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폐리튬이온전지로부터 분리한 양극활물질의 침출 (Leaching of Cathodic Active Materials from Spent Lithium Ion Battery)

  • 이철경;김태현
    • 자원리싸이클링
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    • 제9권4호
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    • pp.37-43
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    • 2000
  • 폐리륨이온전지의 재활용 일환으로 폐전지에서 분리한 양극활물질인 $LiCoO_2$로부터 Li과 Co룹 회수하기 위하여 침출거동올 조사하였다. 전 연구에서 얻은 최적조건에서 $LiCoO_2$를 1M 황산과 질산으료 침출하였을 때 Li과 Co의 침출율이 각각 70-80%, 40%로 Co의 침출율이 낮았다. 환원제를 첨가한 경우 Li과 Co의 침출율이 증가하였는데, 특히 $Na_2S_2O_3$$H_2O_2$ 와 같은 환원제에서 질산침출을 하는 경우 Li괴- Co의 용해가 거의 95% 이상 이루어졌다. 이는 환원제가 $Co^{3+}$$Co^{2+}$로 환원시켜 침출이 용이해졌기 때문으로 생각된다. 변수설험을 통하여 얻은 최적의 조건(광액농도 10g/l 반응온도 $75^{\circ}C$, 교반속도 400 rpm' 1.7 vol% $H_2O_2$)에서 폐리튬이온전지로부터 선별하고 열처리한 $LiCoO_2$ 분말을 침출 실험한 결과, Li과 Co의 침출율이 각각 99% 이상이었으며, 이는 충방전이 거듭되면서 양극활물질인 $LiCoO_2$이 화학적으로 활성화되었거나 Li의 탈착으로 겸정구조가 불안하기 때문으로 생각된다.

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Improving Electrochemical Properties of LiFePO4 by Doping with Gallium

  • Nguyen, Van Hiep;Park, Ju-Young;Gu, Hal-Bon
    • Transactions on Electrical and Electronic Materials
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    • 제15권6호
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    • pp.320-323
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    • 2014
  • Ga-doped $LiFePO_4$ cathode materials were synthesized using a hydrothermal method. The microstructural characteristics and electrochemical performances were systematically investigated using field emission scanning electron microscopy, high-resolution X-ray diffraction, energy dispersive X-ray spectroscopy, charge-discharge cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. Among the as-prepared samples, $LiFe_{0.96}Ga_{0.04}PO_4$ demonstrates the best electrochemical properties in terms of discharge capacity, electrochemical reversibility, and cycling performance with an initial discharge capacity of $125mAh\;g^{-1}$ and high lithium ion diffusion coefficient of $1.38{\times}10^{-14}cm^2s^{-1}$ (whereas for $LiFePO_4$, these were $113mAh\;g^{-1}$ and $8.09{\times}10^{-15}cm^2\;s^{-1}$, respectively). The improved electrochemical performance can be attributed to the facilitation of Li+ ion effective diffusion induced by $Ga^{3+}$ substitution.

소결조제 Li2CO3 첨가에 따른 저온소결(K0.5Na0.5)NbO3 세라믹스의 압전 및 유전 특성 (Piezoelectric and Dielectric Properties of Low Temperature Sintering (K0.5Na0.5)NbO3 Ceramics according to Sintering Aid Li2CO3)

  • 이일하;류주현
    • 한국전기전자재료학회논문지
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    • 제21권10호
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    • pp.906-910
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    • 2008
  • $(K_{0.5}Na_{0.5})NbO_3$ (NKN) ceramics doped with $Li_{2}CO_3$ as sintering aids were manufactured in order to develop the low temperature sintering ceramics for piezoelectric device. The sintering aids were proved to lower the sintering temperature of doped NKN ceramics due to the effect of $Na_{2}CO_{3}-Li_{2}CO_3$ liquid phase. All the specimens showed the orthorhombic phase without secondary phase. And also, the piezoelectric properties of specimens were improved with increasing $Li_{2}CO_3$ contents. At sintering temperature of $930^{\circ}C$, the density, electromechanical coupling factor (kp), mechanical quality factor (Qm) and dielectric constant(${\epsilon}_{\gamma}$), piezoelectric constant of 0.3 wt.% $Li_{2}CO_3$ added specimen showed the optimum values of $4.255 g/cm^3$, 0.37, 234, 309, 136 pC/N, respectively.

