• Journal of the Korean Society of Safety
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• v.38 no.5
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• pp.8-14
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• 2023

Lithium ions can induce the thermal runaway phenomenon and lead to reignition due to electrical, mechanical, and environmental factors such as high temperature, smoke generation, explosions, or flames, which is extremely likely to create safety concerns. Therefore, one of the ways to improve the flame retardancy of the electrolyte is to use a flame-retardant additive. Comparing the associated characteristic value of existing substances with the required experimental value, it was found that these values were either considerably different or were not documented. It is vital to know a substance's combustion characteristic values, flash point, explosion limit, and autoignition temperature (AIT) as well as its combustion characteristics before using it. In this research, the flash point and AIT of materials were measured by mixing a highly volatile and flammable substance, diethyl carbonate (DEC), with flame-retardant dimethyl methylphosphonate (DMMP). The flash point of DEC, which is a pure substance, was 29℃, and that for DMMP was 65℃. Further, the lower explosion limit calculated using the measured flash point of DEC was 1.79 Vol.%, while that for DMMP was 0.79 Vol.%. The AIT was 410℃ and 390℃ for DEC and DMMP, respectively. In particular, since the AIT of DMMP has not been discussed in any previous study, it is necessary to ensure safety through experimental values. In this study, the experimental and regression analysis revealed that the average absolute deviation (ADD) for the flash point of the DEC+DMMP DEC+DMMP system is 0.58 sec and that the flash point tends to increase according to changes in the composition employed. It also revealed that the AAD for the AIT of the mixture was 3.17 sec and that the AIT tended to decrease and then increase based on changes in the composition.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.6
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• pp.1313-1318
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• 2006

The mechanism fur the surface film formation was studied by in situ Atomic Force Microscopy (AFM) observation of a highly oriented pyrolytic graphite (HOPG) basal plane surface during cyclic voltammetry at a slow scan-rate of 0.5 mV $s^{-1}$ in 1 moi $dm^{-3}$ (M) $LiPF_6$ dissolved in a mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). Decomposition of the electrolyte solution began at a potential around 2.15 V vs. $Li^+$/Li on step edges. In the potential range 0.95-0.8 V vs. $Li^+$/Li, flat areas (hill-like structures) and large swelling appeared on the surface. It is considered that these two features were formed by the intercalation of solvated lithium ions and their decomposition beneath the surface, respectively. At potentials more negative than 0.80 V vs. $Li^+$/Li, particle-like precipitates appeared on the basal plane surface. After the first cycle, the thickness of the precipitate layer was 30 nm. The precipitates were considered to be decomposition of the lithium salt ($LiPF_6$) and solvent molecules (EC and DEC), and to have an important role in suppressing further solvent decomposition on the basal plane.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.511-516
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• 2004

A Li$[Co_{0.17}Li_{0.28}Mn_{0.55}]O_2$ cathode compound was prepared by a simple combustion method. The X-ray diffraction pattern showed that this compound could be classified as ${\alpha} -NaFeO_2$ structure type with the lattice constants of a = 2.8405(9) ${\AA}$ and c = 14.228(4) ${\AA}$. According to XANES analysis, the oxidation state of Mn and Co ions in the compound were 4+ and 3+, respectively. During the first charge process, the irreversible voltage plateau at around 4.65 V was observed. The similar voltage-plateau was observed in the initial charge profile of other solid solution series between $Li_2MnO_3\;and\;LiMnO_2$ (M=Ni, Cr...). The first discharge capacity was 187 mAh/g and the second discharge capacity increased to 204 mAh/g. As the increase of cycling number, one smooth discharge profile was converted to two distinct sub-plateaus and the discharge capacity was slowly decreased. From the Co and Mn K-edge XANES spectra measured at different cyclic process, it can be concluded that irreversible transformation of phase is occurred during continuous cycling process.

• Korean Journal of Metals and Materials
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• v.46 no.3
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• pp.174-181
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• 2008

The stability of the cathode materials for Li secondary battery is an important factor for its cyclability. The present paper focuses on the structural stability of $LiNi_{0.5}Mn_{1.5}O_4$ during lithiation/delithiation of Li ions and compared to that of $LiMn_{2}O_4$. $LiMn_{2}O_4$ and $LiNi_{0.5}Mn_{1.5}O_4$ powders are synthesized using a solgel method and their structural and electrochemical properties are investigated by XRD, SEM, and charge-discharge tests. $Li_xMn_2O_4$ and $Li_xNi_{0.5}Mn_{1.5}O_4$(x = 0.9,0.5,0.1) specimens are obtained after charge/discharge tests by controlling the cut-off voltage for XRD and TEM investigation. The charge-discharge tests shows that initial capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is 125 mAh/g and that of LiMn2O4 is around 100 mAh/g. The capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is maintained 95% of its initial capacity whereas the capacity of $LiMn_{2}O_4$ is maintained 65% of its initial capacity.

