• Journal of the Korean Ceramic Society
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• v.37 no.5
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• pp.466-472
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• 2000

As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

• Journal of the Korean Electrochemical Society
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• v.8 no.4
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• pp.172-176
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• 2005

Recently, many researches on the high-voltage 5 V class cathode material have focused on $LiNi_{0.5}Mn_{1.5}O_4$, where $Mn^{3+}$ in the existing $LiMn_2O_4 (Li[Mn^{3+}][Mn^{4+}]O_4)$ is replaced by $Ni^{2+}(Li[Ni^{2+}]_{0.5}[Mn^{4+}]_{1.5}O_4)$ in order to utilize $Ni^{2+}/Ni^{4+}$ redox reaction in the 5V region. The partial substitution of Mn in $LiMn_2O_4$ for other transition metal element, $LiM_yMn_{1-y}O_4$(M=Cr, Al, Ni, Fe, Co, Cu, Ga etc) is known as a good solution to overcome the problems associated with $LiMn_2O_4$ like the gradual capacity fading. In this study, we synthesized $LiNi_{0.5}Mn_{1.5}O_4$ through a mechanochemical process and investigated its morphological, crystallographic and electrochemical characteristics. The results showed that 4 V peaks had been found in the cyclic volammograms of the synthesized powders due to the existence of $Mn^{3+}$ from the incomplete substitution of $Ni^{2+}$ for $Mn^{3+}$ implying that the mechanochemical activation alone was not good enough to synthesize an exact stoichiometric compound of $LiNi_{0.5}Mn_{1.5}O_4$. The synthetic condition of mechanochemical process, such as type of starting materials, ball-mill and calcination condition was optimized for the best electrochemical performance.

• Journal of Powder Materials
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• v.25 no.4
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• pp.296-301
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• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.22 no.4
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• pp.194-199
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• 2012

The $LiMn_{1.5}Ni_{0.5}O_4$, substituting a part of Mn with Ni in the $LiMn_2O_4$, the spinel structure has good charge-discharge cycle stability and high discharge capacity at 4.7 V. In this study $LiMn_{1.5}Ni_{0.5}O_4$ powders were synthesized by polymerization complex method. The effect on the characteristics of synthesized $LiMn_{1.5}Ni_{0.5}O_4$ powders was studied with citric acid (CA) : metal ion (ME) molar ratio (5 : 1, 10 : 1, 15 : 1, 30 : 1) and calcination temperature ($500{\sim}900^{\circ}C$). Single phase of $LiMn_{1.5}Ni_{0.5}O_4$ was observed from XRD analysis on the powders calcined at low ($500^{\circ}C$) and high temperatures ($900^{\circ}C$). The crystalline size and crystallinity increased with calcination temperature. At low calcination temperature the particle size decreased and specific surface area increased as the CA molar ratio increased. On the other hand, high particle growth rate at high calcination temperature interfered the particle size reduction and specific surface area increase induced by the increase of CA molar ratio.

• Journal of the Korean Ceramic Society
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• v.41 no.10 s.269
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• pp.735-741
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• 2004

$LiMn_{1.92}Co_{0.08}O_4$ and $LiNi_{0.7}Co_{0.3}O_2$ synthesized by a simplified combustion method had good electrochemical properties. Mixtures $LiMn_{1.92}Co_{0.08}O_4$-x wt$\%$ $LiNi_{0.7}Co_{0.3}O_2$ (x=9, 23, 33, 41, and 47) were prepared by milling for 30 min and their electrochemical properties were investigated. The electrode with x=9 had a relatively large first discharge capacity (109.9 mAh/g at 0.1 C) and good cycling performance. The decrease in the discharge capacity of the mixture electrodes with cycling is considered to result mainly from the degradation of $LiNi_{0.7}Co_{0.3}O_2$, caused by coating of $LiNi_{0.7}Co_{0.3}O_2$ with Mn dissolved from $LiMn_{1.92}Co_{0.08}O_4$.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.29 no.5
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• pp.298-302
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• 2016

In this work, $LiMn_2O_4$ and $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode materials are mixed by some specific ratios to enhance the practical capacity, energy density and cycle performance of battery. At present, the most used cathode material in lithium ion batteries for EVs is spinel structure-type $LiMn_2O_4$. $LiMn_2O_4$ has advantages of high average voltage, excellent safety, environmental friendliness, and low cost. However, due to the low rechargeable capacity (120 mAh/g), it can not meet the requirement of high energy density for the EVs, resulting in limiting its development. The battery of $LiMn_2O_4-LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ (50:50 wt%) mixed cathode delivers a energy density of 483.5 mWh/g at a current rate of 1.0 C. The accumulated capacity from $1^{st}$ to 150th cycles was 18.1 Ah/g when the battery is cycled at a current rate of 1.0 C in voltage range of 3.2~4.3 V.

• 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).

• Journal of the Korean Ceramic Society
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• v.55 no.1
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• pp.21-35
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• 2018

Spinel $LiNi_{0.5}Mn_{1.5}O_4$ has received great attention as one of the most outstanding cathode materials for Li-ion batteries (LIBs) because of its high energy density resulting from the operating voltage of ~ 4.7 V (vs. $Li^+/Li$) based on the $Ni^{2+}/Ni^{4+}$ redox reaction. However, $LiNi_{0.5}Mn_{1.5}O_4$ is known to suffer from undesirable side reactions with the electrolyte at high voltage as well as Mn dissolution from the structure. These issues prevent the realization of the optimal electrochemical performance of $LiNi_{0.5}Mn_{1.5}O_4$. Extensive research has been conducted to overcome these issues. This review presents an overview of the various surface-modification methods available to improve the electrochemical properties of $LiNi_{0.5}Mn_{1.5}O_4$ and provides perspectives on further research aimed at the application of $LiNi_{0.5}Mn_{1.5}O_4$ as a cathode material in commercialized LIBs.

• Journal of the Korean Electrochemical Society
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• v.16 no.3
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• pp.162-168
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• 2013

$Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) nano-composite is a promising cathode material for xEV application due to its high theoretic capacity. However high voltage operating system of $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn) has worked as a hurdle in its application because of the inherent demerits, such as cycle life degradation and gas evolution. In order to enhance cell performance of $Li_2MnO_3-LiMO_2$(M=Ni, Co, Mn)/graphite cell, we examined electrolyte mainly composed of FEC, fluroalkyl ether and $LiPF_6$ (F-based EL). F-based EL showed much better discharging retention ratio than 1.3 M $LiPF_6$ EC/EMC/DMC (3/4/3, v/v/v) (STD). Furthermore gas evolution, especially CO and $CO_2$ during $60^{\circ}C$ storage for 30 days was dramatically reduced owing to thermal stable SEI formation effect of F-based EL.

• Journal of the Korean Electrochemical Society
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• v.11 no.3
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• pp.197-210
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• 2008

The cathode materials for lithium ion battery have been developed in accordance with the battery performance. $LiCoO_2$ initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of $LiCoO_2$. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are $LiNi_{1-x}{M_xO_2}$, $Li[Ni_{x}Mn_{y}Co_{z}]O_{2}$, $Li[{Ni}_{1/2}{Mn}_{1/2}]O_{2}$. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. ${LiMn}_{2}{O}_{4}$ and $LiFePO_4$ are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite.