• Ceramist
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• v.22 no.4
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• pp.402-416
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• 2019

The development of next-generation secondary batteries, including lithium-ion batteries (LIB), requires performance enhancements such as high energy/high power density, low cost, long life, and excellent safety. The discovery of new materials with such requirements is a challenging and time-consuming process with great difficulty. To pursue this challenging endeavor, it is pivotal to understand the structure and interface of electrode materials in a multiscale level at the atomic, molecular, macro-scale during charging / discharging. In this regard, various advanced material characterization tools, including the first-principle calculation, high-resolution electron microscopy, and synchrotron-based X-ray techniques, have been actively employed to understand the charge storage- and degradation-mechanisms of various electrode materials. In this article, we introduce and review recent advances in in-situ synchrotron-based x-ray techniques to study electrode materials for LIBs during thermal degradation and charging/discharging. We show that the fundamental understanding of the structure and interface of the battery materials gained through these advanced in-situ investigations provides valuable insight into designing next-generation electrode materials with significantly improved performance in terms of high energy/high power density, low cost, long life, and excellent safety.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.32 no.4
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• pp.341-348
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• 2019

This paper reports the microstructure and electrochemical properties of Si-Al-Fe ternary amorphous alloys prepared by rapid solidification as an anode for lithium secondary batteries. The microstructure was analyzed using XRD and HR-TEM with EDS mapping. In accordance with DSC analysis, annealing was performed to crystallize the active nano-Si in the amorphous alloy. Thus, nano-Si forms (~80 nm) embedded in the matrix alloy, such as $Fe_2Al_3Si_3$, $FeSi_2$, and $Fe_{0.42}Si_{2.67}$, were successfully synthesized. The electrode based on the Si-Al-Fe ternary alloy delivered an initial discharge capacity of approximately $700mAh^{g-1}$, and exhibited a high Coulombic efficiency of 99.0~99.6% from the $2^{nd}$ to $70^{th}$ cycles.

• Korean Journal of Materials Research
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• v.28 no.5
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• pp.273-278
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• 2018

Lithium-ion batteries have been considered the most important devices to power mobile or small-sized devices due to their high energy density. $LixCoO_2$ has been studied as a cathode material for the Li-ion battery. However, the limitation of its capacity impedes the development of high capacity cathode materials with Ni, Mn, etc. in them. The substitution of Mn and Ni for Co leads to the formation of solid solution phase $LiNi_xMn_yCo_{1-x-y}O_2$ (NMC, both x and y < 1), which shows better battery performance than unsubstituted $LiCoO_2$. However, despite a high discharge capacity in the Ni-rich compound (Ni > 0.8 in the metal site), poor cycle retention capability still remains to be overcome. In this study, aiming to improve the stability of the physical and chemical bonding, we investigate the stabilization effect of Ca in the Ni-rich layered compound $Li(Ni_{0.83}Co_{0.12}Mn_{0.05})O_2$, and then Ca is added to the modified secondary particles to lower the degree of cationic mixing of the final particles. For the optimization of the final grains added with Ca, the Ca content (x = 0, 2.5, 5.0, 10.0 at.%) versus Li is analyzed.

• Journal of the Korean Electrochemical Society
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• v.26 no.1
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• pp.11-18
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• 2023

As the use of lithium-ion secondary batteries is rapidly increasing due to the rapid growth of the electric vehicle market, the disposal and recycling of spent batteries after use has been raised as a serious problem. Since stored energy must be removed in order to recycle the spent batteries, an effective discharging process is required. In this study, graphite and NCM622 were used as active materials to manufacture coin-type half cells and full cells, and the electrochemical behavior occurring during overdischarge was analyzed. When the positive and negative electrodes are overdischarged respectively using a half-cell, a conversion reaction in which transition metal oxide is reduced to metal occurs first in the positive electrode, and a side reaction in which Cu, the current collector, is corroded following decomposition of the SEI film occurs in the negative electrode. In addition, a side reaction during overdischarge is difficult to occur because a large polarization at the initial stage is required. When the full cell is overdischarged, the cell reaches 0 V and the overdischarge ends with almost no side reaction due to this large polarization. However, if the full cell whose capacity is degraded due to the cycle is overdischarged, corrosion of the Cu current collector occurs in the negative electrode. Therefore, cycled cell requires an appropriate treatment process because its electrochemical behavior during overdischarge is different from that of a fresh cell.