Carbon nanoballs: formation mechanism and electrochemical performance as an electrode material for the air cathode of a Li-air battery

  • Kang, Jun
    • Journal of Advanced Marine Engineering and Technology
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    • 제39권8호
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    • pp.838-842
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    • 2015
  • The Li-air battery is a promising candidate for the most energy-dense electrochemical power source because it has 5 to 10 times greater energy storage capacity than that of Li-ion batteries. However, the Li-air cell performance falls short of the theoretical estimate, primarily because the discharge terminates well before the pore volume of the air electrode is completely filled with lithium oxides. Therefore, the structure of carbon used in the air electrode is a critical factor that affects the performance of Li-air batteries. In a previous study, we reported a new class of carbon nanomaterial, named carbon nanoballs (CNBs), consisting of highly mesoporous spheres. Structural characterization revealed that the synthesized CNBs have excellent a meso-macro hierarchical pore structure, with an average diameter greater than 10 nm and a total pore volume more than $1.00cm^3g^{-1}$. In this study, CNBs are applied in an actual Li-air battery to evaluate the electrochemical performance. The formation mechanism and electrochemical performance of the CNBs are discussed in detail.

Development of a Dike Line Selection Method Using Multispectral Orthoimages and Topographic LiDAR Data Taken in the Nakdong River Basins

  • Choung, Yun Jae
    • 한국측량학회지
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    • 제33권3호
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    • pp.155-161
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    • 2015
  • Dike lines are important features for describing the detailed shapes of dikes and for detecting topographic changes on dike surfaces. Historically, dike lines have been generated using only the LiDAR data. This paper proposes a new methodology for selecting an appropriate dike line on various dike surfaces using the topographic LiDAR data and multispectral orthoimages taken in the Nakdong River basins. The fi rst baselines were generated from the given LiDAR data using the modified convex hull algorithm and smoothing spline function, and the second baselines were generated from the given orthoimages by the Canny operator. Next, one baseline was selected among the two baselines at 10m intervals by comparing their elevations, and the selected baseline at 10m interval was defined as the dike line segment. Finally, the selected dike line segments were connected to construct the 3D dike lines. The statistical results show that the dike lines generated using both the LiDAR data and multispectral orthoimages had the improved horizontal and vertical accuracies than the dike lines generated only using the LiDAR data on the various dike surfaces.

Effect of Counter Anions on Solid Electrolyte Interphase Formation on Graphite Electrodes in Propylene Carbonate-based Electrolyte Solutions

  • Song, Hee-Youb;Kim, Seong In;Nogales, Paul Maldonado;Jeong, Soon-Ki
    • Journal of Electrochemical Science and Technology
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    • 제10권1호
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    • pp.55-60
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    • 2019
  • Herein, the effect of counter anions on the formation of a solid electrolyte interphase (SEI) in a propylene carbonate (PC)-based electrolyte solution was investigated. Although the reversible capacities were different, reversible intercalation and de-intercalation of lithium ions occurred in the graphite negative electrode in the PC-based electrolyte solutions containing 1 M $LiClO_4$, $LiPF_6$, $LiBF_4$, and $LiCF_3SO_3$ at low temperature ($-15^{\circ}C$). This indicated that the surface films acted as an effective SEI to suppress further co-intercalation and decomposition reactions at low temperature. However, the SEIs formed at the low temperature were unstable in 1 M $LiPF_6$ and $LiBF_4/PC$ at room temperature ($25^{\circ}C$). On the other hand, increasing reversible capacity was confirmed in the case of $LiCF_3SO_3/PC$ at room temperature, because the SEI formed at the low temperature was still maintained. These results suggest that counter anions are an important factor to consider for the formation of effective SEIs in PC-based electrolyte solutions.

착체중합법을 이용한 LiMn1.5Ni0.5O4 분말합성 및 특성평가 (Synthesis and characterization of LiMn1.5Ni0.5O4 powders using polymerization complex method)

  • 신재호;김진호;황해진;김응수;조우석
    • 한국결정성장학회지
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    • 제22권4호
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    • pp.194-199
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    • 2012
  • 스피넬 구조로 이루어진 $LiMn_2O_4$에서 Mn의 일부분을 Ni로 치환한 $LiMn_{1.5}Ni_{0.5}O_4$은 4.7 V 전압 영역에서 높은 방전 용량 및 우수한 충 방전 사이클 특성을 가진다. 본 연구에서는 착체중합법을 이용하여 $LiMn_{1.5}Ni_{0.5}O_4$를 합성하였다. Citric acid : metal의 몰비(5 : 1, 10 : 1, 15 : 1, 30 : 1) 및 하소 온도($500{\sim}900^{\circ}C$) 변화에 따라 합성된 $LiMn_{1.5}Ni_{0.5}O_4$ 분말의 특성을 조사하였다. 합성된 분말의 XRD 분석을 통해 저온($500^{\circ}C$) 및 고온($900^{\circ}C$) 영역에서 모두 단일상인 $LiMn_{1.5}Ni_{0.5}O_4$ 결정상을 관찰할 수 있었고, 하소 온도가 증가함에 따라 결정화 및 결정자 크기도 함께 증가하였다. 합성된 $LiMn_{1.5}Ni_{0.5}O_4$ 분말의 형상 및 비표면적 분석 결과, 저온영역에서는 CA 몰비가 증가할수록 입자사이즈는 감소하고 비표면적은 증가하는 것을 확인할 수 있었다. 반면에 고온영역에서는 온도 증가에 따른 입자 성장에너지가 CA 몰비 증가에 따른 입자 사이즈 감소 및 비표면적 증가 효과를 감소시키는 것을 관찰하였다.

