• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.06a
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• pp.294-295
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• 2007

$LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ material was surface modified with Zr-phosphate. Scanning electron microscope, energy dispersive spectroscopy and electrochemical studies indicate that surface modification improve the rate capability. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode.

• Journal of the Korean Ceramic Society
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• v.42 no.9 s.280
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• pp.602-606
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• 2005

[ $LiCoO_{2}$ ] is the most common cathode electrode materials in Lithium-ion batteries. $LiCo_{0.97}Mg_{0.03}O_2$ was synthesized by the solid-state reaction method. We investigated crystal structures, electrical conductivities and electrochemical properties. The crystal structure of $LiCo_{0.97}Mg_{0.03}O_2$ was analyzed by X-ray powder diffraction and Rietveld refinement. The material showed a single phase of a layered structure with the space group R-3m. The lattice parameter(a, c) of $LiCo_{0.97}Mg_{0.03}O_2$ was larger than that of $LiCoO_2$. The electrical conductivity of sintered samples was measured by the Van der Pauw method. The electrical conductivities of $LiCoO_2$ and $LiCo_{0.97}Mg_{0.03}O_2$ were $2.11{\times}10^{-4}\;S/cm$ and $2.41{\times}10^{-1}\;S/cm$ at room temperature, respectively. On the basis of the Hall effect analysis, the increase in electrical conductivities of $LiCo_{0.97}Mg_{0.03}O_2$ is believed due to the increased carrier concentrations, while the carrier mobility was almost invariant. The electrochemical performance was investigated by coin cell test. $LiCo_{0.97}Mg_{0.03}O_2$ showed improved cycling performance as compared with $LiCoO_2$.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2603-2607
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• 2009

$LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ (x = 0, 0.1, 1/6, 1.2, 0.3) were synthesized by the solid-state reaction method. The crystal structure was analyzed by X-ray powder diffraction and Rietveld refinement. $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ samples give single phases of hexagonal layered structures with a space group of R-3m for x = 0.1, 1/6, 0.2, and 0.3. The lattice constants of a and c-axis were decreased with the increase in Co contents in samples. The thickness of MO2 slab was decreased and inter-slab distance was increased with the increase in Co contents in $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$. According to XPS analysis, the valence states of Mn, Co, and Ni in the sample are mainly +4, +3, and +3, respectively. The discharge capacity of 202 mAh/g at 0.1C-rate in the potential range of 4.7 - 3.0 V was obtained in $LiNi_{0.3}Co_{0.4}Mn_{0.3}O_2$ sample, and $LiNi_{0.4}Co_{0.2}Mn_{0.4}O_2$ gives excellent cycle performance in the same potential range.

• Resources Recycling
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• v.14 no.6 s.68
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• pp.37-43
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• 2005

[ $LiCoO_{2}$ ] nanoparticles were synthesized from leach liquor of lithium ion battery waste using flame spray pyrolysis. Electrode Materials containing lithium and cobalt could be concentrated with thermal and mechanical treatment. After dissolution of used cathode materials of the lithium battery with nitric acid, the molar ratio of Li/Co in the leach liquor was adjusted at 1.0 by adding a fresh $LiNO_{3}$ solution. The nanoparticles synthesized by the flame spray pyrolysis showed clear crystallinity and were nearly spherical, and their average primary particle diameters ranged from 11 to 35 nm. The average particle diameter increased with an increase in the molar concentration of the precursor. Raising the maximum flame temperature by controlling the gas flow rates also led to an increase in the average diameter of the particles. The $LiCoO_{2}$ powder was proved to have good characteristics as cathode active materials in charge/discharge capacity and cyclic performance.

• Journal of the Korean Ceramic Society
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• v.40 no.6
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• pp.507-512
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• 2003

