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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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Changes in sedimentary structure and elemental composition in the Nakdong Estuary, Korea (낙동강 하구역 퇴적구조 및 원소조성 변화에 관한 연구)

  • Kim, Yunji;Kang, Jeongwon;Park, Seonyoung
    • Journal of Wetlands Research
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    • v.23 no.3
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    • pp.213-223
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    • 2021
  • To understand the sedimentary environment of Scirpus planiculmis habitat (Myeongji and Eulsuk tidal flats) in the Nakdong Estuary, this study analyzed the statistical parameters (sorting, skewness, and kurtosis) of grain size data and the major (Al, Fe, Mn, Mg, Ca, Na, K, Ti, and P), minor (Li, Sc, V, Cr, Co, Ni, Cu, Zn, Sr, Zr, Cs, Pb, Th, and U), and rare earth elements (REEs) in sediment cores. For Myeongji, the sediment structure of the upper part of the cores was poorly sorted, more finely skewed, and more leptokurtic due to construction of the West gate. By contrast, the Eulsuk cores all differed due to the contrasting floodgate operation patterns of the West and East gates. The linear discriminate function (LDF) results corresponded to the statistical parameters for grain size. At the Eulsuk tidal flat (sites ES05 and ES11), elemental distributions were representative of Al-, Fe- and Ca-associated profiles, in which the elements are largely controlled by the accumulation of their host minerals (such as Na- and K-aluminosilicate and ferromagnesium silicate) and heavy detrital minerals at the sites. Detrital minerals including the aluminosilicates are major factors in the elemental compositions at ES05, diluting the REE contents. However, clay minerals and Fe-oxyhydroxides, as well as REE-enriched heavy minerals, appeared to be controlling factors of the elemental composition at ES11. Therefore, the mineral fractionation process is important in determining the elemental composition during sedimentation, which reflects the depositional condition of riverine-saline water mixing at both sites.

Studies on the Separation and Preconcentration of Metal Ions by Chelating Resin containing (Polystyrene-divinylbenzene)-thiazolylazo Phenol Derivatives(I) ((Polystyrene-divinylbenzene)-thiazolylazo phenol형 킬레이트 수지에 의한 금속이온의 분리 및 농축에 관한 연구(I))

  • Lim, Jae-Hee;Kim, Min-Kyun;Lee, Chang-Hun;Lee, Won
    • Analytical Science and Technology
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    • v.9 no.3
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    • pp.279-291
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    • 1996
  • The new chelating resins, XAD-2, 4, 16-TAC and XAD-2, 4, 16-TAO were synthesized by Amberlite XAD-2, XAD-4, and XAD-16 macroreticular resins with 2-(2-thiazolylazo)-p-cresol(TAC) and 4-(2-thiazolylazo)orcinol(TAO) as functional groups and were characterized by elemental analysis and FT-IR spectrometry. It was found that the content of functional group in chelating resin was 0.60mmol/g in XAD-16-TAC and 0.68mmol/g in XAD-16-TAO respectively. The chelating resins were stable in acidic and alkaline solution and can be reused over 10 times. The sorption behavior of some metalions to two chelating resins was investigated by batch method, which included batch equilibrium, effect of pH, coexisting ions and masking agent. For the optimum condition of sorption, the time required for equilibrium was about 1 hour and optimum pH was 5. In the presence of anions such as ${SO_4}^{2-}$ and $CH_3COO^-$, the sorption of U(VI) ion was slightly reduced but other anions such as $Cl^-$ and $NO{_3}^-$ revealed no interference effect. Also, sorption capacity of U(VI) ion was decreased by addition of $CO{_3}^{2-}$ ion because of complex formation of $[UO_2(CO_3)_3]^{4-}$, but alkali metals and alkali earth metals including Na(I), K(I), Mg(II), and Ca(II) were not affected for the sorption extent. Masking agent, NTA showed better separation efficiency of U(VI) ion from coexisting metal ions such as Th(IV), Zr(IV), Hf(IV), Cu(II), Cd(II), Pb(II), Ni(II), Zn(II) and Mn(II) than EDTA, CDTA.

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휨 구조의 압전 마이크로-켄틸레버를 이용한 진동 에너지 수확 소자

