• Applied Chemistry for Engineering
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• v.18 no.3
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• pp.291-295
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• 2007

The oxidation treatment of needle cokes with 70 wt% of nitric acid and sodium chlorate ($NaClO_3$) was attempted to achieve an electrochemically active material with a large capacitance. The structure of needle cokes was changed to graphite oxide after oxidation treatment of needle cokes with acidic solution having the composition ratio, $NaClO_3$/needle cokes, of 7.5, and the inter-layer distance of the oxidized needle cokes was extended to $6.9{\AA}$with increasing oxygen content. On the other hand, the electrochemical performance of oxidized needle cokes as a polarized electrode for an Electric Double Layer Capacitor (EDLC) was examined with an electrolyte of 1.2 M $TEABF_4$ (tetraethylammonium tetrafluoroborate) and $TEABF_4$ (triethylmethylammonium tetrafluoroborate) in acetonitrile. The capacitor cell using 1.2 M $TEABF_4$/acetonitrile has exhibited smaller electric resistance of $0.05{\Omega}$, and larger capacitance per weight and volume of 32.0 F/g and 25.5 F/mL at the two-electrode system in the potential range 0~2.5 V than that of the capacitor cell using $TEABF_4$. The observed electrochemical performance was discussed with the correlation between the inter-layer distance in graphite oxide structure and the anionic size of electrolyte.

• 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.

• Carbon letters
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• v.1 no.2
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• pp.76-81
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• 2000

Physical properties of artificial graphite electrodes were evaluated along three different directions; circumferential (X), radial (Y), and axial (Z) directions. Four kinds of commercial electrode products were used in this study for the evaluation; pole (AP) and nipple (AN) of manufacturer A, pole (BP) and nipple (BN) of manufacturer B. The mechanical, electrical, and thermal properties in X and Y directions were very similar to each other. In Z direction, however, the mechanical properties, including flexural strength and compressive strength, were higher, and electric resistance and thermal expansion were much lower than those in the other directions. The microstructures observed by optical microscope and scanning electron microscope revealed that the differences in properties by the measuring direction were caused by the preferential alignment of needle cokes along the Z direction. When comparing the properties of the electrode samples in the same direction, the mechanical properties mainly depended on the bulk density or porosity of the samples as well as preferential alignment of needle cokes.

• The Transactions of the Korean Institute of Electrical Engineers C
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• v.49 no.6
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• pp.328-334
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• 2000

A lithium ion secondary battery using carbon as a negative electrode has been developed. Further improvements to increase the cell capacity are expected by modifying the structure of the carbonaceous material. There are hopes for the development of large capacity lithium ion secondary batteries with long cycle, high energy density, high power density, and high energy efficiency. In the present paper, needle cokes from petroleum were examined as an anode of lithium ion secondary battery. Petroleum cokes, MCL(Molten Caustic Leaching) treated in Korea Institute Energy Research, were carbonized at various temperatures of 0, 500, 700, $19700^{\circ}C$ at heating rate of $2^{\circ}C$/min for lh. The electrolyte was used lM liPF6 EC/DEC (1:1). The voltage range of charge & discharge was 0.0V(0.05V) ~ 2.0V. The treated petroleum coke at $700^{\circ}C$ had an initial capacity over 560mAh.g which beyond the theoretical maximum capacity, 372mAh/g for LiC6. This phenomena suggests that carbon materials with disordered structure had higher cell capacity than that the graphitic carbon materials.

• Applied Chemistry for Engineering
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• v.18 no.5
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• pp.522-526
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• 2007

Structural features and electrochemical performances of cokes pyrolized from oxidized cokes were examined, and compared with KOH-activated coke. Needle cokes ($d_{002}=3.5{\AA} $), having a graphene layer structure, were changed to a single phase of graphite oxide after oxidation treatment with an acidic solution having an $NaCLO_3$/needle coke composition ratio of above 7.5, and the inter-layer distance of the oxidized coke was expanded to $6.9{\AA} $ with increasing oxygen content. After heating at $200^{\circ}C$, the oxidized coke was pyrolized to the graphene layer structure with inter-layer distance of $3.6{\AA} $. However, the change of the inter-layer distance of the needle coke was not observed in the KOH activation process. On the other hand, an intercalation of electrolyte ions into the pyrolized coke, observed at first charge, occurred at 1.0 V, in which the value was lower than that of KOH-activation coke. The cell capacitor using pyrolized coke exhibited a lower internal resistance of $0.57{\Omega}$ in 1 kHz, and a larger capacitance per weight and volume of 30.3 F/g and 26.9 F/ml at the two-electrode system in the potential range 0~2.5 V than those of the cell capacitor using KOH-activation of coke. This better electrochemical performance may be associated with structure defects in the graphene layer derived from the process of the inter-layer expansion and shrinkage.

• Korean Journal of Materials Research
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• v.10 no.11
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• pp.743-748
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• 2000

Amorphous carbons(neddle cokes), which are used as anode materials for lithium ion secondary batteries, were graphitized or heat-treated at high temperature in $N_2$ atmosphere and in Ar atmosphere, after adding $B_2O_3$. After then, using transmission eletron microscopy, their surface micro-structures and the formations and distributions of the second phases were analyzed. It was studied that such analyzed results were related to the cell capacities and efficiencies.

• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.34-39
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• 2009

In this study, a needle coke was oxidized in a mixture of dilute nitric acid and sodium chlorate ($NaClO_3$) solutions and followed by heat treatment. The samples were analyzed with using XRD, FESEM, elemental analyzer, BET, and Raman spectroscopy. Double layer capacitance was measured with the charge and discharge measurements. The consisting layers of the needle coke were expanded to single phase showing only (001) diffraction peak by the acid treatment for 24 hours. The oxidized coke returned to a graphite structure appearing (002) peak after heat treatment above $200^{\circ}C$. The structure returned could be more easily accessible to the ions by the first charge, and improve the double layer capacitance at the second charge. The two-electorde cell from acid treated coke and $300^{\circ}C$ heat treatment exhibited the maximum capacitances of 32.1 F/g and 29.5 F/ml at the potential of $0{\sim}2.5\;V$.

• Applied Chemistry for Engineering
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• v.19 no.4
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• pp.407-412
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• 2008

As an activation procedure, in this study, the oxidation treatment of needle cokes with a dilute nitric acid and sodium chlorate $(NaClO_3)$, combined with heat treatment, was attempted. The structures of acid-treated and pyrolyzed coke were examined with XRD, FESEM, elemental analyzer, BET, and Raman spectroscopy. The behavior of double layer capacitance was investigated with the analysis of charge and discharge. The structure of needle coke treated with acid was revealed to a single phase of (001) diffraction peak after 24 h. On the other hand, thecoke oxidized by heat treatment was reduced to a graphite structure of (002) at $300^{\circ}C$. The distorted graphene layer structure, derived from the process of oxidation and reduction of the inter-layer, makes the pores by the electric field activation at the first charge, and generates the double layer capacitance from the second charge. The cell using pyrolyzed coke with 24 h acid treatment and $300^{\circ}C$ heat treatment exhibited the maximum capacitance per weight and volume of 33 F/g and 30 F/mL at the two-electrode system in the potential range of 0~2.5 V.