• Journal of Electrochemical Science and Technology
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• v.12 no.4
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• pp.377-386
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• 2021

The Li-rich oxides are promising cathode materials due to their high energy density. However, characteristics such as low rate capability, unstable cyclic performance, and rapid capacity fading during cycling prevent their commercialization. These characteristics are mainly attributed to the phase instability of the host structure and undesirable side reactions at the cathode/electrolyte interface. To suppress the phase transition during cycling and interfacial side reactions with the reactive electrolyte, K (potassium) doping and Nb oxide coating were simultaneously introduced to a Li-rich oxide (Li_1.2Ni_0.13Co_0.13Mn_0.54O₂). The capacity and rate capability of the Li-rich oxide were significantly enhanced by K doping. Considering the X-ray diffraction (XRD) analysis, the interslab thickness of LiO₂ increased and cation mixing decreased due to K doping, which facilitated Li migration during cycling and resulted in enhanced capacity and rate capability. The K-doped Li-rich oxide also exhibited considerably improved cyclic performance, probably because the large K⁺ ions disturb the migration of the transition metals causing the phase transition and act as a pillar stabilizing the host structure during cycling. The Nb oxide coating also considerably enhanced the capacity and rate capability of the samples, indicating that the undesirable interfacial layer formed from the side reaction was a major resistance factor that reduced the capacity of the cathode. This result confirms that the introduction of K doping and Nb oxide coating is an effective approach to enhance the electrochemical performance of Li-rich oxides.

• Bulletin of the Korean Chemical Society
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• v.30 no.8
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• pp.1719-1723
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• 2009

The LiFeP$O_4$ powder was synthesized by using the solid state reaction method with Fe($C_2O_4){\cdot}2H_2O,\;(NH_4)_2HPO_4,\;Li_2CO_3$, and chitosan as a carbon precursor material for a cathode of a lithium-ion battery. The chitosan added LiFePO4 powder was calcined at 350 ${^{\circ}C}$ for 5 hours and then 800 ${^{\circ}C}$ for 12 hours for the calcination. Then we calcined again at 800 ${^{\circ}C}$ for 12 hours. We characterized the synthesized compounds via the crystallinity, the valence states of iron ions, and their shapes using TGA, XRD, SEM, TEM, and XPS. We found that the synthesized powders were carbon-coated using TEM images and the iron ion is substituted from 3+ to 2+ through XPS measurements. We observed voltage characteristics and initial charge-discharge characteristics according to the C rate in LiFeP$O_4$ batteries. The obtained initial specific capacity of the chitosan added LiFeP$O_4$ powder is 110 mAh/g, which is much larger than that of LiFeP$O_4$ only powder.

• Journal of the Korean Electrochemical Society
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• v.18 no.4
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• pp.143-149
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• 2015

Carbon-coated $Li_2MnSiO_4$ powders as the active materials for the cathode were synthesized by planetary ball milling and solid-state reaction, and their phase formation behavior and charge-discharge properties were investigated. Calcination temperature and atmosphere were controlled in order to obtain the ${\beta}-Li_2MnSiO_4$ phase, which was active electrochemically, and the carbon-coated $Li_2MnSiO_4$ active material powders with near single phase ${\beta}-Li_2MnSiO_4$ could be fabricated. The particles of the synthesized powders were secondary particles composed of primary ones of about 100 nm size. The carbon incorporation was essential to enable the Li ions to be inserted and extracted from $Li_2MnSiO_4$ active materials, and the initial capacity of 192 mAh/g could be obtained in the $Li_2MnSiO_4$ active materials with 4.8 wt% of carbon.

• Bulletin of the Korean Chemical Society
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• v.21 no.11
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• pp.1125-1132
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• 2000

The pH effect of the precursor solution on the preparation of $LiCoO_2$ by a solution phase reaction containing malonic acid was carried out. Layered $LiCoO_2$ powders were obtained with the precursors prepared at the different pHs (4, 7, and 9) and heat-treated at $700^{\circ}C(LiCoO_2-700)$ or $850^{\circ}C(LiCoO_2-850)$ in air. pHs of the media for precursor synthesis affects the charge/discharge and electrochemical properties of the $LiCoO_2electrodes.$ Upon irrespective of pH of the precursor media, X-ray diffraction spectra recorded for $LiCoO_2-850$ powder showed higher peak intensity ratio of I(003)/I(104) than that of $LiCoO_2-700$, since the better crystallization of the former crystallized better. However, $LiCoO_2$ synthesized at pH 4 displayed an abnormal higher intensity ratio of I(003)/I(104) than those synthesized at pH 7 and 9. The surface morphology of the $LiCoO_2-850$ powders was rougher and more irregular than that of $LiCoO_2-700$ made from the precursor synthesized at pH 7 and 9. The $LiCoO_2electrodes$ prepared with the precursors synthesized at pH 7 and 9 showed a better electrochemical and charge/discharge characteristics. From the AC impedance spectroscopic experiments for the electrode made from the precursor prepared in pH 7, the chemical diffusivity of Li ions (DLi+) in $Li0.58CoO_2determined$ was 2.7 ${\times}$10-8 $cm^2s-1$. A cell composed of the $LiCoO_2-700$ cathode prepared in pH 7 with Lithium metal anode reveals an initial discharge specific capacity of 119.8 mAhg-1 at a current density of 10.0 mAg-1 between 3.5 V and 4.3 V. The full-cell composed with $LiCoO_2-700$ cathode prepared in pH 7 and the Mesocarbon Pitch-based Carbon Fiber (MPCF) anode separated by a Cellgard 2400 membrane showed a good cycleability. In addition, it was operated over 100 charge/discharge cycles and displayed an average reversible capacity of nearly 130 mAhg-1.