, XPS and BET. The electrochemical properties were investigated by cycling performance, rate performance, CV and EIS test. As a result, the SiOx@C-7030 manufactured by coating carbon at SiOx : C = 70 : 30 on a 100 nm SiOx with the smallest particle size showed the best electrochemical properties with a discharge capacity of 1055 mAh/g and a capacity retention rate of 81.9% at 100 cycles. It was confirmed that cycle stability was impoved by reducing particle size and carbon coating.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.6
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• pp.1313-1318
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• 2006

The mechanism fur the surface film formation was studied by in situ Atomic Force Microscopy (AFM) observation of a highly oriented pyrolytic graphite (HOPG) basal plane surface during cyclic voltammetry at a slow scan-rate of 0.5 mV $s^{-1}$ in 1 moi $dm^{-3}$ (M) $LiPF_6$ dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). Decomposition of the electrolyte solution began at a potential around 2.15 V vs. $Li^+$/Li on step edges. In the potential range 0.95-0.8 V vs. $Li^+$/Li, flat areas (hill-like structures) and large swelling appeared on the surface. It is considered that these two features were formed by the intercalation of solvated lithium ions and their decomposition beneath the surface, respectively. At potentials more negative than 0.80 V vs. $Li^+$/Li, particle-like precipitates appeared on the basal plane surface. After the first cycle, the thickness of the precipitate layer was 30 nm. The precipitates were considered to be decomposition of the lithium salt ($LiPF_6$) and solvent molecules (EC and DEC), and to have an important role in suppressing further solvent decomposition on the basal plane.

• Applied Chemistry for Engineering
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• v.33 no.5
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• pp.496-501
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• 2022

In this study, an anode material for lithium secondary batteries was manufactured using petroleum-based residual oil, which is a petroleum refining by-product. Among petroleum-based residual oils, pyrolysis fuel oil (PFO), fluidized catalyst cracking-decant oil (FCC-DO), and vacuum residue (VR) were used as carbon precursors. The physicochemical characteristics of petroleum-based residual oil were confirmed through Matrix-assisted laser desorption/ionization Time-of-Flight (MALDI-TOF) and elemental analysis (EA), and the structural characteristics of anode materials manufactured from residual oil were evaluated using X-ray crystallography (XRD) and Raman spectroscopic techniques. VR was found to contain a wide range of molecular weight distributions and large amounts of impurities compared to PFO and FCC-DO, and PFO and FCC-DO exhibited almost similar physicochemical characteristics. From the XRD analysis results, carbonized PFO and FCC-DO showed similar d₀₀₂ values. However, it was confirmed that FCC-DO had a more developed layered structure than PFO in Lc (Length of a and c axes in the crystal system) and La values. In addition, FCC-DO showed the best cycle characteristics in electrochemical characteristics evaluation. According to the physicochemical and electrochemical results of the petroleum-based residual oil, FCC-DO is a better carbon precursor for a lithium secondary battery than PFO and VR.

• 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.14 no.1
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• pp.27-32
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• 2011

The electorchemical properties of $Li_4Ti_5O_{12}$ added with Cr was tested. The addition or substitution of atoms to $Li_4Ti_5O_{12}$ are expected to modify the crystal structure, and therefore to change the electrochemical performances of $Li_4Ti_5O_{12}$. After the spinel structure $Li_4Ti_{5-x}Cr_xO_{12}$ (x = 0~0.2) were obtained via sol-gel method, the gel was heated in a muffle furnace at $800{\sim}850^{\circ}C$ for 12 h in air. The physical properties of the samples were characterized by TG-DTA, XRD, SEM, FT-IR, and the electrochemical properties were tested with battery cycler at 0.01~2.0 V range. The $Li_4Ti_5O_{12}$ exhibited 169.9 mAh/g at 1C and capacity recovery was 97.5% of the initial capacity at 0.1C. $Li_4Ti_{4.9}Cr_{0.1}O_{12}$ (Cr 1% added) showed best performance of 193.8 mAh/g at 1C and the capacity recovery was increased to 98.8% of the initial capacity at 0.1C.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.131-137
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• 2012

