• 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 Korean Magnetic Resonance Society Conference
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• 2002.08a
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• pp.85-85
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• 2002

Lithiated transition metal oxides such as LiMn2O4, Lil-xMnO$_2$, LiNiO$_2$, LiCoO$_2$, and their solid solution phases are used as cathode materials for lithium rechargeable batteries. We prepared the cathode materials using a novel eutectic self-mixing method without any artificial mixing procedures. This method provides an extraordinarily simple way to make the cathode materials, and it is possible to prepare at very low temperature such as 25$0^{\circ}C$. Furthermore, the cathode materials produced have discharge capacities that are much better than cathode materials prepared by previously reported synthetic methods. The spontaneous and homogeneous mixing is verified by $^{7}$ Li magic-angle-spinning (MAS) NMR spectroscopy.

• Journal of Electrochemical Science and Technology
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• v.7 no.4
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• pp.306-315
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• 2016

Amorphous vanadium titanates (aVTOs) are examined for use as a negative electrode in lithium-ion batteries. These amorphous mixed oxides are synthesized in nanosized particles (<100 nm) and flocculated to form secondary particles. The $V^{5+}$ ions in aVTO are found to occupy tetrahedral sites, whereas the $Ti^{4+}$ ions show fivefold coordination. Both are uniformly dispersed at the atomic scale in the amorphous oxide matrix, which has abundant structural defects. The first reversible capacity of an aVTO electrode ($295mAhg^{-1}$) is larger than that observed for a physically mixed electrode (1:2 $aV_2O_5$ | $aTiO_2$, $245mAhg^{-1}$). The discrepancy seems to be due to the unique four-coordinated $V^{5+}$ ions in aVTO, which either are more electron-accepting or generate more structural defects that serve as $Li^+$ storage sites. Coin-type Li/aVTO cells show a large irreversible capacity in the first cycle. When they are prepared under nitrogen (aVTO-N), the population of surface hydroxyl groups is greatly reduced. These groups irreversibly produce highly resistive inorganic compounds (LiOH and $Li_2O$), leading to increased irreversible capacity and electrode resistance. As a result, the material prepared under nitrogen shows higher Coulombic efficiency and rate capability.

• Journal of the Korean Ceramic Society
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• v.36 no.2
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• pp.172-177
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• 1999

Graphite and carbonaceous materials showed an excellent capability as a negative electrode in Li-ion batteries because Li-ion can be intercalated and de-intercalated reversibly within most carbonaceous materials of layered structure. Also, the electrochemical potential of Li-intercalated carbon anode is almost identical with that of Li metal. In the present study, mesocarbon microbeads(MCMB) were used as anode electrode and its properties of charge/discharge and interfacial reaction with electrolyte were studied by Potentiostat/Galvanostat test, FT-IR analysis, XRD and SEM. The passivation film of solid-state was formed as the interface between electrode and electrolyte as the cell reaction began and, once formed, became thicker with repeated charge/discharge process. Also, the relationship between the passivation film formed at the electrode interface and storage capacity was discussed.

• Korean Journal of Materials Research
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• v.14 no.8
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• pp.587-594
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• 2004

Three-dimensionally ordered macroporous (3DOM) structures of the $LiCoO_2$ electrode materials for Li secondary batteries were fabricated by using the close-packed arrays of PMMA spheres served as templates. In order to successfully fabricate the cathode materials with highly ordered array form, the metal citrates were applied to new precursors. The precursor/template composites were prepared by the infiltration with metal citrate precursors into the voids of template. By removing the PMMA templates, then, the inverse opal structures with the uniform pores of narrow size distribution were resulted. It was confirmed that the 3DOM $LiCoO_2$ material is to take a single phase of rocksalt (R3m) structure. In addition, 3DOM $LiNiO_2$ and $LiMn_{2}O_4$ cathode materials were fabricated using an identical preparation procedure. Also, the morphology of the 3DOM cathode materials calcined at $500^{\circ}C\;to\;700^{\circ}C$ was observed by scanning electron microscope.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.24 no.3
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• pp.94-98
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• 2014

