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Evaluations of Si based ternary anode materials by using RF/DC magnetron sputtering for lithium ion batteries

  • Hwang, Chang-Muk;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.302-303
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    • 2010
  • Generally, the high energy lithium ion batteries depend intimately on the high capacity of electrode materials. For anode materials, the capacity of commercial graphite is unlike to increase much further due to its lower theoretical capacity of 372 mAhg-1. To improve upon graphite-based negative electrode materials for Li-ion rechargeable batteries, alternative anode materials with higher capacity are needed. Therefore, some metal anodes with high theoretic capacity, such as Si, Sn, Ge, Al, and Sb have been studied extensively. This work focuses on ternary Si-M1-M2 composite system, where M1 is Ge that alloys with Li, which has good cyclability and high specific capacity and M2 is Mo that does not alloy with Li. The Si shows the highest gravimetric capacity (up to 4000mAhg-1 for Li21Si5). Although Si is the most promising of the next generation anodes, it undergoes a large volume change during lithium insertion and extraction. It results in pulverization of the Si and loss of electrical contact between the Si and the current collector during the lithiation and delithiation. Thus, its capacity fades rapidly during cycling. Si thin film is more resistant to fracture than bulk Si because the film is firmly attached to the substrate. Thus, Si film could achieve good cycleability as well as high capacity. To improve the cycle performance of Si, Suzuki et al. prepared two components active (Si)-active(Sn, like Ge) elements film by vacuum deposition, where Sn particles dispersed homogeneously in the Si matrix. This film showed excellent rate capability than pure Si thin film. In this work, second element, Ge shows also high capacity (about 2500mAhg-1 for Li21Ge5) and has good cyclability although it undergoes a large volume change likewise Si. But only Ge does not use the anode due to its costs. Therefore, the electrode should be consisted of moderately Ge contents. Third element, Mo is an element that does not alloys with Li such as Co, Cr, Fe, Mn, Ni, V, Zr. In our previous research work, we have fabricated Si-Mo (active-inactive elements) composite negative electrodes by using RF/DC magnetron sputtering method. The electrodes showed excellent cycle characteristics. The Mo-silicide (inert matrix) dispersed homogeneously in the Si matrix and prevents the active material from aggregating. However, the thicker film than $3\;{\mu}m$ with high Mo contents showed poor cycling performance, which was attributed to the internal stress related to thickness. In order to deal with the large volume expansion of Si anode, great efforts were paid on material design. One of the effective ways is to find suitably three-elements (Si-Ge-Mo) contents. In this study, the Si based composites of 45~65 Si at.% and 23~43 Ge at.%, and 12~32 Mo at.% are evaluated the electrochemical characteristics and cycle performances as an anode. Results from six different compositions of Si-Ge-Mo are presented compared to only the Si and Ge negative electrodes.

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Synthesis, Spectroscopic, and Biological Studies of Chromium(III), Manganese(II), Iron(III), Cobalt(II), Nickel(II), Copper(II), Ruthenium(III), and Zirconyl(II) Complexes of N1,N2-Bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide (N1,N2-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide의 크롬(III), 망간(II), 철(III), 코발트(II), 니켈(II), 구리(II), 루테늄(III) 및 산화 지르코늄(II) 착물에 대한 합성과 분광학 및 생물학적 연구)

  • Al-Hakimi, Ahmed N.;Shakdofa, Mohamad M.E.;El-Seidy, Ahemd M.A.;El-Tabl, Abdou S.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.418-429
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    • 2011
  • Novel chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), ruthenium(III), and zirconyl(II) complexes of $N^1,N^2$-bis(3-((3-hydroxynaphthalen-2-yl)methylene-amino)propyl)phthalamide ($H_4L$, 1) have been synthesized and characterized by elemental, physical, and spectral analyses. The spectral data showed that the ligand behaves as either neutral tridentate ligand as in complexes 2-5 with the general formula $[H_4LMX_2(H_2O)]{\cdot}nH_2O$ (M=Cu(II), Ni(II), Co(II), X = Cl or $NO_3$), neutral hexadentate ligand as in complexes 10-12 with the general formula $[H_4LM_2Cl_6]{\cdot}nH_2O$ (M=Fe(III), Cr(III) or Ru(III)), or dibasic hexadentate ligand as in complexes 6-9 with the general formula $[H_2LM_2Cl_2(H_2O)_4]{\cdot}nH_2O$ (M = Cu(II), Ni(II), Co(II) or Mn(II), and 13 with general formula $[H_4L(ZrO)_2Cl_2]{\cdot}8H_2O$. Molar conductance in DMF solution indicated the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complexes 2, 5, and 6 showed $g_{\parallel}$ >g> $g_e$, indicating distorted octahedral structure and the presence of the unpaired electron in the $N^1,N^2$ orbital with significant covalent bond character. For the dimeric copper(II) complex $[H_2LCu_2Cl_2(H_2O)_4]{\cdot}3H_2O$ (6), the distance between the two copper centers was calculated using field zero splitting parameter for the parallel component that was estimated from the ESR spectrum. The antibacterial and antifungal activities of the compounds showed that, some of metal complexes exhibited a greater inhibitory effect than standard drug as tetracycline (bacteria) and Amphotricene B (fungi).

