• Title/Summary/Keyword: Li-Ion

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Enhanced Si based negative electrodes using RF/DC magnetron sputtering for bulk lithium ion batteries

  • Hwang, Chang-Muk;Park, Jong-Wan
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.277-277
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    • 2010
  • The capacity of the carbonaceous materials reached ca. $350\;mAhg^{-1}$ which is close to theorestical value of the carbon intercalation composition $LiC_6$, resulting in a relatively low volumetric Li capacity. Notwithstanding the capacities of carbon, it will not adjust well to the need so future devices. Silicon shows the highest gravimetric capacities (up to $4000\;mAhg^{-1}$ for $Li_{21}Si_5$). 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. We focused on electrode materials in the multiphase form which were composed of two metal compounds to reduce the volume change in material design. A combination of electrochemically amorphous active material in an inert matrix (Si-M) has been investigated for use as negative electrode materials in lithium ion batteries. The matrix composited of Si-M alloys system that; active material (Si)-inactive material (M) with Li; M is a transition metal that does not alloy with Li with Li such as Ti, V or Mo. We fabricated and tested a broad range of Si-M compositions. The electrodes were sputter-deposited on rough Cu foil. Electrochemical, structural, and compositional characterization was performed using various techniques. The structure of Si-M alloys was investigated using X-ray Diffractometer (XRD) and transmission electron microscopy (TEM). Surface morphologies of the electrodes are observed using a field emission scanning electron microscopy (FESEM). The electrochemical properties of the electrodes are studied using the cycling test and electrochemical impedance spectroscopy (EIS). It is found that the capacity is strongly dependent on Si content and cycle retention is also changed according to M contents. It may be beneficial to find materials with high capacity, low irreversible capacity and that do not pulverize, and that combine Si-M to improve capacity retention.

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Nanoscale Characterization of a Heterostructure Interface Properties for High-Energy All-Solid-State Electrolytes (고에너지 전고체 전해질을 위한 나노스케일 이종구조 계면 특성)

  • Sung Won Hwang
    • Journal of the Semiconductor & Display Technology
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    • v.22 no.1
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    • pp.28-32
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    • 2023
  • Recently, the use of stable lithium nanostructures as substrates and electrodes for secondary batteries can be a fundamental alternative to the development of next-generation system semiconductor devices. However, lithium structures pose safety concerns by severely limiting battery life due to the growth of Li dendrites during rapid charge/discharge cycles. Also, enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against oxide solid electrolytes. For the development of next-generation system semiconductor devices, solid electrolyte nanostructures, which are used in high-density micro-energy storage devices and avoid the instability of liquid electrolytes, can be promising alternatives for next-generation batteries. Nevertheless, poor lithium ion conductivity and structural defects at room temperature have been pointed out as limitations. In this study, a low-dimensional Graphene Oxide (GO) structure was applied to demonstrate stable operation characteristics based on Li+ ion conductivity and excellent electrochemical performance. The low-dimensional structure of GO-based solid electrolytes can provide an important strategy for stable scalable solid-state power system semiconductor applications at room temperature. The device using uncoated bare NCA delivers a low capacity of 89 mA h g-1, while the cell using GO-coated NCA delivers a high capacity of 158 mA h g−1 and a low polarization. A full Li GO-based device was fabricated to demonstrate the practicality of the modified Li structure using the Li-GO heterointerface. This study promises that the lowdimensional structure of Li-GO can be an effective approach for the stabilization of solid-state power system semiconductor architectures.

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Alkali Metal Ion Catalysis and Inhibition in Nucleophilic Substitution Reactions of 3,4-Dinitrophenyl Diphenylphosphinothioate with Alkali Metal Ethoxides in Anhydrous Ethanol: Effect of Changing Electrophilic Center from P=O to P=S