NCM계 리튬이온 배터리 양극재의 그라파이트 첨가 탄산화 배소와 수침출에 의한 Li 회수 (Lithium Recovery from NCM Lithium-ion Battery by Carbonation Roasting with Graphite Followed by Water Leaching)

  • 이소연;이대현;이소영;손호상
    • 자원리싸이클링
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    • 제31권4호
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    • pp.26-33
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    • 2022
  • 리튬이온배터리의 수요가 증가함에 따라 향후 발생할 폐리튬이온배터리 중의 유가금속 회수가 필요하다. 대량의 폐리튬이온배터리 리사이클링에는 건식제련이 적합하지만 Li이 슬래그나 분진으로 손실되는 문제점이 있다. 본 연구에서는 폐리튬이온배터리의 NCM계 양극재로부터 Li을 회수하기 위해 그라파이트 첨가에 따른 탄산화 배소와 수침출 거동에 대해 조사하였다. 그라파이트를 10 wt% 첨가 시, Ar 및 CO2 분위기에서 승온 중 약 850 K에서 급격한 무게 감소와 함께 CO 및 CO2 가스가 배출되었다. 급격한 무게 감소 후 NCM은 금속 산화물 및 순금속으로 분해되고 환원되었다. 따라서 블랙파우더(NCM+그라파이트)의 탄산화 배소에서는 NCM의 분해에 의해 O2가 발생하면서 Li2O, NiO 등의 산화물이 생성되고, 이어서 Li2O가 CO2와 반응하여 Li2CO3를 생성하며, NiO의 일부는 그라파이트에 의해 환원되어 금속 Ni을 생성한다. 그리고 탄산화 배소 후 수침출에 의해 약 99.95 % 순도의 Li2CO3를 최대 94.5 %까지 회수하였다.

Chemical Vapor Deposition of β-LiGaO2 Films on Si(100) Using a Novel Single Precursor

  • Sung, Myung M.;Kim, Chang G.;Kim, Yun-Soo
    • Bulletin of the Korean Chemical Society
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    • 제25권4호
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    • pp.480-484
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    • 2004
  • $LiGaO_2$ films have been grown on Si (100) substrates using a new single precursor $[Li(OCH_2CH_2OCH_3)_2-Ga(CH_3)_2]_2$ under high vacuum conditions $(5{\times}10^{-6}Torr)$. The $[Li(OCH_2CH_2OCH_3)_2Ga(CH_3)_2]_2$ was synthe-sized and characterized by using spectroscopic methods and single-crystal X-ray diffraction analysis. The chemical composition, crystalline structure, and morphology of the deposited films were investigated by X-ray photoelectron spectroscopy, X-ray diffraction, and scanning electron microscopy. The results show that polycrystalline $LiGaO_2$ films preferentially oriented in the [010] direction can be deposited on Si (100) at 500-550$^{\circ}C$ by metal organic chemical vapor deposition (MOCVD). The single precursor $[LiOCH_2CH_2OCH_3)_2-Ga(CH_3)_2]_2$ has been found suitable for chemical vapor deposition of $LiGaO_2$ thin films on Si substrates.

전고상박막전지를 위한 (Li,La)TiO3 고체전해질의 제조와 특성 (Lithium Lanthanum Titanate Solid Electrolyte for All-Solid-State Lithium Microbattery)

  • 안준구;윤순길
    • 한국전기전자재료학회논문지
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    • 제17권9호
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    • pp.930-935
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    • 2004
  • $({Li}_{0.5}0{La}_{0.5}){TiO}_3$ (LLTO) solid electrolyte was grown on LiCo{O}_2 (LCO) cathode films deposited on $Pt/Ti{O}-2/Si{O}_2/Si$ substrate using pulsed laser deposition for all-solid-state lithium microbattery. LLTO solid electrolyte exhibits an amorphous phase at various deposition temperatures. LLTO films deposited at 10$0^{\circ}C$ showed a clear interrace without any chemical reaction with LCO, and showed an initial discharge capacity of 50 $\mu$Ah/cm$^2$-$\mu$m and capacity retention of 90 % after 100 cycles with Li anode in 1mol$ LiCl{O}_4$ in propylene carbonate (PC). The increase of capacity retention in LLTO/LCO structure than LCO itself was attributed to the structural stability of LCO cathode films by the stacked LLTO. The cells of LLTO/LCO with LLTO grown at $100^{\circ}C$ showed a good cyclic property of 63.6 % after 300 cycles. An amorphous LLTO solid electrolyte is possible for application to solid electrolyte for all-solid-state lithium microbattery.