• Journal of the Korean Electrochemical Society
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• v.17 no.4
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• pp.222-228
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• 2014

Ni-rich system $Li[Ni_{1-x-y}Co_xMn_y]O_2$ of lithium secondary battery cathode material keep a high discharge capacity. However, by the Ni content increases, there is a problem that the electrochemical properties and stability of the structure are reduced. In order to solve these problems, research for positive ion doping is performed. The one of the cathode material, barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01), was synthesized by the precursor, $Ni_{0.6}Co_{0.1}Mn_{0.3}(OH)_2$, from the co-precipitation method. The barium doped materials have studied the structural and electrochemical properties. The analysis of structural properties, results of X-ray diffraction analysis, and those results confirmed the change of the lattice from the binding energy in the structure by barium doping. Increased stability of the layered structure was observed by $I_{(006)}+I_{(102)}/I_{(101)}$(R-factor) ratio decrease. we expected that the electrochemical characteristics are improved. 23 mAh/g discharge capacity of barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01) electrode is higher than discharge capacity of $Li[Ni_{0.6}Co_{0.1}Mn_{0.3}]O_2$ due to decrease overvoltage. And, through the structural stability was confirmed that improved the cycle characteristics. We caused a reduction in charge transfer resistance between the electrolyte and the electrode was confirmed that the C-rate characteristics are improved.

• Journal of the Korean Electrochemical Society
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• v.2 no.3
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• pp.156-162
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• 1999

Various types of iron oxide based materials as a cathode of lithium secondary battery have been prepared and their electrochemical characteristics have been also observed. In order to understand the fundamental characteristics of iron oxide electrode, three kinds of iron oxides such as iron oxides formed by direct oxidation of iron plate or iron powders and FeOOH powders were tested with cyclic voltammetry. The oxidation and reduction peaks due to the reaction of intercalation and deintercalation were not observed for the iron oxide prepared with iron plate and FeOOH powders. In case of iron oxide prepared from iron powders, only one reduction peak was observed. A layered form of $LiFeO_2$ was synthesized directly from $FeCl_3\cdot6H_2O,\;NaOH\;and\;LiOH$ and LiOH by hydrothermal reaction. The effect of NaOH on the electrode performance was examined. When increasing NaOH, it provides the electrode with less discharge capacity and efficiency, however, decreasing rate of discharge capacity became smaller. $LiFeO_2$ synthesized with the molar ratio of $NaOH/FeCl_3/LiOH$, 2/1/7 showed the largest capacity, but the discharging efficiency was sharply decreased after 30 cycles.

• Journal of the Korean Electrochemical Society
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• v.19 no.3
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• pp.101-106
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• 2016

In this study, we prepared an ionic liquid composite solid polymer electrolyte (PEO-LiTFSI-$Pyr_{14}TFSI$) with poly(ethylen oxide), lithium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide by blending-cross linking process. Although the PEO-LiTFSI-$Pyr_{14}TFSI$ composite solid polymer electrolyte displayed a small peak at 4.4 V, it had high electrochemical oxidation stability up to 5.7 V. Ionic conductivity of the PEO-LiTFSI-$Pyr_{14}TFSI$ composite solid polymer electrolyte increased with increasing temperature from $10^{-6}S\;cm^{-1}$ at $30^{\circ}C$ to $10^{-4}S\;cm^{-1}$ at $70^{\circ}C$. To investigate the electrochemical properties, the PEO-LiTFSI-$Pyr_{14}TFSI$ composite solid polymer electrolyte assembled with $LiFePO_4$ cathode and Li-metal anode. At 0.1 C-rate, the cell delivered $40mAh\;g^{-1}$ for $30^{\circ}C$, $69.8mAh\;g^{-1}$ for $40^{\circ}C$ and $113mAh\;g^{-1}$ for $50^{\circ}C$, respectively. The PEO-LiTFSI-$Pyr_{14}TFSI$ solid polymer electrolyte exhibited good charge-discharge performance in Li/SPE/$LiFePO_4$ cells at $50^{\circ}C$.

