• Journal of the Korean Electrochemical Society
• /
• v.15 no.2
• /
• pp.95-100
• /
• 2012

$LiFePO_4$ is an attractive cathode material due to its low cost, good cyclability and safety. But it has low ionic conductivity and working voltage impose a limitation on its application for commercial products. In order to solve these problems, the iron($Fe^{2+}$)site in $LiFePO_4$ can be substituted with other transition metal ions such as $Mn^{2+}$ in pursuance of increase the working voltage. Also, reducing the size of electrode materials to nanometer scale can improve the power density because of a larger electrode-electrolyte contact area and shorter diffusion lengths for Li ions in crystals. Therefore, we chose electrospinning as a general method to prepare $Li[Fe_{0.9}Mn_{0.1}]PO_4$ to increase the surface area. Also, there have been very a few reports on the synthesis of cathode materials by electrospinning method for Lithium ion batteries. The morphology and nanostructure of the obtained $Li[Fe_{0.9}Mn_{0.1}]PO_4$ nanofibers were characterized using scanning electron microscopy(SEM). X-ray diffraction(XRD) measurements were also carried out in order to determine the structure of $Li[Fe_{0.9}Mn_{0.1}]PO_4$ nanofibers. Electrochemical properties of $Li[Fe_{0.9}Mn_{0.1}]PO_4$ were investigated with charge/discharge measurements, electrochemical impedance spectroscopy measurements(EIS).

• Journal of the Mineralogical Society of Korea
• /
• v.28 no.2
• /
• pp.127-133
• /
• 2015

Li-bearing muscovite is commonly found along with trioctahedral lepidolite in granitic pegmatites. Structurally, $Li^+$ ions can replace $K^+$ ions in the interlayer (Int) of muscovite or incorporate into vacancies of the dioctahedral sheet (Sub). However, detailed mechanism of the lithium incorporation into muscovite is challenging to investigate using experimental techniques alone. In the current study, density functional theory (DFT) has been applied to examine the crystal structure and energy variation when $Li^+$ resides in the interlayer or the octahedral sheet. Depending on the position of $Li^+$ (i.e., Int vs. Sub), DFT showed significant differences in the mica's structures such as lattice parameters, sheet thickness, interlayer separation, and OH angles with respect to the ab plane. DFT further showed that, in pure muscovite, $Li^+$ has a lower energy when it is located in Int than Sub. By contrast, in the case of $Fe^{2+}$ substitution into the octahedral sheet, $Li^+$ has a lower energy in Sub than in Int. These results imply that $Li^+$ incorporates into the Al octahedral sheets only when the octahedral sheets possess structural charges, suggesting cation substitution in the octahedral sheets plays an important role in the Li incorporation mechanism into muscovite. They can also explain the experimental observation about the positive relationship between $Fe^{2+}$ and $Li^+$ amounts in Li-bearing muscovite.

• Journal of the Korean Chemical Society
• /
• v.41 no.9
• /
• pp.488-494
• /
• 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.

• Proceedings of the Korea Crystallographic Association Conference
• /
• 2002.11a
• /
• pp.16-16
• /
• 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).

• Bulletin of the Korean Chemical Society
• /
• v.19 no.1
• /
• pp.39-44
• /
• 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 $4.6{\times}10^{-8}\; cm^2/sec$.

• Resources Recycling
• /
• v.31 no.1
• /
• pp.12-20
• /
• 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%.

• Bulletin of the Korean Chemical Society
• /
• v.27 no.9
• /
• pp.1310-1314
• /
• 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.

• Proceedings of the Materials Research Society of Korea Conference
• /
• 1994.11a
• /
• pp.79-80
• /
• 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.

• The Korean Journal of Ceramics
• /
• v.6 no.3
• /
• pp.272-275
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.11 no.6
• /
• pp.564-567
• /
• 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.