  • An, Jun-Sung;NamKoong, Gil;Kang, Ji-Sun;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2423-2427
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    • 2011
  • Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for nucleophilic substitution reactions of 3,4-dinitrophenyl diphenylphosphinothioate 9 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] is linear for the reaction of 9 with EtOK. However, the plot curves downwardly for those with EtOLi and EtONa while it curves upwardly for the one with EtOK in the presence of 18-crown-6-ether (18C6). Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-}$ ${\approx}$ $k_{EtOK}$ < $k_{EtOK/18C6}$, indicating that the reaction is inhibited by $Li^+$ and $Na^+$ ions but is catalyzed by 18C6-crowned $K^+$ ion. The reactivity order found for the reactions of 9 contrasts to that reported previously for the corresponding reactions of 1, i.e., $k_{EtOLi}$ > $k_{EtONa}$ > $E_{EtOK}$ > $k_{EtO^-}$ ${\approx}$ $k_{EtOK/18C6}$, indicating that the effect of changing the electrophilic center from P=O to P=S on the role of $M^+$ ions is significant. A four-membered cyclic transition-state has been proposed to account for the $M^+$ ion effects found in this study, e.g., the polarizable sulfur atom of the P=S bond in 9 interacts strongly with the soft 18C6-crowned $K^+$ ion while it interacts weakly with the hard $Li^+$ and $Na^+$ ions.

Salt Effect of Metal Ion Substituted Membranes for Water-Alcohol Systems Using Pervaporation Processes (투과증발공정을 이용한 물-알코올계에 대한 금속이온이 치환된 이온교환막의 염효과 연구)

  • 임지원;전지현
    • Membrane Journal
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    • v.11 no.3
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    • pp.133-139
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    • 2001
  • The hydorgen ions in PVA/SSA membranes were substituted with monovalent metal ions, $Li^{+}$, $Na^{+}$, $K^{+}$, divalent metal ion forms, $Mg^{2+}$, $Ca^{2+}$, $Ba^{2+}$, trivalent metal ion forms, $Al^{+}$. The effect of exchange with metal ions was investigated through the swelling measurement and pervaporative experiments for water-ethanol and water-methanol mixtures at various operating conditions. In addition, ESCA analysis was carried out to study the substitution of the metal ions in membranes. The swelling ratio decerased in the sequence of $Li^{+}$, $Na^{+}$, $K^{+}$ and this might be due to the 'salting-out` effect while the swelling ratios for divalnet and trivalent ion-substituted membranes were affected by the combined effect of salting-out, electrostatic crosslinking and extent of metal ion substitution. For the pervaporation performance, PVA/SSA-$H^{+}$membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. The typical results of the flux, 59 g/$m^{2}$hr and the separation factor, 44 were obtained at $50^{\circ}C$ for 90% ethanol aqueous mixture. For water-methanol solutions, the PVA/SSA membranes substituted with monovalent PVA/SSA membranes substituted with divalent and tribalent metal ions, both `salting-out` and electrostatic effects affected the pervaporative results.

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Adhesion Layer 사용으로 인한 Si Thin Film Anode 전극의 신뢰성 향상