• Journal of the Korean Electrochemical Society
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• v.15 no.4
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• pp.222-229
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• 2012

We studied the electrochemical phenomena and increase of capacity according to the polymer composite electrode of two different polymeric materials with different the voltage range and capacity. Polyaniline (PANI) with relatively high voltage and small capacity and poly [1,2] bis-thio[1,8]-naphthylidine (PTND) with slightly low voltage and large capacity were used as polymer composite electrode materials. After PTND was synthesized, PANI was synthesized on the surface of PTND. The synthesis and the fine structure were analyzed by FT-IR, XPS, FE-SEM, and FE-TEM. Charge/discharge capacity and cyclic voltammetry measurements were carried out for the electrochemical performance as a polymer cathode active material for lithium secondary batteries. The discharge capacities of PANI/PTND after 1,5, and 10 cycles at 1.3~4.0 V voltage range and room temperature 167 mAh/g, 90 mAh/g, and 81 mAh/g. When we compared with PANI (80, 67, and 62 mAh/g), the discharge capacity after 10 cycles was improved about 30%. After 50 cycles, the discharge capacity of PANI/PTND was 67 mAh/g.

• Korean Chemical Engineering Research
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• v.58 no.1
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• pp.52-58
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• 2020

Electrochemical characterization and thermal stability were investigated for MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ cathode. The ratio of MgF₂ was controlled by 0.5, 1, 3 wt%. Cyclic voltammetry, charge-discharge profiles, rate capability, cycle life were measured for electrochemical properties. DSC analysis was measured for thermal stability. The first discharge capacities of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were decreased at 0.1C-rate compared to pristine LiNi_0.8Co_0.15Al_0.05O₂. But the rate capability and cycle life of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ were improved at 2C-rate. In DSC analysis result, the exothermic temperature of MgF₂ coated LiNi_0.8Co_0.15Al_0.05O₂ was increased and peak height was decreased.

• Korean Journal of Materials Research
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• v.17 no.8
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• pp.447-451
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• 2007

We investigated the dependence of the various annealing conditions and thickness ($6\sim45nm$) of the Ti-doped $Al_2O_3$ coating on the electrochemical properties and the capacity fading of Ti-doped $Al_2O_3$ coated $LiCoO_2$ films. The Ti-doped-$Al_2O_3$-coating layer and the cathode films were deposited on $Al_2O_3$ plate substrates by RF-magnetron sputter. Microstructural and electrochemical properties of Ti-doped-$Al_2O_3$-coated $LiCoO_2$ films were investigated by transmission electron microscopy (TEM) and a dc four-point probe method, respectively. The cycling performance of Ti-doped $Al_2O_3$ coated $LiCoO_2$ film was improved at higher cut-off voltage. But it has different electrochemical properties with various annealing conditions. They were related on the microstructure, surface morphology and the interface condition. Suppression of Li-ion migration is dominant at the coating thickness >24.nm during charge/discharge processes. It is due to the electrochemically passive nature of the Ti-doped $Al_2O_3$ films. The sample be made up of Ti-doped $Al_2O_3$ coated on annealed $LiCoO_2$ film with additional annealing at $400^{\circ}C$ had good adhesion between coating layer and cathode films. This sample showed the best capacity retention of $\sim92%$ with a charge cut off of 4.5 V after 50 cycles. The Ti-doped $Al_2O_3$ film was an amorphous phase and it has a higher electrical conductivity than that of the $Al_2O_3$ film. Therefore, the Ti-doped $Al_2O_3$ coated improved the cycle performance and the capacity retention at high voltage (4.5 V) of $LiCoO_2$ films.

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.774-780
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• 1998

For the stabilization of the spinel structured $LiMn_2O_4$, a fraction of manganese was substituted with various metals such as Mg, Fe, V, W, Cr, Mo with Mn that had a similar ionic radii ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$). The $LiM_xMn_{2-x}O_4$ showed a substantial improvement as lower capacity loss than that of the spinel structured $LiMn_2O_4$ when it was used as a cathode material. And with the partial substitution, the chemical diffusion coefficient for $LiMg_{0.05}Mn_{1.9}O_4$ and $LiCr_{0.1}Mn_{1.9}O_4$ was increased by and order of magnitude compared to that of the $LiMn_2O_4$ with spinel structure. The results showed that significant improvement can be made on the electrochemical characteristics as the structure of the $LiMn_2O_4$ electrode material was stabilized by the partial substitution.

