• Journal of Powder Materials
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• v.30 no.6
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• pp.516-520
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• 2023

Highly safe lithium-ion batteries (LIBs) are required for large-scale applications such as electrical vehicles and energy storage systems. A highly stable cathode is essential for the development of safe LIBs. LiFePO₄ is one of the most stable cathodes because of its stable structure and strong bonding between P and O. However, it has a lower energy density than lithium transition metal oxides. To investigate the high energy density of phosphate materials, vanadium phosphates were investigated. Vanadium enables multiple redox reactions as well as high redox potentials. LiVPO₄O has two redox reactions (V⁵⁺/V⁴⁺/V³⁺) but low electrochemical activity. In this study, LiVPO₄O is doped with fluorine to improve its electrochemical activity and increase its operational redox potential. With increasing fluorine content in LiVPO₄O_1-xF_x, the local vanadium structure changed as the vanadium oxidation state changed. In addition, the operating potential increased with increasing fluorine content. Thus, it was confirmed that fluorine doping leads to a strong inductive effect and high operating voltage, which helps improve the energy density of the cathode materials.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.34 no.3
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• pp.92-97
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• 2024

To improve the efficiency of water splitting systems for hydrogen production, the high overvoltages of electrochemical reactions caused by catalysts in the oxygen evolution reaction (OER, Oxygen Evolution Reaction) must be reduced. Among them, LDH (Layered Double Hydroxide) compounds containing transition metal such as Ni, are attracting attention as catalyst materials that can replace precious metals such as platinum that are currently used. In this study, nickel foam, an inexpensive metallic porous material, was used as a support, and NiCo LDH (Layered Double Hydroxide) nanocrystals were synthesized through a hydrothermal synthesis process. In addition, changes in the shape, crystal structure, and water decomposition characteristics of the Mo-doped NiCo LDH nanocrystal samples synthesized by doping Mo to improve OER properties were observed.

• Journal of the Mineralogical Society of Korea
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• v.15 no.1
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• pp.1-10
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• 2002

The present study is focused on the granite weathering and soil formation, and the heavy metal contamination in soils in the Onsan industrial area. For profile study, soil sampling was conducted on each depth and experimental analyses have been conducted on those samples. X-ray diffraction analyses show that clay minerals consist mainly of kaolin minerals, vermiculite, and minor illite. Most of kaolin minerals in the lower kiwi of the profile consist of halloysite as confirmed by formamide intercalation, but the content of halloysite decreases gradually toward the surface since it has been transformed to kaolinite in the upper part of the profile. Thermal treatment by heating at $110^{\circ}C,\;300^{\circ}C,\;and\;550^{\circ}C$ shows a diffuse and broad peak the between 10 and $14\;{\AA}$ region in X-ray diffractograms. This suggests the possible existence of the hydroxy-Al interlayerecl vermiculite. Na-citrate extraction method reaconfirms this result showing transition of $14\;{\AA}$ peak to $10\;{\AA}$ In by removing the interlayer materials and restoring the vermiculite to its original state. The occurrence of hydroxy-Al interlayered vermiculite is also supported by soil pH distribution room 3.9 In the lower part to 3.6 in the upper part of the profile. Sequential extraction experiment was conducted to investigate the states of heavy metals in soils. The experiment shows that relatively high amounts of heavy metals are concentrated in the upper part of the profile and that most of them are bound to Fe/Mn oxides and organic matters while less concentration in clay minerals. The result indicates that most of heavy metal pollutants are concentrated in the surface soil and that the low concentrations of heavy metals in clays are mainly due to the low adsorption capacities of clay minerals such as kaolin minerals and hydroxy-Al interlayered vermiculite in acidified soil condition.

