• 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).

• Korean Chemical Engineering Research
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• v.55 no.2
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• pp.242-246
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• 2017

The application of composite cathode materials including $LiFePO_4$ (lithium iron phosphate) of olivine crystal structure, which has high thermal stability, were investigated as alternatives for hybrid battery-capacitors with a $LiMn_2O_4$ (spinel crystal structure) cathode, which exhibits decreased performance at high temperatures due to Mn-dissolution. However, these composite cathode materials have been shown to have a reduction in capacity by conducting life cycle experiments in which a $LiFePO_4$/activated carbon cell was charged and discharged between 1.0 V and 2.3 V at two temperatures, $25^{\circ}C$ and $60^{\circ}C$, which caused a degradation of the anode due to the lowered voltage in the anode. To avoid the degradation of the anode, composite cathodes of $LiFePO_4/LiMn_2O_4$ (50:50 wt%), $LiFePO_4$/activated carbon (50:50 wt%) and $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (50:50 wt%) were prepared and the life cycle experiments were conducted on these cells. The composite cathode including $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ of layered crystal structure showed stable voltage behavior. The discharge capacity retention ratio of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was about twice as high as that of a $LiFePO_4/LiMn_2O_4$ cell at thermal stability experiment for a duration of 1,000 hours charged at 2.3 V and a temperature of $80^{\circ}C$.

• 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 $2.8\sim4.3V$.

• 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.

• Korean Journal of Materials Research
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• v.28 no.7
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• pp.371-375
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• 2018

The manganese-, nickel-, and aluminum-doped cobalt ferrite powders, $Mn_{0.2}Co_{0.8}Fe_2O_4$, $Ni_{0.2}Co_{0.8}Fe_2O_4$, and $Al_{0.2}CoFe_{1.8}O_4$, are fabricated by the sol-gel method, and the crystallographic and magnetic properties of the powders are studied in comparison with those of $CoFe_2O_4$. All the ferrite powders are nano-sized and have a single spinel structure with the lattice constant increasing in $Mn_{0.2}Co_{0.8}Fe_2O_4$ but decreasing in $Ni_{0.2}Co_{0.8}Fe_2O_4$ and $Al_{0.2}CoFe_{1.8}O_4$. All the $M{\ddot{o}}ssbauer$ spectra are fitted as a superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. The values of the magnetic hyperfine fields of $Ni_{0.2}Co_{0.8}Fe_2O_4$ are somewhat increased in the A and B sites, while those of $Mn_{0.2}Co_{0.8}Fe_2O_4$ and $Al_{0.2}CoFe_{1.8}O_4$ are decreased. The variation of $M{\ddot{o}}ssbauer$ parameters is explained using the cation distribution equation, superexchange interaction and particle size. The hysteresis curves of the ferrite powders reveal a typical soft ferrite pattern. The variation in the values of saturation magnetization and coercivity are explained in terms of the site distributions, particle sizes and the spin magnetic moments of the doped ions.

• Analytical Science and Technology
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• v.28 no.3
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• pp.182-186
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• 2015

In this study, the porous CuO/MnO₂ catalyst was prepared through the co-precipitation process from an aqueous solution of potassium permanganate (KMnO₄), manganese(II) acetate (Mn(CH₃COO)₂·4H₂O) and copper(II) acetate (Cu(CH₃COO)₂·H₂O). The phase change in MnO₂ was analyzed according to the reaction molar ratio of KMnO₄ to Mn(CH₃COO)₂. The reaction mole ratio of KMnO₄ to Mn(CH₃COO)₂·4H₂O was varied at 0.3:1, 0.6:1, and 1:1. The aqueous solution of Cu(CH₃COO)₂ was injected into a mixed solution of KMnO₄ and Mn(CH₃COO)₂ to 10~75 wt% relative to MnO₂. The Cu ion co-precipitates as CuO with MnO₂ in a highly dispersed state on MnO₂. The physicochemical property of the prepared CuO/MnO₂ was analyzed by using the TGA, DSC, XRD, SEM, and BET. The different phase types of MnO₂ were prepared according to the reaction mole ratio of KMnO₄ to Mn(CH₃COO)₂·4H₂O. The results confirmed that the porous CuO/MnO₂ catalyst with γ-phase MnO₂ was produced in the reaction mole ratio of KMnO₄ to Mn(CH₃COO)₂ as 0.6:1 at room temperature.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2541-2543
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• 2014

• Electrical & Electronic Materials
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• v.14 no.12
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• pp.7-10
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• 2001

Orthorhombic type LiCo$_{x}$Mn$_{1-x}$ O$_2$(0$\leq$x$\leq$0.14) oxides have been synthesized by hydrothermal treatment of (Co$_{x}$Mn$_{1-x}$ )$_3$O$_4$precursors and LiOH aqueous solution at 17$0^{\circ}C$. As-synthesized powders showed well-ordered $\beta$-MaMnO$_2$structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic LiCo$_{0.1}$Mn$_{0.9}$O$_2$, comparing to orthorhombic LiMnO$_2$./TEX>.EX>.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11b
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_{2}$(0 ${\times}$ 0.14) oxides have been synthesized by hydrothermal treatment of $(Co_{x}Mn_{1-x})_{3}O_{4}$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}-NaMnO_{2}$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_{2}$, comparing to orthorhombic $LiMnO_2$.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.11a
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• pp.7-10
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• 2001

Orthorhombic type $LiCo_{x}Mn_{1-x}O_2$ (0 x 0.14) oxides have been synthesized by hydrothermal treatment of ($Co_{x}Mn_{1-x}$)$_3O_4$ precursors and LiOH aqueous solution at $170^{\circ}C$. As-synthesized powders showed well-ordered ${\beta}$-$NaMnO_2$ structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic $LiCo_{0.1}Mn_{0.9}O_2$, comparing to orthorhombic $LiMnO_2$.