• Journal of the Mineralogical Society of Korea
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• v.16 no.3
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• pp.223-232
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• 2003

The co-precipitation method is applied to synthesize the cathode material Li[L $i_{x}$M $n_{1-x-y}$C $r_{y}$ ] $O_2$ for lithium rechargeable batteries at $650^{\circ}C$ (CR650) and 8$50^{\circ}C$ (CR850), respectively. Rietveld indices indicate that $R_{wp}$ with respect to $R_{exp}$ ( $R_{wp}$/ $R_{exp}$) are 9.2%/10.1% for CR650 and 15.9%/9.76% for CR850, respectively. $R_{B}$ and S (GofF) shows 10.9%, 8.54% and 1.9, 1.6, respectively. Rietveld structure refinement reveals that layer structure of LiMn $O_2$ (R3m) coexists with lower symmetry of Li[L $i_{1}$3/M $n_{2}$3/] $O_2$ (C2/c) due to superlattice ordering of Li and Mn in metal-transition containing layers. Unit-cell parameters are calculated as a=2.8520(2)$\AA$, c=14.248(2)$\AA$, V=100.40(l)$\AA^3$ for CR650, and a=2.8504(1)$\AA$, c=14.2371(7)$\AA$, V=100.179(8)$\AA^3$ for CR850. Final chemistry is obtained as Li[L $i_{0.35}$M $n_{0.56}$C $r_{0.09}$] $O_2$ (CR650) and Li[L $i_{0.27}$M $n_{0.61}$C $r_{0.13}$] $O_2$ (CR850), respectively.y...y..vely.y...y..

• Journal of the Korean Electrochemical Society
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• v.20 no.4
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• pp.67-74
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• 2017

Layered Ni-rich NCM cathode materials $Li[Ni_xCo_{(1-x)/2}Mn_{(1-x)/2}]O_2$ ($x{\geq}0.6$) have advantages of high energy density and cost competitive over $LiCoO_2$. The discharge capacity of NCM increases proportionally to the Ni contents. However, there is a problem that it is difficult to realize the stable electrochemical performance due to cation mixing. In this study, synthesis conditions for the layered Ni-rich NCMs are investigated to achieve deliver the ones having good electrochemical performances. Synthesis parameters are atmosphere, lithium source, synthesis time, synthesis temperature and Li/M (M=transition metal) ratio. The degree of cation mixing gets worse as the Ni content is increased from $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ (NCM6) to $Li[Ni_{0.8}Co_{0.1}Mn_{0.1}]O_2$ (NCM8). It is confirmed that higher level of cation mixing affects negatively on the electrochemical performance of NCMs. Optimum synthesis conditions are explored for NCMx (x=6, 7, 8) in order to reduce the cation mixing. Under optimized conditions for three representative NCMx, a high initial discharge capacity and a good cycle life are obtained for $180mAh{\cdot}g^{-1}$, 96.2% (50 cycle) in NCM6, $187mAh{\cdot}g^{-1}$, 94.7% (50 cycle) in NCM7, and $201mAh{\cdot}g^{-1}$, 92.7% (50 cycle) in NCM8, respectively.

• Applied Chemistry for Engineering
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• v.23 no.2
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• pp.131-137
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• 2012

Polyaniline (PANI) and polypyrrole (Ppy) hollow sphere structures with controlled shell thicknesses can be easily synthesized than those of using a layer-by-layer method for cathode active material of lithium-ion batteries. Polystyrene (PS) core was synthesized by emulsion polymerization using an anion surfactant. The shell thicknesses of PANI and Ppy were controlled by amounts of aniline and pyrrole monomers. PS was removed by an organic solution. This structure increased in contact with an electrolyte and a specific capacity in lithium-ion batteries. But polymers have disadvantages such as the difficult control of molecular weights and low densities. These disadvantages were completed by controlled shell thicknesses. The amount of aniline monomer increased from 1.2, 2.4, 3.6, 4.8 to 6.0 mL, and the shell thicknesses were 30.2, 38.0, 42.2, 48.2, and 52.4 nm, respectively. And the amount of pyrrole monomer was 0.6, 1.2, 2.4 and 3.6 mL, the shell thicknesses were 16.0, 22.0, 27.0 and 34.0 nm, respectively. In the cathode materials with controlled shell thicknesses, shell thicknesses of the PANI hollow spheres were 30.2, 42.2, and 52.4 nm, and discharge specific capacities of after 10 cycle were ~18, ~29, and ~62 mAh/g, respectively. The shell thicknesses of the Ppy hollow spheres were 16.0, 22.0, 27.0 and 34.0 nm, and discharge specific capacities of after 15 cycle were ~15, ~36, ~56, and ~77 mAh/g, respectively. Thus, shell thicknesses of PANI and Ppy increased, the specific capacities increased.