• Journal of the Mineralogical Society of Korea
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• v.16 no.3
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• pp.223-232
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• 2003

The co-precipitation method is applied to synthesize the cathode material Li[L $i_{x}$M $n_{1-x-y}$C $r_{y}$ ] $O_2$ for lithium rechargeable batteries at $650^{\circ}C$ (CR650) and 8$50^{\circ}C$ (CR850), respectively. Rietveld indices indicate that $R_{wp}$ with respect to $R_{exp}$ ( $R_{wp}$/ $R_{exp}$) are 9.2%/10.1% for CR650 and 15.9%/9.76% for CR850, respectively. $R_{B}$ and S (GofF) shows 10.9%, 8.54% and 1.9, 1.6, respectively. Rietveld structure refinement reveals that layer structure of LiMn $O_2$ (R3m) coexists with lower symmetry of Li[L $i_{1}$3/M $n_{2}$3/] $O_2$ (C2/c) due to superlattice ordering of Li and Mn in metal-transition containing layers. Unit-cell parameters are calculated as a=2.8520(2)$\AA$, c=14.248(2)$\AA$, V=100.40(l)$\AA^3$ for CR650, and a=2.8504(1)$\AA$, c=14.2371(7)$\AA$, V=100.179(8)$\AA^3$ for CR850. Final chemistry is obtained as Li[L $i_{0.35}$M $n_{0.56}$C $r_{0.09}$] $O_2$ (CR650) and Li[L $i_{0.27}$M $n_{0.61}$C $r_{0.13}$] $O_2$ (CR850), respectively.y...y..vely.y...y..

• Journal of the Korean Magnetics Society
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• v.14 no.1
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• pp.38-44
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• 2004

The iron doped colossal magnetoresistance materials with La-Ba-Mn-O perovskites structure have been synthesized by chemical reaction of sol-gel methods. Their crystallographic and magnetic properties have been studied with x-ray diffraction, VSM, RBS, Mossbauer spectroscopy, and magnetoresistance measurements. The crystal structure of the La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$ at room temperature was determined to be orthorhombic of Pnma. The lattice parameters a$\_$0/ and c$\_$0/ increased gradually, but b$\_$0/ deceased with increase of iron substitution. The magnetization and coercivity deceased, also the Curie temperature decreased from 360 K as x increased from 0.00 to 0.05. Magnetoresistence measurements were carried out, and the maximum MR ($\Delta$$\rho$/$\rho$(0)) was observed at 281 K, about 9.5 % in 10 kOe. The temperature of maximum resistance (R$\_$MAX/) decreased with increasing substitution of Fe ions and a semiconductor-metal transition temperature (T$\_$SC-M/) decreased too. This phenomena show that ferromagnetic transition temperature decreased by substituting Fe for Mn ions, it decreases double exchange interaction. This result accords with magnetic structure of neutron diffraction. Mossbauer spectra of La$\_$0.67/Ba$\_$0.33/Mn$\_$0.99/Fe$\_$0.01/ $O_3$were taken at various temperatures ranging from 15 to 350 K. With lowering temperature of the sample, two magnetic phases were increased and finally it showed the two sharp sextets of spectra at 15 K. The isomer shift at all temperature range is about 0.3 mm/s relative to Fe metal, which means that both Fe ions are Fe$\^$3+/ states.Fe$\^$3+/ states.

• Journal of the Korean Electrochemical Society
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• v.20 no.4
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• pp.67-74
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• 2017

Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.100-101
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• 2012

The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

• Economic and Environmental Geology
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• v.30 no.4
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• pp.289-301
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• 1997