• Proceedings of the KIEE Conference
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• 2005.07c
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• pp.1989-1991
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• 2005

Lithium titanium oxide as anode material for energy storage prepared by novel synthesis method. $Li_4Ti_5O_{12}$ based spinel-framework structures are of great interest material for lithium-ion batteries. We describe here $Li_4Ti_5O_{12}$ a zero-strain insertion material was prepared by novel sol-gel method and by high energy ball milling (HEBM) of precursor to from nanocrystalline phases. According to the X-ray diffraction and scanning electron microscopy analysis, uniformly distributed $Li_4Ti_5O_{12}$ particles with grain sizes of 100nm were synthesized. Lithium cells, consisting of $Li_4Ti_5O_{12}$ anode and lithium cathode showed the 173 mAh/g in the range of $1.0{\sim}3.0V$. Furthermore, the crystalline structure of $Li_4Ti_5O_{12}$ didn't transfer during the lithium intercalation and deintercalation process.

• 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.10 no.6
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• pp.9-14
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• 2001

A sulfuric acid leaching of $LiCoO_2$as cathodic active materials of lithium ion secondary batteries was investigated in terms of reaction variables. In the absence of a reducing agent, the extraction of cobalt was less than 40% in 2 M sulfuric acid at $75^{\circ}C$ instead of that of lithium could be almost 100% in the same conditions. To improve the Co extraction, hydrogen peroxide was used as a reducing agent in the range 2~20 vol%. When over 10vo1% hydrogen peroxide was added, the extractions of both metals were improved to about 95%. It seems to be due to the reduction of Co(III) to Co(II) that can be readily dissolved. The extractions of Co and Li were increased with increasing $H_2$$SO_4$concentration and temperature, and amount of hydrogen peroxide and with decreasing of pulp density. The optimum leaching conditions were determined at $2 M H_2$$SO_4$concentration, $75^{\circ}C$ operating temperature, 100 g/L. initial pulp density, 20 vol% $H_2$$O_2$addition and 30 min.

• Applied Chemistry for Engineering
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• v.31 no.1
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• pp.97-102
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• 2020

Recently, various degradation mechanisms of lithium secondary battery cathode materials have been revealed. As a result, many studies on overcoming the limitation of cathode materials and realizing new electrochemical properties by controlling the degradation mechanism have been reported. Li-rich layered oxide is one of the most promising cathode materials due to its high reversible capacity. However, the utilization of Li-rich layered oxide has been restricted, because it undergoes a unique atomic structure change during the cycle, in turn resulting in unwanted electrochemical degradations. To understand an atomic structure deterioration mechanism and suggest a research direction of Li-rich layered oxide, we deeply evaluated the atomic structure of 0.4Li₂MnO₃_0.6LiNi_1/3Co_1/3Mn_1/3O₂ Li-rich layered oxide during electrochemical cycles, by using an atomic-resolution analysis tool. During a charge process, Li-rich materials undergo a cation migration of transition metal ions from transition metal slab to lithium slab due to the structural instability from lithium vacancies. As a result, the partial structural degradation leads to discharge voltage drop, which is the biggest drawback of Li-rich materials.

• Proceedings of the KIEE Conference
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• 2007.07a
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• pp.1363-1364
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• 2007

The composites such as Sn-CNTs, $SnSb_{0.5}$-CNTs and $CoSb_3$-CNTs have attracted much attention in the past years owing to their good overall properties. In these samples, intermetallic compounds show high specific capacities. Recently, interest in metal oxides such as $Al_{2}O_{3}$, MgO and $TiO_2$ has been largely stimulated by the realization that they can improve the cycling stability of the Li-ion battery electrodes. The reversible capacity of the $TiO_2$/CNTs composite reaches 168 mAh $g^{-1}$ at the first cycle and remains almost constant during long-term cycling. In this study, a nanocomposite of $TiO_2$/CNTs was prepared by sol-gel method and its electrochemical properties as anode materials for Li-ion batteries were studied by galvanostatic cycling, cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS).

• Journal of the Korean Electrochemical Society
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• v.24 no.2
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• pp.28-33
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• 2021

Many researchers have increased the loading level of electrodes to improve the energy density of secondary batteries. In this study, high-loading NCM523 (LiNi_0.5Co_0.2Mn_0.3O₂) positive electrode is manufactured using a polytetrafluoroethylene (PTFE) binder, not the conventional polyvinylidene fluoride (PVdF) binder, which has been commonly used in lithium-ion batteries. Through the kneading process using PTFE suspension, not the conventional slurry process using PVdF solution in N-methyl-2-pyrrolidinone (NMP), thick electrodes with high loading are easily manufactured. When the PTFE and PVdF-based electrodes are prepared at a loading level of 5.0 mAh/cm², respectively, the PTFE-based electrode shows better cycle performance and rate capability than those of PVdF-based electrodes. The electrode manufactured by the kneading process using a PTFE binder has high electrode porosity due to insufficient roll-press, but the porosity can be lowered by high temperature roll-press over 120℃. However, there is no significant difference in cycle performance according to the roll press temperature. In addition, the cycle performance of the high loading electrode is slightly improved by increasing the content of the conductive material. Overall, the PTFE binder can improve the performance of the high loading electrode, but additional solutions will be needed.