Geochemical Characteristics of Stream Sediments Based on Bed Rocks in the Cheongpung Area (기반암에 따른 청풍지역 하상퇴적물의 지구화학적 특성)

  • Park, Young-Seog;Park, Dae-Woo;Kim, Jong-Kyun;Song, Yeung-Sang;Lee, Jang-Jon
    • Economic and Environmental Geology
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    • v.39 no.6 s.181
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    • pp.675-687
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    • 2006
  • The purpose of this study is to determine the geochemical characteristics of the stream sediments in the Cheongpung area. So that we can understand the natural background and predict the prospects of geochemical disaster, if any. We collected the stream sediments samples by wet sieving along the primary channels and slow dried the collected samples in the laboratory and ground them to pass a 200 mesh using an alumina mortar and pestle for chemical analysis. Miner-alogical characteristics, major, trace and rare earth elements were determined by XRD, XRF, ICP-AES and NAA analysis methods. For geochemical characteristics on the geological group of stream sediments, the studied area was grouped into granitic gneiss area, metatectic gneiss area, Dado tuff area, Yuchi conglomerate area, and Neungju flow area in the Cheongpung area. Contents of major elements for the stream sediments in the Cheongpung area were $SiO_2\;47.31{\sim}72.81\;wt.%,\;A1_2O_3 \;11.26{\sim}21.88\;wt.%,\;Fe_2O_3\;2.83{\sim}8.39\;wt.%,\;CaO\;0.34{\sim}7.54\;wt.%,\;MgO\; 0.55{\sim}3.59\;wt.%,\;K_2O\;1.71{\sim}4.31\;wt.%,\;Na_2O\;0.56{\sim}2.28\;wt.%,\;TiO_2\;0.46{\sim}1.24\;wt.%,\;MnO\;0.04{\sim}0.27\;wt.%,\;P_2O_5\;0.02{\sim}0.45\;wt.%$. The con-tents of trace and rare earth elements for the stream sediments were $Ba\;700ppm{\sim}8990ppm,\;Be\;1.0{\sim}3.50ppm,\;Cu\;6.20{\sim}60ppm,\;Nb\;12{\sim}28ppm,\;Ni\;4.4{\sim}61ppm,\;Pb\;13{\sim}34ppm,\;Sr\;65{\sim}787ppm,\;V\;4{\sim}98ppm,\;Zr\;32{\sim}164ppm,\;Li\;21{\sim}827ppm,\;Co\;3.68{\sim}65ppm,\;Cr\;16.7{\sim}409ppm,\;Cs\;2.72{\sim}37.1ppm,\;Hf\;4.99{\sim}49.2ppm,\;Rb\;71.9{\sim}649ppm,\;Sb\;0.16{\sim}5.03ppm,\;Sc\;4.97{\sim}52ppm,\;Zn\;26.3{\sim}375ppm,\;Ce\;60.6{\sim}373ppm,\;Eu\;0.82{\sim}6ppm,\;Yb\;0.71{\sim}10ppm$.

Characteristics of the Number and the Mass Concentrations and the Elemental Compositions of PM10 in Jeju Area (제주지역 PM10의 수농도 및 질량농도와 원소성분 조성 특성)

  • Kang, Chang-Hee;Hu, Chul-Goo
    • Journal of Environmental Science International
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    • v.23 no.3
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    • pp.447-457
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    • 2014
  • The number concentrations, the mass concentrations and the elemental concentrations of $PM_{10}$ have measured at Gosan site in Jeju, Korea, from March 2010 to December 2010. And the correlation and the factor analysis for the number, the mass and the elemental concentrations of $PM_{10}$ are performed to identify their relationships and sources. The average $PM_{10}$ number concentration is observed $246\;particles/cm^3$($35.7{\sim}1,017\;particles/cm^3$) and the average $PM_{10}$ mass concentration is shown $50.1{\mu}g/m^3$($16.7{\sim}441.4{\mu}g/m^3$) during this experimental period. The number concentrations are significantly decreased with increasing particle size, hence the concentrations for the smaller particles less than $2.5{\mu}m$($PM_{2.5}$) are contributed 99.6% to the total $PM_{10}$ number concentrations. The highest concentration of the 20 elements in $PM_{10}$ determined in this study is shown by S with a mean value of $1,497ng/m^3$ and the lowest concentration of them is found by Cd with a mean value of $0.57ng/m^3$. The elements in $PM_{10}$ are evidently classified into two group based on their concentrations: In group 1, including S>Na>Al>Fe>Ca>Mg>K, the elemental mean concentrations are higher than several hundred $ng/m^3$, on the other hand, the concentrations are lower than several ten $ng/m^3$ in group 2, including Zn>Mn>Ni>Ti>Cr>Co>Cu>Mo>Sr>Ba>V>Cd. The size-separated number concentrations are shown positively correlated with the mass concentrations in overall size ranges, although their correlation coefficients, which are monotonously increased or decreased with size range, are not high. The concentrations of the elements in group 1 are shown highly correlated with the mass concentrations, but the concentrations in group 2 are shown hardly correlated with the mass concentrations. The elements originated from natural sources have been predominantly related to the mass concentrations while the elements from anthropogenic sources have mainly affected on the number concentrations of $PM_{10}$.

