• Title/Summary/Keyword: Lithium ions

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Electrochemical Aspects of Lithium and Sodium Intercalation into Two Dimensional FeMo$O_4$Cl (리튬과 소듐이 층간삽입된 FeMo$O_4$Cl의 전기화학적 성질)

  • Chang, Soon Ho;Song, Seung Wan;Choy, Jin Ho
    • Journal of the Korean Chemical Society
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    • v.41 no.9
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    • pp.488-494
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    • 1997
  • Lithium and sodium ions have been intercalated into two dimensional structure of $FeMoO_4Cl$. The electronic localization and the large difference in unit cell parameter between the pristine material and the intercalates lead to the existence of large biphased domains. In the case of the lithium system, a narrow range of $Li_xFeMoO_4Cl$ ($0.95{\leq}x{\leq}1.06$) solid solution has been found around the $LiFeMoO_4Cl$ composition. The OCV curve fitting has been performed using Armand's model. The occurrence of several parts in the charge-discharge curve is related to the electronic and structural modifications of the material during the intercalation process.

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Synthesis and electrochemical properties of layered $Li[Ni_xCo_{1-2x}Mn_x]O_2$ materials for lithium secondary batteries prepared by mechanical alloying (기계적 합금법을 이용한 리튬 2차 전지용 층상 양극물질 $Li[Ni_xCo_{1-2x}Mn_x]O_2$ 의 합성 및 전기화학적 특성에 관한 연구)

  • 박상호;신선식;선양국
    • Proceedings of the Korea Crystallographic Association Conference
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    • 2002.11a
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    • pp.16-16
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    • 2002
  • The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).

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Cathodic Properties of $LiCoO_2$ Synthesized by a Sol-Gel Method for Lithium Ion Battery

  • 조봉준;정의덕;심윤보
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.39-44
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    • 1998
  • $LiCoO_2$ powder was synthesized in an aqueous solution by a sol-gel method and used as a cathode active material for a lithium ion rechargeable battery. The layered $LiCoO_2$ powders were prepared by igniting in air for 12 hrs at 600 ℃ $(600-LiCoO_2)$ and 850 ℃ $(850-LiCoO_2)$. The structure of the $LiCoO_2$ powder was assigned to the space group R bar 3 m (lattice parameters a=2.814 Å and c=14.04Å). The SEM pictures of $600-LiCoO_2$ revealed homogeneous and fine particles of about 1 μm in diameter. Cyclic voltammograms (CVs) of $600-LiCoO_2$ electrode displayed a set of redox peaks at 3.80/4.05 V due to the intercalation/deintercalation of the lithium ions into/out of the $LiCoO_2$ structure. CVs for the $850-LiCoO_2$ electrode had a major set of redox peaks at 3.88/4.13 V, and two small set of redox peaks at 4.18/4.42 V and 4.05/4.25 V due to phase transitions. The initial charge-discharge capacity was 156-132 mAh/g for the $600-LiCoO_2$ electrode and 158-131 mAh/g for the $850-LiCoO_2$ electrode at the current density of 0.2 mA/cm2. The cycleability of the cell consisting of the $600-LiCoO_2$ electrode was better than that of the $850-LiCoO_2$. The diffusion coefficient of the $Li^+$ ion in the $600-LiCoO_2$ electrode was calculated as $4.6{\times}10^{-8}\; cm^2/sec$.

A Modified Process for the Separation of Fe(III) and Cu(II) from the Sulfuric Acid Leaching Solution of Metallic Alloys of Reduction Smelted Spent Lithium-ion Batteries (폐리튬이온전지의 용융환원된 금속합금상의 황산침출액에서 철(III)과 구리(II)의 분리를 위한 공정 개선)

  • Nguyen, Thi Thu Huong;Tran, Thanh Tuan;Lee, Man Seung
    • Resources Recycling
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    • v.31 no.1
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    • pp.12-20
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    • 2022
  • The smelting reduction of spent lithium-ion batteries results in metallic alloys containing Co, Cu, Fe, Mn, Ni, and Si. A process to separate metal ions from the sulfuric acid leaching solution of these metallic alloys has been reported. In this process, ionic liquids are employed to separate Fe(III) and Cu(II). In this study, D2EHPA and Cyanex 301 were employed to replace these ionic liquids. Fe(III) and Cu(II) from the sulfate solution were sequentially extracted using 0.5 M D2EHPA with three stages of cross-current and 0.3 M Cyanex 301. The stripping of Fe(III) and Cu(II) from the loaded phases was performed using 50% (v/v) and 60% (v/v) aqua regia solutions, respectively. The mass balance results from this process indicated that the recovery and purity percentages of the metals were greater than 99%.