  • O, Min-Seop;Song, Yeong-Hak;U, Chang-Su;Jeong, Jun-Ho;Hyeon, Seung-Min;Lee, Hu-Jeong
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.681-682
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    • 2013
  • 전기는 우리 주변의 에너지 형태 중에서 가장 편리하고 광범위하게 사용되고 있다. 이러한 전기는 전자제품, 전기자동차, 에너지 저장 플랜트 등 매우 많은 분야에서 저장되고 사용되고 있다. 특히 에너지 저장 용량의 확대는 휴대폰, 노트북 PC 등 휴대용 IT 기기의 성장에 결정적인 역할을 하였다. 가볍고 작으면서도 고용량의 전기 에너지 저장 장치가 없었다면, 통신이나 인터넷 그리고 오락 등 다양한 기능을 작은 휴대용 기기에 구현할 수 없었을 것이다. 그러나 시간이 흐를수록 기기의 요구 성능이 높아지고 소비자의 니즈가 더욱더 다양해지고 고도화될수록 단일 부품으로 가장 큰 부피를 차지하는 에너지 저장 장치의 용량과 디자인은 점점 중요해지고 있다. 이러한 에너지 저장 장치에서 가장 친숙한 형태는 2차 전지 계열이다. 납 축전지를 비롯하여, 니켈수소, 니켈카드뮴, electrochemical capacitor와 Li ion 계열 등이 대표적이다. 특히 Li ion 배터리는 모바일, 자동차 및 에너지 저장 그리드 등과 같은 다양한 분야에 가장 많이 적용되고있다. Li ion 배터리에 대하여 현재의 핵심적인 연구분야는 전극 재료(cathode, anode)와 electrolyte에 대한 것이다. Anode 전극 재료 중에서 가장 많이 사용되는 재료는 카본을 기반으로 하는 재료로 안정성에 대한 장점이 있지만 에너지 밀도가 낮다는 단점이 있다. 에너지 저장 용량 증가에 대한 필요성이 증가하기 때문에 현재 많이 사용되고 있는 에너지 밀도가 낮은 카본 재료를 대체하기 위해서 이론 용량이 높다고 알려진 실리콘과 같은 메탈이나 주석 산화물과 같은 천이 금속 산화물에 대하여 많은 연구가 진행되고 있다. 특히 현재까지 알려진 많은 재료 중에서 가장 큰 capacity (~4,000 mAh/g)를 가지고 있다고 알려진 실리콘이 카본의 대체 재료로 많은 연구가 진행되고 있다. 그러나, Li 과 반응을 하며 약 300~400%에 달하는 부피팽창이 발생하고, 이러한 부피 팽창 때문에 충 방전이 진행됨에 따라 current collector로부터 박리되는 현상을 보여 빠른 용량 감소를 보여주고 있다. 본 연구에서는 adhesion layer를 current collector와 실리콘 전극 재료 사이에 삽입하여 충 방전 시 부피팽창에 의한 미세구조의 변화와 electrochemical 특성에 대한 영향을 알아보았다. 실험에 사용한 anode 전극은 상용 Cu foil current collector에 RF/DC magnetron 스퍼터링을 통해 다양한 종류(Ti, Ta 등)의 adhesion layer과 200 nm 두께의 Si 박막을 증착하였다. 또한 Bio-logic Potentiostat/ Galvanostat VMP3 와 WanAtech automatic battery cycler 장비를 사용하여 0.2 C-rate로 half-cell 타입의 코인 셀로 조립한 전극에 대한 충 방전 실험을 진행하였다. Adhesion layer의 사용으로 인해 실리콘 박막과 Cu current collector 사이의 박리 현상을 줄여줄 수 있었고, 충 방전 시 Cu 원자의 실리콘 박막으로의 확산을 통한 brittle한 Cu-Si alloy 형성을 막아 줄 수 있어 큰 특성 향상을 확인할 수 있었다. 또한, 리튬과 실리콘의 반응을 통한 형태와 미세구조 변화를 SEM, TEM 등의 다양한 장비를 사용하여 확인하였고, 이를 통해 adhesion layer의 사용이 전극의 특성향상에 큰 영향을 끼쳤다는 것을 확인할 수 있었다.

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Defect center of $Li^{+}$ ion implanted $Al_2O_3$ ($Li^{+}$ 이온 주입된 $Al_2O_3$의 결함 특성)

  • Kim, Tae-Kyu
    • Progress in Medical Physics
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    • v.5 no.2
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    • pp.13-20
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    • 1994
  • The thermoluminescence(TL) glow curves and the optical absorption of $Al_2O_3$ irradiated with ${\gamma}$-ray, electron, and $Li^{+}$ ion followed by electron irradiation have been investigated to determine the relation of TL peak to its defect type. The TL glow curve of $Al_2O_3$ irradiated with ${\gamma}$-ray shows TL peaks at 380 K, 415 K, and 475 K. The UV photobleached TL glow curve of $Al_2O_3$ irradiated with ${\gamma}$-ray shows that the 380 K and 475 K TL peaks completely disappear while the 415 K TL peak still exists. The electron beam induced TL glow curve of $Al_2O_3$ after $Li^{+}$ ion implantation shows that the TL peak at 440 K is enhanced by a factor of 2 over the TL intensity of unimplanted $Al_2O_3$ while the TL peak at 380 K evidently disappears The implanted $Li^{+}$ ions are assumed to form singly charged interstitial cations and then recombine with electron trapped in F centers to produce F+ centers. The 380 K and 475 K TL peaks are proposed to be associated with F center, while the 415 K and 440 K TL peak are connected with F$^{+}$ center.