Leaching of CMSX-4 Superalloy in Hydrochloric Acid Solutions (염산(鹽酸)에 의한 CMSX-4 초내열합금(超耐熱合金)의 침출(浸出))

  • Kim, Min-Seuk;Lee, Jae-Chun;Kim, Eun-Young;Yoo, Young-Soo
    • Resources Recycling
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    • v.19 no.5
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    • pp.25-30
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    • 2010
  • Leaching of CMSX-4 superalloy was done in hydrochloric acid solutions. The leaching behaviors of main alloy components, such as Ni, Co, Cr, Al, was investigated by controlling acid concentration, temperature, leaching time and pulp density. Increasing acid concentration enhanced the leaching rate till the rate decreased over 3 M acid concentration. Raising temperature increased the leaching amount of the metal components. After the leaching for 60 minutes at $90^{\circ}C$ and 10 g/L pulp density in 4 M acid solution, 93.2% nickel, 89.9% aluminum, 80.4% cobalt, and 79.1% chromium were leached. Nickel and aluminum were preferentially leached out, while the leaching rate of cobalt and chromium were relatively high only after 60 minutes, Increasing pulp density lowered the leaching rate and especially serious on cobalt and chromium, The optimum leaching condition for CMSX-4 was obtained at $90^{\circ}C$, 120 minutes, and less than 125 g/L in 4 M hydrochloric acid solution.

Seasonal Variations of Settling Particles and Metal Fluxes at a Nearshore Site of Marian Cove, King George Island, Antarctica (남극 킹조지섬 마리안소만에서 침강 입자와 금속 플럭스의 계절 변화)

  • Shim, Jeong-Hee;Kang, Young-Chul;Han, Myung-Woo;Kim, Dong-Seon;Chung, Ho-Sung;Lee, Sang-Hoon
    • Ocean and Polar Research
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    • v.24 no.2
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    • pp.123-134
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    • 2002
  • Seasonal variations of settling particles and metal fluxes were monitored at a nearshore site of Marian Cove, King Geroge Island, Antarctica from 28th February 1998 to 22nd January 2000. Near-bottom sediment traps were deployed at 30m water depth of the cove, and sampling bottles were recovered every month by SCUBA divers. Total particulate flux and metal concentrations were determined from the samples. Total particulate flux showed a distinct seasonality, high in austral summer and low in austral winter: the highest flux $(21.97g\;m^{-2}d^{-1})$ was found in February of 1999, and the lowest $(2.47g\;m^{-2}d^{-1})$ in September of 1998, when sea surface was frozen completely. Lithogenic particle flux accounted for 90% of the total flux, and showed a significantly negative correlation with the thickness of snow accumulation around the study site. It was suggested that the most of the lithogenic particles trapped in the bottles was transported by melt water stream from the surrounding land. Fluxes of Al, Fe, Ti, Mn, Zn, Cii, Co, Ni, Cr, Cd, and Pb showed similar seasonal variations with the total flux, and their averaged fluxes were 34000, 9000,960, 180, 13.8, 17.6, 3.0,2.1, 5.4, 0.02, and $1.5nmol\;m^{-2}d^{-1}$ respectively. Among the metals, Cu and Cd showed the most noticeable seasonal patterns. The Cd flux correlated positively with the fluxes of biogenic components while the Cu flux correlated with both the lithogenic and biogenic particle fluxes. The Cu flux peak in the late summer is likely related to a substantial amount of inflow of ice melt water laden with Cu-enriched lithogenic particles. On the other hands, the Cd flux peak in the early spring may be associated with the unusually early occurred phytoplankton bloom.

