• Korean Chemical Engineering Research
• /
• v.58 no.1
• /
• pp.142-149
• /
• 2020

In this study, the electrochemical performance of Graphite/Silicon/Pitch composites as anode material was investigated to improve the low theoretical capacity of artificial graphite. Spherical artificial graphite surface was coated with polyvinylpyrrolidone (PVP) amphiphiles material to synthesize Graphite/Silica material by silica islands growth. The Graphite/Silicon/Pitch composites were prepared by petroleum pitch coating and magnesiothermic reduction. The Graphite/Silicon/Pitch composite electrodes manufactured using poly(vinylidene fluoride) (PVDF), carboxymethyl cellulose (CMC) and polyacrylic acid (PAA) binders. The coin type half cell was assembled using various electrolytes and additives. The Graphite/Silicon/Pitch composites were analysed by X-ray diffraction (XRD), scanning electron microscope (SEM) and a thermogravimetric analyzer (TGA). The electrochemical characteristics of Graphite/Silicon/Pitch composite were investigated by constant current charge/discharge, rate performance, cyclic voltammetry and electrochemical impedance spectroscopy. The Graphite/Silicon/Pitch composites showed high cycle stability at a graphite/silica/pitch ratio (1:4:8 wt%). When the electrode is prepared using PAA binder, the high capacity and stability is obtained. The coin type half cell assembled using EC: DMC: EMC electrolyte showed high initial capacity (719 mAh/g) and excellent cycle stability. The rate performance has an capacity retention (77%) at 2 C/0.1 C and an capacity recovery (88%) at 0.1 C / 0.1 C when the vinylene carbonate (VC) was added.

• Journal of the Korean Electrochemical Society
• /
• v.21 no.2
• /
• pp.39-46
• /
• 2018

Many studies on the electrochemical performance of Li secondary batteries have been obtained using coin-type cells due to the ease of assembly, low cost and ensuring reproducibility. The coin-type cell consists of a case, a gasket, a spacer disk, and a wave spring. These structural features require a greater amount of liquid electrolyte to assemble than other types of cells such as laminated cells and cylindrical cells. Nevertheless, little research has been conducted on the effect of excess liquid electrolytes on the electrochemical performances of Li secondary batteries. In this study, we investigate the effect of different amounts of electrolyte on the coin-type cells. The amount of electrolytes is adjusted to 30 and $100mg\;mAh^{-1}$. Cycle performances at room temperature ($25^{\circ}C$) and high temperature ($60^{\circ}C$) and high voltage are performed to investigate the electrochemical properties of the different amount of electrolytes. In the case of the unit cell including the electrolyte of $30mg\;mAh^{-1}$, the discharging capacity retention characteristic is excellent in comparison with the case of $100mg\;mAh^{-1}$ under the high temperature and high voltage condition. The former shows a larger increase in internal resistance than the latter, confirming that the amount of electrolyte significantly influences the discharge capacity retention characteristics of the battery.

• Korean Chemical Engineering Research
• /
• v.57 no.6
• /
• pp.832-840
• /
• 2019

To improve the electrochemical performances of the cathode materials, boron-doped $LiNi_{0.90}Co_{0.05}Ti_{0.05}O_2$ were synthesized by using concentration gradient precursor. The characteristics of the prepared cathode materials were analyzed by XRD, SEM, EDS, PSA, ICP-OES and electrical conductivity measurement. The electrochemical performances were investigated by initial charge/discharge capacity, cycle stability, C-rate, cyclic voltammetry and electrochemical impedance spectroscopy. The cathode material with 0.5 mol% boron exhibited a capacity of 187 mAh/g (0.5 C) in a voltage range of 2.7~4.3 V(vs. $Li/Li^+$), and an capacity retention of 94.7% after 50 cycles. In the relatively high voltage range of 2.7~4.5 V(vs. $Li/Li^+$), it showed a high capacity of 200 mAh/g and capacity retention of 80.5% after 50 cycles.