  • Na, Ye-Eun;Park, Hyeon-Su;Park, Jong-Cheol
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.476-476
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    • 2014
  • 서론: 저 전력 소모를 필요로 하는 무선 센서 네트워크 관련 기술의 급격한 발달과 함께 자체 전력 수급을 위한 진동 에너지 수확 기술에 대한 연구가 활발히 이루어지고 있다. 다양한 구조와 소재를 압전 외팔보에 적용하여 제안하고 있다. 그 중에서도 진동 기반의 에너지 수확 소자는 주변 환경에서 쉽게 진동을 얻을 수 있고, 높은 에너지 밀도와 제작 방법이 간단하다는 장점을 가지고 있어 많은 분야에 응용 및 적용 가능하다. 기존 연구에서는 2차원적으로 진동 에너지 수확을 위한 휜 구조의 압전 외팔보를 제안 하였다. 휜 구조를 갖는 압전 외팔보는 각각의 짧은 두 개의 평평한 외팔보가 일렬로 연결된 것으로 볼 수 있다. 하나의 짧고 평평한 외팔보는 진동이 가해지면 접선 방향으로 응력이 생겨 최대 휨 모멘텀을 갖게 된다. 그러므로 휜 구조를 갖는 외팔보는 진동이 인가됨에 따라 길이 방향과 수직 방향으로 진동한다. 하지만, 이 구조는 수평 방향으로 가해지는 진동에 대한 에너지를 수확하기에는 한계점을 가진다. 즉, 3축 방향에서 임의의 방향에서 진동 에너지를 수확하기는 어렵다. 본 연구에서는 3축 방향에서 에너지를 효율적으로 수확할 수 있도록 헤어-셀 구조의 압전 외팔보 에너지 수확소자를 제안한다. 제안된 소자는 길이 방향과 수직 방향뿐만 아니라 수평 방향으로도 진동하여 임의의 방향에서 진동 에너지를 수확할 수 있다. 구성 및 공정: 제안하는 소자는 3축 방향에서 임의의 진동을 수확하기 위해서 길이를 길게 늘이고 길이 방향을 따라 휘어지는 구조의 헤어-셀 구조로 제작하였다. 외팔보의 구조는 외팔보의 폭 대비 길이의 비가 충분히 클 때, 추가적인 자유도를 얻을 수 있다. 그러므로 헤어-셀 구조의 에너지 수확 소자는 기본적인 길이 방향, 수직방향 그리고 수평방향에 더불어 추가적으로 뒤틀리는 방향을 통해서 3차원적으로 임의의 주변 진동 에너지를 수확하여 전기적인 에너지로 생성시킬 수 있다. 제작된 소자는 높은 종횡비를 갖는 무게 추($500{\times}15{\times}22{\mu}m3$)와 길이 방향으로 길게 휜 압전 외팔보($1000{\times}15{\times}1.7{\mu}m3$)로 구성되어있다. 공정 과정은 다음과 같다. 먼저, 실리콘 웨이퍼 위에 탄성층을 형성하기 위해 LPCVD SiNx를 $0.8{\mu}m$와 LTO $0.2{\mu}m$를 증착 후, 각각 $0.03{\mu}m$$0.12{\mu}m$의 두께를 갖는 Ti와 Pt을 하부 전극으로 스퍼터링한다. 그리고 Pb(Zr0.52Ti0.48)O3 박막을 $0.35{\mu}m$ 두께로 졸겔법을 이용하여 증착하고 상부 Pt층을 두께 $0.1{\mu}m$로 순차적으로 스퍼터링하여 형성한다. 상/하부 전극은 ICP(Inductively Coupled Plasma)를 이용해 건식 식각으로 패턴을 형성한다. PZT 층과 무게 추 사이의 보호막을 씌우기 위해 $0.2{\mu}m$의 Si3N4 박막이 PECVD 공정법으로 증착되고, RIE로 패턴을 형성된다. Ti/Au ($0.03/0.35{\mu}m$)이 E-beam으로 증착되고 lift-off를 통해서 패턴을 형성함으로써 전극 본딩을 위한 패드를 만든다. 초반에 형성한 실리콘 웨이퍼 위의 SiNx/LTO 층은 RIE로 외팔보 구조를 형성한다. 이후에 진행될 도금 공정을 위해서 희생층으로는 감광액이 사용되고, 씨드층으로는 Ti/Cu ($0.03/0.15{\mu}m$) 박막이 스퍼터링 된다. 도금 형성층을 위해 감광액을 패턴화하고, Ni0.8Fe0.2 ($22{\mu}m$)층으로 도금함으로써 외팔보 끝에 무게 추를 만든다. 마지막으로, 압전 외팔보 소자는 XeF2 식각법을 통해 제작된다. 제작된 소자는 소자의 여러 층 사이의 고유한 응력 차에 의해 휨 변형이 생긴다. 실험 방법 및 측정 결과: 제작된 소자의 성능을 확인하기 위하여 일정한 가속도 50 m/s2로 3축 방향에 따라 입력 주파수를 변화시키면서 출력 전압을 측정하였다. 먼저, 소자의 기본적인 공진 주파수를 얻기 위하여 수직 방향으로 진동을 인가하여 주파수를 변화시켰다. 그 때에 공진 주파수는 116 Hz를 가지며, 최대 출력 전압은 15 mV로 측정되었다. 3축 방향에서 진동 에너지 수확이 가능하다는 것을 확인하기 위하여 제작된 소자를 길이 방향과 수평 방향으로 가진기에 장착한 후, 기본 공진 주파수에서의 출력 전압을 측정하였다. 진동이 길이방향으로 가해졌을 때에는 33 mV, 수평방향으로 진동이 인가되는 경우에는 10 mV의 최대 출력 전압을 갖는다. 제안하는 소자가 수 mV의 적은 전압은 출력해내더라도 소자는 진동이 인가되는 각도에 영향 받지 않고, 3축 방향에서 진동 에너지를 수확하여 전기에너지로 얻을 수 있다. 결론: 제안된 소자는 3축 방향에서 진동 에너지를 수확할 수 있는 에너지 수확 소자를 제안하였다. 외팔보의 구조를 헤어-셀 구조로 길고 휘어지게 제작함으로써 기본적인 길이 방향, 수직방향 그리고 수평방향에 더불어 추가적으로 뒤틀리는 방향에서 출력 전압을 얻을 수 있다. 미소 전력원으로 실용적인 사용을 위해서 무게추가 더 무거워지고, PZT 박막이 더 두꺼워진다면 소자의 성능이 향상되어 높은 출력 전압을 얻을 수 있을 것이라 기대한다.

