• Applied Chemistry for Engineering
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• v.33 no.1
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• pp.58-63
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• 2022

Graphite has been used as an anode material for lithium-ion batteries for the past 30 years due to its low de-/lithiation voltage, high theoretical capacity of 372 mAh/g, low price, and long life properties. Recently, all-solid-state lithium-ion batteries (ASSLB), which are composed of inorganic solid materials with high stability, have received great attention as electric vehicles and next-generation energy storage devices, but research works on graphite that works well for ASSLB systems are insufficient. Therefore, we induced the performance improvement of ASSLB anode electrode graphite material by removing the amorphous carbon present in the carbon material surface, acting as a resistive layer from the graphite. As a result of X-ray diffraction (XRD) analysis using heat treated graphite in air at 400, 500, and 600 ℃, the full width at half maximum (FWHM) at (002) peak was reduced compared to that of bare graphite, indicating that the crystallinity of graphite was improved after heat treatment. In addition, the discharge capacity, initial coulombic efficiency (ICE) and cycle stability increased as the crystallinity of graphite increased after heat treatment. In the case of graphite annealed in air at 500 ℃, the high capacity retention rate of 331.1 mAh/g and ICE of 86.2% and capacity retention of 92.7% after 10-cycle measurement were shown.

• Applied Chemistry for Engineering
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• v.32 no.3
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• pp.290-298
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• 2021

A purification process was performed for the application of natural graphite as an anode material. The influence of the structural change and impurity content of graphite according to the process on the anode electrochemical characteristics was investigated. Natural graphite was chemically/physically purified by acid-treatment which used different amounts of solution of ammonium fluoride/sulfuric acid in the same ratio and thermal treatment used different temperatures (800~2500 ℃). Acid-treatment had limitation to remove impurities, and identified that all impurity contents was removed except some traces of atom such as Si by after progressed thermal-treatment until 2500 ℃. The anode materials characteristic of graphite treated by purification process was improved, and changes in the structure and impurity contents affected dominantly the capacity, rate property and initial Coulombic efficiency. Consequently, the complex purification process improved the graphite structure and also the performance of lithium ion battery by controlling the excessive formation of solid electrolyte interphase and expanding Li⁺ insertion space originated from the effective removal of impurities.

• Korean Chemical Engineering Research
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• v.59 no.3
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• pp.410-416
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• 2021

To improve the capacity and stability of natural graphite, the electrochemical performances were investigated by using the prepared natural graphite coated with petroleum pitch for anode materials. The pitch coated natural graphite was prepared using a dry speed mixer by adjusting the rotation speed of the mixer, time, composition of graphite and softening point of the pitch. The physical properties of the anode material were analyzed using SEM, TEM, and PSD. The electrochemical performances were investigated by cycle, C-rate, EIS and CV test. When the pitch coated natural graphite was tested in the condition of 9000 RPM, 10 wt%, 2 h, and softening point of 150 ℃, it showed the highest capacity of 324.5 mAh/g at 0.1 C and a capacity retention rate of 98.9% after 50 cycles. In the test for evaluating rate performance, the capacity retention rate (5 C/0.1 C) was 80.3% and was improved by about 1.7 times over the pristine natural graphite.

• Journal of the Korean Electrochemical Society
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• v.2 no.4
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• pp.221-226
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• 1999

Two needle cokes (NC-A and NC-B) that differ in both the texture and impurity content to each other were graphitized at $2000-3000{\circ}C$, and the average particle size, size distribution and surface area were compared after milling. Their anodic properties in Li secondary batteries were also analyzed. Two materials showed a higher degree of graphitization with an increase in the preparation temperature, however, the NC-B series was less graphitized than NC-A due to the presence of impurities and less ordered mosaic texture. The mein particle size of the milled powder was proportional to the degree of graphitization, but the surface area showed the opposite trend. The highly graphitized materials yielded powders of lower uniformity in the size distribution. The discharge capacity of the resulting carbons steadily decreased in the temperature range of 1000 to $2000^{\circ}C$ due to the depletion of carbonaceous interlayers that contain crystal defects. A later increase in the discharge capacity was observed at $>2000^{\circ}C$, which arises from the formation of graphitic interlayers. The milling process gave rise to a sloping discharge curve at >1.0 V, but this was converted to a plateau at <0.25V after a repeated cycling or additional heat-treatment at $1000^{\circ}C$. The discharge at >1.0V likely comes from the disordered surface structure formed during the milling process. The evolution of a plateau at <0.25 V suggests that this disordered structure transforms to a more ordered graphitic one upon a cell cycling or heat-treatment.