• Korean Chemical Engineering Research
• /
• v.60 no.3
• /
• pp.327-333
• /
• 2022

In this study, silicon/carbon nanotube/carbon (Si/CNT/C) composites for anode were prepared to improve the volume expansion of silicon used as a high-capacity anode material. Si/CNT were prepared by electrostatic attraction of the positively charged Si and negatively charged CNT and then hydrothermal synthesis was performed to obtain the spherical Si/CNT/C composites. Poly(vinylidene fluoride) (PVDF), polyacrylic acid (PAA), and styrene butadiene rubber (SBR) were used as binders for electrode preparation, and coin cell was assembled using 1.0 M LiPF₆ (EC:DMC:EMC = 1:1:1 vol%) electrolyte and fluoroethylene carbonate (FEC) additive. The physical properties of Si/CNT/C anode materials were analyzed using SEM, EDS, XRD and TGA, and the electrochemical performances of lithium-ion batteries were investigated by charge-discharge cycle, rate performance, dQ/dV and electrochemical impedance spectroscopy tests. Also, it was confirmed that both capacity and rate performance were significantly improved using the PAA/SBR binder and 10 wt% FEC-added electrolyte. It is found that Si/CNT/C have the reversible capacity of 914 mAh/g, the capacity retention ratio of 83% during 50 cycles and the rate performance of 70% in 2 C/0.1 C.

• Korean Chemical Engineering Research
• /
• v.60 no.3
• /
• pp.446-451
• /
• 2022

In this study, to improve capacity and cycle stability, the pitch coated nano silicon sheets/CNT composites were prepared through electrostatic bonding of nano silicon sheets and CNT. Silica sheets were synthesized by hydrolyzing TEOS on the crystal planes of NaCl, and then nano silicon sheets were prepared by using magnesiothermic reduction method. To fabricate the nano silicon sheets/CNT composites, the negatively charged CNT after the acid treatment was used to assemble the positively charged nano silicon sheets modified with APTES. THF as a solvent was used in the coating process of PFO pitch. The physical properties of the prepared anode composites were analysed by FE-SEM, XRD and EDS. The electrochemical performances of the synthesized anode composites were performed by current charge/discharge, rate performances, differential capacity and EIS tests in the electrolyte LiPF₆ dissolve solvent (EC:DMC:EMC = 1:1:1 vol%). It was found that the anode material with high capacity and stability could be synthesized when high composition of silicon and conductivity of CNT were used. The pitch coated nano silicon sheets/CNT anode composites showed initial discharge capacity of 2344.9 mAh/g and the capacity retention ratio of 81% after 50 cycles. The electrochemical property of pitch coated anode material was more improved than that of the nano silicon sheets/CNT composites.

• Applied Chemistry for Engineering
• /
• v.34 no.5
• /
• pp.529-533
• /
• 2023

The fundamental electrochemical properties and adsorption capabilities of the carbonized product derived from coffee grounds, a prevalent form of lignocellulose abundantly generated in our daily lives, have been extensively investigated. The structure and morphology of the resultant carbonized product, obtained through a carbonization process conducted at a relatively low temperature of 600 ℃, were meticulously examined using a scanning electron microscope. Raman spectroscopy measurements yielded a relative crystallinity (D/G ratio) of the carbon product of 0.64. Electrical measurements revealed a linear ohmic relationship within the carbonized product. Furthermore, the viability of utilizing this carbonized material as an anode in lithium-ion batteries was evaluated through half-cell charge/discharge experiments, demonstrating an initial specific capacity of 520 mAh/g. Additionally, the adsorption performance of the carbon material towards a representative dye molecule was assessed via UV spectroscopy analyses. Supplementary experiments corroborated the material's ability to adsorb a distinct model molecule characterized by differing surface polarity, achieved through surface modification. This article presents pivotal findings that hold substantial implications for forthcoming research endeavors centered around the recycling of lignocellulose waste.

• Korean Chemical Engineering Research
• /
• v.62 no.1
• /
• pp.19-26
• /
• 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
• /
• v.7 no.6
• /
• pp.1313-1318
• /
• 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
• /
• v.33 no.5
• /
• pp.496-501
• /
• 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
• /
• v.27 no.3
• /
• pp.223-231
• /
• 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.