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Surface Treatment of LiFePo4 Cathode Material for Lithium Secondary Battery

  • Son, Jong-Tae
    • Journal of the Korean Electrochemical Society
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    • v.13 no.4
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    • pp.246-250
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    • 2010
  • In this study, nano-crystallized $Al_2O_3$ was coated on the surface of $LiFePO_4$ powders via a novel dry coating method. The influence of coated $LiFePO_4$ upon electrochemical behavior was discussed. Surface morphology characterization was achieved by transmission electron microscopy (TEM), clearly showing nano-crystallized $Al_2O_3$ on $LiFePO_4$ surfaces. Furthermore, it revealed that the $Al_2O_3$-coated $LiFePO_4$ cathode exhibited a distinct surface morphology. It was also found that the $Al_2O_3$ coating reduces capacity fading especially at high charge/discharge rates. Results from the cyclic voltammogram measurements (2.5-4.2 V) showed a significant decrease in both interfacial resistance and cathode polarization. This behavior implies that $Al_2O_3$ can prevent structural change of $LiFePO_4$ or reaction with the electrolyte on cycling. In addition, the $Al_2O_3$ coated $LiFePO_4$ compound showed highly improved area-specific impedance (ASI), an important measure of battery performance. From the correlation between these characteristics of bare and coated $LiFePO_4$, the role of $Al_2O_3$ coating played on the electrochemical performance of $LiFePO_4$ was probed.

Li-doped Y2SiO5:Ce, Blue-emitting Phosphor (Li-이온이 도핑된 Y2SiO5:Ce 청색 형광체)

  • Park, Jung-Cheol;Jeon, Gi-Wan
    • Journal of the Korean Chemical Society
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    • v.50 no.3
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    • pp.232-236
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    • 2006
  • The Y1.99-xMxCe0.01SiO5(M=Li, La, Nd, and Gd) phosphors were synthesized by solid-state reaction at 1350oC for 10h under reducing atmosphere in order to improve properties of blue emitting phosphors. Compared with commercial blue phosphors, the Y2SiO5:Ce blue phosphors substituted with various elements showed significant enhancement of the emission intensity. Particularly, 1 mol% Li doped Y2SiO5:Ce phosphors indicated the maximum emission intensity in the photoluminescence spectra. Thanks to SEM analyses revealed that the morphology of Y2SiO5:(Ce,Li) blue phosphors was a pseudo-spherical with particle size of 3m.

Stability of Li[Co0.1Ni0.15Li0.2Mn0.55]O2 Cathode Material for Lithium Secondary Battery (리튬 2차 전지용 Li[Co0.1Ni0.15Li0.2Mn0.55]O2 양극물질의 안정성 고찰)

  • Park, Yong-Joon
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.20 no.5
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    • pp.443-449
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    • 2007
  • The structural and thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ electrode during cycling process was studied. The sample was prepared by simple combustion method. Although there were irreversible changes on the initial cycle, O3 stacking for $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ structure was retained during the first and subsequent cycling process. Impedance of the test cell was decreased after the first charge-discharge process, which would be of benefit to intercalation and deintercalation of lithium ion on subsequent cycling. As expected, cycling test for 75 times increased impedance of the cell a little, instead, thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ was improved. Moreover, based on DSC analysis, the initial exothermic peak was shifted to high temperature range and the amount of heat was also decreased after cycling test, which displayed that thermal stability was not deteriorated during cycling.

Electrical conductivity of olivine type LiFe0.965Cr0.03B0.005PO4 and LiFe0.965Cr0.03Al0.005PO4 powders (올리빈형 LiFe0.965Cr0.03B0.005PO4 and LiFe0.965Cr0.03Al0.005PO4 분말의 전기전도도)

  • Kim, Chang-Sam
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.20 no.3
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    • pp.141-146
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    • 2010
  • $LiFePO_4$ doped with Cr showed improved electrochemical properties as a cathode material of lithium-ion batteries compared to the undoped. The improvement was thought that the doping would raise the electronic conductivity of the compounds. The electrical conductivity of $LiFe_{0.965}Cr_{0.03}B_{0.005}PO_4$ and $LiFe_{0.965}Cr_{0.03}Al_{0.005}PO_4$ powder was measured in the temperature range from 30 to $80^{\circ}C$. The doped powders were synthesized via mechanochemical milling and subsequent heat treatment at 675~$750^{\circ}C$ for 5~10h. The doping enhanced grain growth and electrical conductivity. The electrical conductivity of the $LiFe_{0.965}Cr_{0.03}Al_{0.005}PO_4$ powder at $30^{\circ}C$ was $1{\times}10^{-8}S/cm$, which was higher two orders of magnitude than that of the undoped.