$LiCoO_2$ thin film has received diverse attention as cathodes material of thin-film micro-batteries. In this study, $LiCoO_2$ thin films were synthesized on Au substrates by sol-gel spin coating method and an annealing process. Their structures were studied using X-ray diffraction and Raman Spectroscopy. The particle morphologies of these thin films were observed by Scaning electron microscope. From the results of X-ray diffractometry and Raman Spectroscopy analyses, it was found that as-grown films had the structure of spinel (LT-$LiCoO_2$) and layered-Rock-salt (HT-$LiCoO_2$) at $550^{\circ}C$ and $750^{\circ}C$ respectively. The annealed films at $650^{\circ}C$ were presumed to be the mixed state of these two types. Throlugh the scanning electron microscope, It was estimated that the particle size in as-grown films at $750^{\circ}C$, were larger crystilline particle than in those at the other lower temperature and well distributed in the film.

• Transactions of the Korean hydrogen and new energy society
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• v.13 no.3
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• pp.242-248
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• 2002

SnCo alloy powder prepared by high energy ball milling is examined as an anode material for lithium-ion batteries. As the ball-milling time increased, the crystallinity of SnCo decreased. XRD and TEM SADP showed that nanocrystalline and amorphous phase coexisted after 16 h ball-milling. As the crystallinity decreased, the cycleability increased. At first cycle, there are 4 plateau potentials. The observation of voltage plateau at about 0.68 V confirms the formation of Sn-Li alloy and Co metal. It is considered that The plateau potentials below 0.68 V were reaction between Li and Sn. The change of chemical diffusion coefficient showed that the structure of SnCo alloy abruptly changed at first cycle, and maintained after 2nd cycle.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.11a
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• pp.210-215
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• 2002

This thesis is contents on the crystal grown by the solide phase method at $925^{\circ}C$ with orthorhombic structure that $LiMnO_{2}$ active material synthesised with precurse $Mn_{2}O_{3}$ and $LiOH.H_{2}O$ material to get three voltage level. The porosity analysis of the grown crystal in secondary batteries $LiMnO_{2}$ thin film is $1.323E+02\AA$ of the average pore diameter of powder particles and its structure to be taken the pore diameter was prepared. Adding voltage area to get properties of charge and discharge of which experiment result of $LiMnO_{2}$ thin film area 2.2V~4.3V, current and scan speed were 0.1mAh/g and $0.2mV/cm^{2}$ respectively, and properties of the charge and discharge to be got optimum experiment condition parameter and density rate of Li for analyze that unit discharge capacity with metal properties is 87mAh/g was 96.9[ppm] at 670.784[nm] wavelength, and density rate of Mn analyzed 837[ppm] at 257.610[nm]. It can be estimated the quality of thin film that wrong cell reject from the bottle of electrolyte. The results of SEM and XRD were the same that of original researchers.

• Journal of the Korean Electrochemical Society
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• v.7 no.1
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• pp.1-8
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• 2004

This paper deals with the recent development of high-voltage cathode materials of mono- and di- metal ions substituted spinel $LiMn_2O_4$ for lithium batteries. $LiCu_xMn_{2-x}O_4(0{\leq}x{\leq}0.5)$ shows reversible intercalation/deintercalation in two potential regions, $3.9\~43\;and\;4.8-5.0V$ and stable electrochemical cycling behavior but with low capacity. $LiNi_{0.5}Mn_{1.5}O_4$ obtained by a sol-gel process delivers a capacity of 127mAh $g^{-1}$ on the first cycle and sustains a value of 124 mAh $g^{-1}$ even after the 60th cycle. The $Li_xCr_yMn_{2-y}O_4(0{\leq}x{\leq}0.5)$ solid-solutions exhibit enhanced specific capacity, larger average voltage, and improved cycling behaviors for low Cr content. $LiCr_yMn_{2-y}O_4$ presents a reversible Li deintercalation process at 4.9V, whose capacity is proportional to the Cr content in the range of $0.25{\leq}x{\leq}0.5$ and delivers higher capacities. $LiM_yCr_{0.5-y}Mn_{1.5}O_4(M=Fe\;or\;Al)$ shows that the capacity retention is lowered compared with lithium manganate. The cumulative capacities obtainable with Al-substitutted materials are less than those with Fe-substituted materials. $LiCr_xNi_{0.5-x}Mn_{1.5}O_4(x=0.1)$ delivers a high initial capacity of 1$152mAh\;g^{-1}$ with excellent cycleability.

• 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.