The LiN $i_{l-y}$ $Co_{y}$ $O_2$ samples were synthesized at 80$0^{\circ}C$ and 85$0^{\circ}C$, by the solid-state reaction method, from the various starting materials LiOH, L $i_2$C $O_3$, NiO, NiC $O_3$, $Co_3$ $O_4$, CoC $O_3$, and their electrochemical properties are investigated. The LiN $i_{l-y}$ $Co_{y}$ $O_2$ pre-pared from L $i_2$C $O_3$, NiO, and $Co_3$ $O_4$ exhibited the $\alpha$-NaFe $O_2$ structure of the rhombohedral system (space group; R3m). As the Co content increased, the lattice parameters a and c decreased. The reason is that the radius of Co ion is smaller than that of Ni ion. The increase in da shows that two-dimensional structure develops better as the Co content increases. The LiN $i_{0.7}$ $Co_{03}$. $O_2$［HOO(800,0.3)] synthesized at 80$0^{\circ}C$from LiOH, NiO, and $Co_3$ $O_4$ exhibited the largest first discharge capacity 162 mAh/g. The size of particles increases roughly as the valve of y increases. The samples with the larger particles have the larger first discharge capacities. The cycling performances of the samples with the first discharge capacity larger than 150 mAh/g were investigated. The LiN $i_{0.9}$ $Co_{0.1}$ $O_2$［COO(850,0.1)］ synthesized at 85$0^{\circ}C$ from L $i_2$C $O_3$, NiO, and $Co_3$ $O_4$ showed an excellent cycling performance. The sample with the larger first discharge capacity will be under the more severe lattice destruction, due to the expansion and contraction of the lattice during intercalation and deintercalation, than the sample with the smaller first discharge capacity. As the first discharge capacity increases, the capacity fading rate thus increases.increases.s.s.s.

• Transactions on Electrical and Electronic Materials
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• v.7 no.2
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• pp.76-80
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• 2006

Well-defined orthorhombic $LiMnO_2\;and\;LiCo_{0.1}Mn_{0.9}O_2$ were synthesized by a solid-state reaction and quenching process. X-ray diffraction (XRD) results revealed that the as-synthesized powders showed an orthorhombic phase of a space group with Pmnm. The $Li/LiMnO_2\;and\;Li/LiCo_{0.1}Mn_{0.9}O_2$ cells were constituted and cycled galvanostatically in the voltage range of 2.0-4.3 V vs. $Li/Li^+$ at a current density of $0.5\;mA\;cm^{-2}$ at room temperature and $50^{\circ}C$, respectively. The results demonstrated that the highest specific capacity of $Li/LiMnO_2$ cells at room temperature and $50^{\circ}C$ was 95 and $155\;mAh\;g^{-1}$, respectively. As for $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells, the highest specific capacity at room temperature and $50^{\circ}C$ was 160 and $250\;mAh\;g^{-l}$, respectively. It could be seen that the performance of $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells was better than that of $Li/LiMnO_2$ cells.

• Proceedings of the Materials Research Society of Korea Conference
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• 2003.11a
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• pp.124-124
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• 2003

To improve the electrochemical properties of thin-film LiCoO$_2$ cathodes, metal oxides were coated on the LiCoO$_2$ thin films using f sputtering. Galvanostatic charge-discharge experiments showed the enhanced cycling behaviors in the metal-oxide coated LiCoO$_2$ thin films than the uncoated ones. These results are because the metal-oxide coating layer suppresses the degradation of Li-diffusion kinetics during cycling, which is related to the protection of cathode surface from the electrolytes [l-3]. The variation in the metal-oxide coating thickness ranging from 10 to 300 nm did not affect the electrochemical properties. Changes of lattice constants in the coated and bare LiCoO$_2$ thin films at different charged states will also be discussed.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• Journal of the Korean Electrochemical Society
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• v.16 no.2
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• pp.59-64
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• 2013

Using $Na_2CO_3$ and $MeSO_4$ (Me = Ni, Co and Mn) as starting materials, the precursor of $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ has been synthesized by carbonate co-precipitation. The precursor was mixed with $Li_2CO_3$, and calcined at 750, 850, and$950^{\circ}C$ in air. Effect of calcinations temperature on characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ cathode materials was investigated. The structure and characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ were determined by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and electrochemical measurements. The X-ray diffraction (XRD) results show that the intensity ratio of $I_{(003)}/I_{(104)}$ increased and the R-factor ratio decreased with the increase of calcinations temperature. And Scanning electron microscopy (SEM) result show that the primary particle size increased. Especially, the $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ calcined at $950^{\circ}C$ for 24 H shows excellent electrochemical performances with reversible specific capacity of $165.3mAhg^{-1}$ [cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] and good capacity retention of 95.4% after 50th charge/discharge cycles[cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)].

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.7
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• pp.650-654
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• 2006

[ $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ ] cathode material was synthesized by a mixed hydroxide method. Structural characterization was carried out using X-ray diffraction studies. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. DSC (Differential scanning calorimetry) data showed that exothermic reactions of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ charged to 4.3 V versus Li started at high temperatures$(280\sim390^{\circ}C)$. The cell of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ mixed cathode delivered a discharge capacity of 150 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of 134 mAh/g was obtained at a 2 C rate. The reversible capacity after 100th cycles was 126 mAh/g when a cell was cycled at a current rate of 0.5 C in $2.8\sim4.3V$.