Polyaniline (PANI) and polypyrrole (Ppy) hollow sphere structures with controlled shell thicknesses can be easily synthesized than those of using a layer-by-layer method for cathode active material of lithium-ion batteries. Polystyrene (PS) core was synthesized by emulsion polymerization using an anion surfactant. The shell thicknesses of PANI and Ppy were controlled by amounts of aniline and pyrrole monomers. PS was removed by an organic solution. This structure increased in contact with an electrolyte and a specific capacity in lithium-ion batteries. But polymers have disadvantages such as the difficult control of molecular weights and low densities. These disadvantages were completed by controlled shell thicknesses. The amount of aniline monomer increased from 1.2, 2.4, 3.6, 4.8 to 6.0 mL, and the shell thicknesses were 30.2, 38.0, 42.2, 48.2, and 52.4 nm, respectively. And the amount of pyrrole monomer was 0.6, 1.2, 2.4 and 3.6 mL, the shell thicknesses were 16.0, 22.0, 27.0 and 34.0 nm, respectively. In the cathode materials with controlled shell thicknesses, shell thicknesses of the PANI hollow spheres were 30.2, 42.2, and 52.4 nm, and discharge specific capacities of after 10 cycle were ~18, ~29, and ~62 mAh/g, respectively. The shell thicknesses of the Ppy hollow spheres were 16.0, 22.0, 27.0 and 34.0 nm, and discharge specific capacities of after 15 cycle were ~15, ~36, ~56, and ~77 mAh/g, respectively. Thus, shell thicknesses of PANI and Ppy increased, the specific capacities increased.

• Journal of the Korean Electrochemical Society
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• v.14 no.4
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• pp.208-213
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• 2011

Solid polymer electrolytes using $BF_3LiMA$ as monomer were synthesized by usual one step radical polymerization in THF solvent. The effect of $BF_3LiMA$ concentration on ionic conductivity and electrochemical stability was investigated by AC impedance measurement and linear sweep voltammetry. As a result, the highest ionic conductivity reached $7.71{\times}10^{-6}S\;cm^{-1}$ at $25^{\circ}C$ was obtained in 12.9 wt% of $BF_3LiMA$ content. Further increase or decrease of $BF_3LiMA$ content result to decrease the ionic conductivity due to the brittle matrix properties in former case and the insufficient number of charge carrier in the latter case. Furthermore, since the counter-anion was immobilized in the self-doped solid polymer electrolytes, high electrochemical stability up to 6.0 V was observed even in $60^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.65-70
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• 2014

In this study, crosslinked poly(POEM-co-AMPSLi-co-GMA)s were prepared by epoxy coupling of GMA after radical copolymerization of AMPS, POEM and GMA followed by acid-base titration reaction between sulfonic acid of AMPS and $Li_2CO_3$. It was observed that the crystalline melting temperature of POEM was effected by mol% of components and shifted to lower value by lithiation of AMPS group. The ionic conductivity of crosslinked polymer electrolyte was decreased by addition of GMA but maintained over $1.0{\times}10^{-6}S\;cm^{-1}$ until 16 mol%. Particularly, the self-doped polymer electrolyte with 2 mol% of GMA showed its ionic conductivity as high as $4.08{\times}10^{-6}S\;cm^{-1}$ at room temperature and electrochemical stability up to 6 V. In addition, 0.11 MPa of modulus and 270% of elongation were obtained from the free standing film of crosslinked polymer electrolyte.

• Journal of the Korean Chemical Society
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• v.63 no.6
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• pp.446-452
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• 2019

We have developed a method that can leach Co, Mn, and Ni in the cathode active material safely using lactic acid. When cathode active material was leached by lactic acid, lactic acid showed the highest efficiency at 2 N than 1 N and above 4 N concentration. When the cathode active material was added incrementally into the solution of lactic acid, the maximum solubility was 30 g/L at 2 N concentration. Oxalic acid was added in the solution of lactic acid and it showed that rare metals represent the most economical recovery efficiency at 4 g/L. Based on this study, it was found that the optimal condition for recovery of rare metals from cathode active material is oxalic acid : cathode active material = 7 : 1 as a ratio of weight. In addition, it was observed that the precipitate produced by oxalic acid is a polynuclear crystalline material bonded with 3 components of Co, Ni, and Mn.

• Applied Chemistry for Engineering
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• v.27 no.4
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• pp.415-420
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• 2016

To enhance electrochemical performances of anode materials, the surface of coal tar pitch (CTP) was modified by incorporating heteroatoms through chemical treatment with phosphoric acid ($H_3PO_4$). The prepared anode materials with modified CTP was analyzed by XRD, FE-SEM and XPS. The electrochemical performances of modified CTP were investigated by constant current charge/discharge test, rate performance, cyclic voltammetry and impedance tests using the electrolyte of $LiPF_6$ dissolved in the mixed organic solvents (ethylene carbonate : dimethyl carbonate = 1 : 1 vol% + vinylene carbonate 3 wt%). The coin cell using modified CTP ($H_3PO_4/CTP$ = 3 : 100 in weight) has better initial capacity and initial efficiency (489 mAh/g, 82%) than those of other composition coin cells. Also, it was found that the capacity retention was 86% after 30 cycles and the rate capability was 87% at 2 C/0.1 C.