Effects of Sulfur Substitution on Chemical Bonding Nature and Electrochemical Performance of Layered LiMn0.9Cr0.1O2-xSx

  • Lim, Seung-Tae;Park, Dae-Hoon;Lee, Sun-Hee;Hwang, Seong-Ju;Yoon, Young-Soo;Kang, Seong-Gu
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1310-1314
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    • 2006
  • Sulfur-substituted $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$ $(0\;\leq\;x\;\leq\;0.1)$ layered oxides have been prepared by solid state reaction under inert atmosphere. From powder X-ray diffraction analyses, all the present lithium manganates were found to be crystallized with monoclinic-layered structure. Electrochemical measurements clearly demonstrated that, in comparison with the pristine $LiMn_{0.9}Cr_{0.1}O_2$, the sulfur-substituted derivatives exhibit smaller discharge capacities for the entire cycle range but the recovery of discharge capacity after the initial several cycles becomes faster upon sulfur substitution. The effect of the sulfur substitution on the chemical bonding nature of $LiMn_{0.9}Cr_{0.1}O_{2-x}S_x$has been investigated using X-ray absorption spectroscopic (XAS) analyses at Mn and Cr K-edges. According to Mn K-edge XAS results, the trivalent oxidation state of manganese ion remains unchanged before and after the substitution whereas the local structure around manganese ions becomes more distorted with increasing the substitution rate of sulfur. On the other hand, the replacement of oxygen with sulfur has negligible influence on the local atomic arrangement around chromium ions, which is surely due to the high octahedral stabilization energy of $Cr^{+III} $ ions. Based on the present experimental findings, we have suggested that the decrease of discharge capacity upon sulfur substitution is ascribable to the enhanced structural distortion of $MnO_6$ octahedra and/or to the formation of covalent Li-S bonds, and the accompanying improvement of cyclability would be related to the depression of Mn migration and/or to the pillaring effect of larger sulfur anion.

EFFECTS OF ISOELECTRONIC IMPURITIES ON THE LIGHT EMISSION OF THE THIN-FILM ELECTROLUMINESCENCT DEVICES (박막 EL소자의 광방사에 있어서 등전자 불순물의 효과)

  • 박연수;곽민기;김현근;손상호;이상윤;이상걸
    • Proceedings of the Materials Research Society of Korea Conference
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    • 1994.11a
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    • pp.79-80
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    • 1994
  • A systematic study on isoelectronic impurities in thin-film eletroluminescent devices (TFELD) has been made on the basis of the experimental analysis aimed at a survey for the blue-emitting materials. Codoping effects of isoelectronic impurities, such as oxygen(O), tellurium(Te), and lithium(Li), on the emissive characteristics of ZnS:Ce$^{3+}$ and ZnS:Tm$^{3+}$TFELD have been investigated by means of the X-ray diffraction studies, the Auger electron spectroscopy, the cathodoluminescent spectra, and the electroluminescent spectra. Experiment results reveal that oxygen codoping gives rise to an increase of the luminance, due to a suppression of the nonradiative energy transfer via sulfur vacancies Te codoping in ZnS:Ce$^{3+}$ TFELD result in a large change in the crystal field around Ce$^{3+}$ ions. Li codoping in ZnS:Tm$^{3+}$ TFELD causes the luminance to increase slightly, due to a lowering in the symmetry of Tm$^{3+}$ions. Likewise, the experimental results suggest strongly that an Auger-type enegy loss via lattece defects such an sulfur vacancies acts as a non-emissive in TFELD.ve in TFELD.