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Reproductive Cycle of the Echiuroid Worm Urechis unicinctus(von Drasche) in Southern Korea (한국산 개불, Urechis unicinctus (von Drasche)의 생식주기)

  • 최상덕;김호진;이원교;곽은주;윤호섭;라성주;이인곤
    • Journal of Aquaculture
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    • v.13 no.2
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    • pp.169-174
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    • 2000
  • Reproductive cycle of U. unicinctus was studied from September 1998 to August 1999, using gonadosomatic index (CSI) as an indicator. In November, the CSI values were maximum for male (6.2) and female (7.0), respectively; the values were lowest for them (1.0 and 0.5) during the successive february. Subsequently, they rapidly increased and attained peak by March-April. The values decreased again in both sexes and remained unchanged until August. The index increased in October to attain the peak by November. The CSI values clearly indicated that there are two spawning events in a year, namely the first one during April-May and the second one in December. Reproductive cycle was classified into the following successive stages: in female, multipication (January~February, June ~Setember), maturation (March~April, November), spent (May and December), degeneration and resting (June and January), and in male, multiplication January ~ february, June ~September), maturation (March~April, October~November), spent (May and December) and degeneration and resting (January and June). Histological observations revealed that oocytes in the ovary matured simultaneously in November and March. At the same time, the envelopes of matured testis became thinner than those in the early stage.

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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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Application of Science for Interpreting Archaeological Materials(III) Characterization of Some Western Asia Glass Vessels from South Mound of Hwangnamdaechong (고고자료의 자연과학 응용(III) 황남대총(남분)의 일부 서역계 유리제품에 대한 과학적 특성 분류)

  • Kang, Hyung Tae;Cho, Nam Chul
    • Korean Journal of Heritage: History & Science
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    • v.41 no.1
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    • pp.5-19
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    • 2008
  • Thirty six samples of Western asia glass vessel shards which were excavated from South Mound of Hwangnamdaechong were each measured for thickness, pore size and specific gravity and analyzed for ten major compositions and thirteen trace elements. The glass samples with colorless, greenish blue and dark purple blue were well classified by principal component analysis(PCA). All glass shards of Hwangnamdaechong belonged to Soda glass system ($Na_2O-CaO-SiO_2$) which have the range of 14~17% $Na_2O$ and 5~6% CaO. The corelation coefficients of (MgO, $K_2O$) and (MnO, CuO) showed above 0.90. The concentrations of thirteen trace elements apparently differentiated from colorless, greenish blue and dark blue glasses. We found that thirteen trace elements were very important indices for studying raw material of glass and the origin of glass making. Colorless glass : The specific gravity is $1.50{\pm}0.04$. Circle or oval circle pores are observed with regular direction in internal zone and the longest one is about 0.35 mm. The raw material of sodium must be the plant ash because sodium glasses contain HCLA(High CaO, Low $Al_2O_3$) and HMK(high MgO, high $K_2O$) and suggested to Sasanian glass. The total amount of coloring agent of colorless glass is below 1 % which is too small to attribute to the color. Greenish blue glass : The specific gravity is $1.58{\pm}0.04$. The fine pores which are 0.1~0.2mm are dispersed in internal zone. Sodium glasses are distributed to HCLA and HMK. Therefore the greenish blue glass also have used plant ash for raw material of sodium with the same as colorless glass. It was also suggested to the glass of Sasanian. The total amount of coloring agent of greenish blue glass is about 4% under the influence of working MnO, $Fe_2O_3$ and CuO. Dark purple blue glass : The specific gravity is $1.48{\pm}0.19$. There are rarely pores in internal zone. They are distributed to HCLA and LMK(Low MgO, Low $K_2O$) and suggested to Roman glass. The raw material of sodium is estimated to natron. The total amount of coloring agents of greenish blue is about 3% by $Fe_2O_3$ and CuO. These studies for western asia glass shards from South Mound of Hwangnamdaechong could be used in the future as the standard data which could be compared with those of other several graves in Korea and dispersed in foreign areas.