The Boguk cobalt mine is located within the Cretaceous Gyeongsang Sedimentary Basin. Major ore minerals including cobalt-bearing minerals (loellingite, cobaltite, and glaucodot) and Co-bearing arsenopyrite occur together with base-metal sulfides (pyrrhotite, chalcopyrite, pyrite, sphalerite, etc.) and minor amounts of oxides (magnetite and hematite) within fracture-filling $quartz{\pm}actinolite{\pm}carbonate$ veins. These veins are developed within an epicrustal micrographic granite stock which intrudes the Konchonri Formation (mainly of shale). Radiometric date of the granite (85.98 Ma) indicates a Late Cretaceous age for granite emplacement and associated cobalt mineralization. The vein mineralogy is relatively complex and changes with time: cobalt-bearing minerals with actinolite, carbonates, and quartz gangues (stages I and II) ${\rightarrow}$ base-metal sulfides, gold, and Fe oxides with quartz gangues (stage III) ${\rightarrow}$ barren carbonates (stages IV and V). The common occurrence of high-temperature minerals (cobalt-bearing minerals, molybdenite and actinolite) with low-temperature minerals (base-metal sulfides, gold and carbonates) in veins indicates a xenothermal condition of the hydrothermal mineralization. High enrichment of Co in the granite (avg. 50.90 ppm) indicates the magmatic hydrothermal derivation of cobalt from this cooling granite stock, whereas higher amounts of Cu and Zn in the Konchonri Formation shale suggest their derivations largely from shale. The decrease in temperature of hydrothermal fluids with a concomitant increase in fugacity of oxygen with time (for cobalt deposition in stages I and II, $T=560^{\circ}C-390^{\circ}C$ and log $fO_2=$ >-32.7 to -30.7 atm at $350^{\circ}C$; for base-metal sulfide deposition in stage III, $T=380^{\circ}-345^{\circ}C$ and log $fO_2={\geq}-30.7$ atm at $350^{\circ}C$) indicates a transition of the hydrothermal system from a magmatic-water domination toward a less-evolved meteoric-water domination. Sulfur isotope data of stage II sulfide minerals evidence that early, Co-bearing hydrothermal fluids derived originally from an igneous source with a ${\delta}^{34}S_{{\Sigma}S}$ value near 3 to 5‰. The remarkable increase in ${\delta}^{34}S_{H2S}$ values of hydrothermal fluids with time from cobalt deposition in stage II (3-5‰) to base-metal sulfide deposition in stage III (up to about 20‰) also indicates the change of the hydrothermal system toward the meteoric water domination, which resulted in the leaching-out and concentration of isotopically heavier sulfur (sedimentary sulfates), base metals (Cu, Zn, etc.) and gold from surrounding sedimentary rocks during the huge, meteoric water circulation. We suggest that without the formation of the later, meteoric water circulation extensively through surrounding sedimentary rocks the Boguk cobalt deposits would be simple veins only with actinolite + quartz + cobalt-bearing minerals. Furthermore, the formation of the meteoric water circulation after the culmination of a magmatic hydrothermal system resulted in the common occurrence of high-temperature minerals with later, lower-temperature minerals, resulting in a xenothermal feature of the mineralization.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.63-70
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• 2010

Transition metal based spent catalysts (Ni-Mo and Co-Mo), which were scrapped from the petrochemical industry, were reused for the removal processes of volatile organic compounds (VOCs). Especially the optimum regeneration procedures were determined using the removal efficiency of VOCs. In this work, the spent Ni-Mo and spent Co-Mo catalysts were pretreated with different physic-chemical treatment procedure: 1) acid aqueous solution, 2) alkali solution, 3) chemical agent and 4) steam. The various characterization methods of spent and its regenerated catalysts were performed using nitrogen adsorption, X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive spectrometry (EDS). It was found that all spent catalysts were found to be potentially applicable catalysts for catalytic oxidation of benzene. The experimental results also indicated that among the employed physico-chemical pretreatment methods, the oxalic acid aqueous (0.1 N, $C_2H_2O_4$) pretreatment appeared to be the most efficient in increasing the catalytic activity, although the catalytic activity of spent Ni-Mo and spent Co-Mo catalysts in the oxidation of benzene were greatly dependent on the pretreatment conditions. The pretreated spent catalysts at optimum condition could be also applied for removing other aromatic compounds (Toluene/Xylene).

• Journal of the Korean Chemical Society
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• v.37 no.2
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• pp.228-236
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• 1993

The effect of ferric ion on the reaction of CH_3$MgI with benzylbromide was investigated by determining the product ratio between cross-coupling product, ethylbenzene (A) and homocoupling product, bibenzyl (B) in the presence of ferric ion. When CH_3$MgI prepared with pure magnesium was used, the ratio of A to B was 22 to 78 and with reagent grade magnesium, the ratio became 33 to 67 indicating that metallic impurities in magnesium affect the reaction mechanism to lead less homocoupling product, B. The ratio changes became significant when ferric chloride was added in the reaction mixture in catalytic amounts and the ratio of A to B reached to 80 to 20 at maximum. The reaction in the presence of ferric ion seems to follow mainly an ionic mechanism which involves iron-benzyl bromide ${\pi}$-complex formation. The complex formation is expected to be able to enhance ionic attack of CH_3$MgI on benzyl carbon to give more A.