Heavy Metal Contents and Safety Evaluation of Commercial Salts in Seoul (서울시 유통 소금의 중금속 함량 및 안전성 평가)

  • Kim, Ae-Kyung;Cho, Sung-Ja;Kwak, Jae-Eun;Kum, Jin-Young;Kim, Il-Young;Kim, Jung-Hun;Chae, Young-Zoo
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.41 no.1
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    • pp.129-135
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    • 2012
  • This study was to investigate the heavy metal content of 55 commercial salts in the Seoul area. There were 22 types of solar sea salt, 17 types of processed salt and 16 types of reworked salt. Looked at another way, there were 22 types of domestic salt and 33 types of salt imported from France, the U.S., Japan, Australia, New Zealand, and Argentina. The samples were measured using both a mercury analyzer and an Inductively-Coupled Plasma Optical Emission Spectrometer (ICP-OES). The average heavy metal contents for commercial salts were Pb $0.281{\pm}0.344$, Cd $0.035{\pm}0.221$, Cr $0.364{\pm}0.635$, Cu $0.182{\pm}0.313$, As $0.046{\pm}0.062$, Ni $0.155{\pm}0.247$, Al $5.753{\pm}10.746$, Co $0.028{\pm}0.211$ and Hg $0.001{\pm}0.001$ mg/kg. The leads were detected highly in solar sea salt rather than in processed salt or reworked salt. Also chrome, arsenic and nickel were found more in processed salt. There were large differences in aluminum content between imported solar sea salt and processed salt. Aluminum was highly detected in French products, showing that salt can be affected by regional differences. The weekly average intakes of Pb, Cd, Cr, Cu, and Hg from commercial salt were 1.652% (0.000~6.754), 0.372% (0.000~7.214), 3.177% (0.000~26.279), 0.008% (0.001~0.049), and 0.031% (0.000~0.094) respectively compared with Provisional Tolerable Weekly Intakes established by the Joint FAO/WHO Expert Committee for the evaluation of food safety. The content of heavy metals from commercial salts was determined to be at safe levels.

Geochemistry and Genesis of the Guryonsan(Ogcheon) Uraniferous Back Slate (구룡산(九龍山)(옥천(決川)) 함(含)우라늄 흑색(黑色) 점판암(粘板岩)의 지화학(地化學) 및 성인(成因))

  • Kim, Jong Hwan
    • Economic and Environmental Geology
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    • v.22 no.1
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    • pp.35-63
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    • 1989
  • Geochemical characteristics of the Guryongsan (Ogcheon) uraniferous black slate show that this is an analogue to the conventional Chattanooga and Alum shales in occurrences. Whereas, its highest enrichment ratio in metals including uranium, among others, is explained by the cyclic sedimentation of the black muds and quartz-rich silts, and the uniform depositional condition with some what higher pH condition compared to the conditions of the known occurrences. The cyclic sedimentation, caused by the periodic open and close of the silled basin, has brought about the flush-out) of the uranium depleted water and the recharge with the new metal-rich sea water, which consequently contributed to the high concentration of metals in mud. The metal-rich marine black muds, which mostly occur in the early to middle Palaeozoic times, is attributed by the geologic conditions which related to the atmospheric oxygen contents, and these are scarcely met in the late Precambrian and/or with the onset of Palaeozoic era in the geologic evolution of the earth.

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Physico-Chemical Properties of Aggregate By-Products as Artificial Soil Materials (골재 부산물의 용토재 활용을 위한 특성 분석)

  • Yang, Su-Chan;Jung, Yeong-Sang;Kim, Dong-Wook;Shim, Gyu-Seop
    • Korean Journal of Soil Science and Fertilizer
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    • v.40 no.5
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    • pp.418-428
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    • 2007
  • Physical and chemical properties of the aggregate by-products including sludge and crushed dust samples collected from the 21 private companies throughout the country were analyzed to evaluate possible usage of the by-products as artificial soil materials for plantation. The pH of the materials ranged from 8.0 to 11.0. The organic matter content was $2.85g\;kg^{-1}$, and the total nitrogen content and available phosphate content were low as 0.7 percents and $12.98mg\;kg^{-1}$, respectively. Exchangeable $Ca^{2+}$, $Mg^{2+}$, $K^+$, and $Na^+$ were 2.29, 0.47, 0.02 and $0.05cmol\;kg^{-1}$, respectively. Heavy metal contents were lower than the limits regulated by environmental law of Korea. Textural analysis showed that most of the materials were silt loam with low water holding capacity ranged from 0.67 to 7.41 percents, and with low hydraulic conductivity ranged from 0.4 to $2.8m\;s^{-1}$. Mineralogical analysis showed that the aggregate by product materials were mostly composed of silicate, alumina and ferric oxides except calcium oxide dominant materials derived from limestones. The primary minerals were quartz, feldspars and dolomites derived from granite and granitic gneiss materials. Some samples derived from limestone material showed calcite and graphite together with the above minerals. According to the result, it can be concluded that the materials could be used as the artificial soil material for plantation after proper improvement of the physico-chemical properties and fertility.