• Journal of the Korean Electrochemical Society
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• v.13 no.1
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• pp.19-33
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• 2010

The surface film, which is formed on graphite negative electrodes during the initial charging, is a key component in lithium secondary batteries. The battery reactions are strongly affected by the nature of the surface film. It is thus very important to understand the physicochemical properties of the surface film. On the other hand, the surface film formation is a very complicated interfacial phenomenon occurring at the graphite/electrolyte interface. In studies on electrode surfaces in lithium secondary batteries, in-situ experimental techniques are very important because the surface film is highly reactive and unstable in the air. In this respect electrochemical atomic force microscopy (ECAFM) is a useful tool for direct visualizing electrode/solution interfaces at which various electrochemical reactions occur under potential control. In the present review, mechanism of surface film formation and its correlation with electrolyte are summarized on the basis of in-situ ECAFM studies for understanding of the nature of the surface film on graphite negative electrodes.

• 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%).

• 한국전기화학회:학술대회논문집
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• 2000.04a
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• pp.47-47
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• 2000

• 한국전기화학회:학술대회논문집
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• 1998.10a
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• pp.83-83
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• 1998

• Analytical Science and Technology
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• v.14 no.3
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• pp.197-202
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• 2001

The characteristics of the electrochemically Li intercalated synthetic graphite were determined from the studies with XRD method, DSC and solid $^7Li-NMR$ spectrophotometric analysis. From the results of X-ray diffraction method, it was found that the compounds in the stage 1 structure were predominantly formed. The enthalpy and entropy changes of the compounds can be obtained from the differential scanning calorimetric analysis results. From these results, it was found that exothermic and endothermic reactions of lithium intercalated into synthetic graphite are related to thermal stability of lithium ion between carbon graphene layers. From the $^7Li-NMR$ data, scientific observation found that bands are shift toward higher frequencies with increasing lithium concentration because non-occupied electron shells of Li increased in charge carrier density. Line widths of the Li intercalated synthetic graphite compounds decreased slowly because of non-homogeneous local magnetic order and the random electron spin direction for substituted Li.

• Journal of the Korean Electrochemical Society
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• v.15 no.1
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• pp.19-26
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• 2012

SEI (solid electrolyte interphase) layers are generated on a graphite negative electrode from three different electrolytes and low-temperature ($-30^{\circ}C$) charge/discharge performance of the graphite electrode is examined. The electrolytes are prepared by adding 2 wt% of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) into a standard electrolyte solution. The charge-discharge capacity of graphite electrode shows the following decreasing order; FEC-added one>standard>VC-added one. The polarization during a constant-current charging shows the reverse order. These observations illustrate that the SEI film resistance and charge transfer resistance differ according to the used additives. This feature has been confirmed by analyzing the chemical composition and thickness of three SEI layers. The SEI layer generated from the standard electrolyte is composed of polymeric carbon-oxygen species and the decomposition products ($Li_xPF_yO_z$) of lithium salt. The VC-derived surface film shows the largest resistance value even if the salt decomposition is not severe due to the presence of dense film comprising C-O species. The FEC-derived SEI layer shows the lowest resistance value as the C-O species are less populated and salt decomposition is not serious. In short, the FEC-added electrolyte generates the SEI layer of the smallest resistance to give the best low-temperature performance for the graphite negative electrode.