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Growth and Characterization of $K_3LiNb_6O_{17}$ Single Crystals

  • Tae Hoon Kim;Seong Hyun Kim;Min Su Jang;Jung Nam Kim;Ji Hyun Ro
    • The Korean Journal of Ceramics
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    • v.6 no.3
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    • pp.272-275
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    • 2000
  • Starting from the stoichiometric composition of $K_2$CO$_3$: Li$_2$CO$_3$: Nb$_2$O$_5$=3 : 2 : 5 with the mole ratio, $K_3$LiNb$_6$O$_17$ 17/ single crystals were grown using the Czochralski method. Although the starting melt composition corresponds to the $K_3$Li$_2$Nb$_5$O$_15$ crystals, the chemical composition of the as grown crystals appears to be $K_2.95$Li$_1.33$Nb$_6.17$O$_17$ or $K_2.60$Li$_1.17$Nb$_{5.44}$ 5.44/O$_{15}$ which relatively contain fewer Li ions than $K_3$Li$_2$Nb$_5$O$_15$ crystals. We investigated the influence of the deficiency of the Li ions in the tetragonal tungsten bronze structure through the measurements of DE loop, temperature dependent dielectric constant, differential thermal analysis and temperature dependent X-ray diffraction pattern.

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Structural and Magnetic Studies on Electrochemically Lithiated $PrBa_2Cu_3O_y$

  • Choy, Jin-Ho;Chun, Sung-Ho;Kang, Seong-Gu
    • Bulletin of the Korean Chemical Society
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    • v.11 no.6
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    • pp.564-567
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    • 1990
  • A lithiated compound $Li_{0.1}Pr^{3+}Ba_2Cu_3O_y$ has been successfully prepared by electrochemical method, which is achieved with a two electrode cell of the type: Metal(Li)/($Li^+\;,\;ClO_4^-$) + propylene carbonate/$PrBa_2Cu_3O_y$. All Pr ions in the lithiated compound are stabilized with a trivalent state as the other rare earths (Ⅲ) substituted in the 90K superconductor lattice ($Y_{1-x}Ln_x^-Ba_2Cu_3O_{7-{\delta}}$). Powder X-ray diffraction analysis shows that both compounds, $PrBa_2Cu_3O_y$ and $Li_{0.1}PrBa_2Cu_3O_y$ are isostructural with the 90 K superconductor, ($YBa_2Cu_3O_{7-{\delta}}$), nevertheless both of them are non-metallic and also non-superconducting down to 10 K. Magnetic susceptibility ${\chi}$ vs. temperature data indicate that Curie contribution from the magnetic ions (Pr and Cu) is weakened on the one hand, but on the other hand temperature-independent part of susceptibility ${\chi}_o$ increases depending upon the rate of lithium intercalation in $PrBa_2Cu_3O_y$ lattice.

Electrochemical Behaviors of Bi3+ Ions on Inert Tungsten or on Liquid Bi Pool in the Molten LiCl-KCl Eutectic

  • Kim, Beom Kyu;Park, Byung Gi
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.20 no.1
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    • pp.33-41
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    • 2022
  • Liquid Bi pool is a candidate electrode for an electrometallurgical process in the molten LiCl-KCl eutectic to treat the spent nuclear fuels from nuclear power plants. The electrochemical behavior of Bi3+ ions and the electrode reaction on liquid Bi pool were investigated with the cyclic voltammetry in an environment with or without BiCl3 in the molten LiCl-KCl eutectic. Experimental results showed that two redox reactions of Bi3+ on inert W electrode and the shift of cathodic peak potentials of Li+ and Bi3+ on liquid Bi pool electrode in molten LiCl-KCl eutectic. It is confirmed that the redox reaction of lithium with respect to the liquid Bi pool electrode would occur in a wide range of potentials in molten LiCl-KCl eutectic. The obtained data will be used to design the electrometallurgical process for treating actinide and lanthanide from the spent nuclear fuels and to understand the electrochemical reactions of actinide and lanthanide at liquid Bi pool electrode in the molten LiCl-KCl eutectic.

Analysis for Atomic Structural Deterioration and Electrochemical Properties of Li-rich Cathode Materials for Lithium Ion Batteries (리튬이차전지용 리튬과잉계 양극 산화물의 충방전 과정 중 원자 구조 열화 과정과 전기화학 특성에 대한 분석)

  • Park, Seohyeon;Oh, Pilgun
    • Applied Chemistry for Engineering
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    • v.31 no.1
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    • pp.97-102
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    • 2020
  • Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li2MnO3_0.6LiNi1/3Co1/3Mn1/3O2 Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.