• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.679-682
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• 2002

Layered Na0.7[Ni0.05Mn0.95]O2 compounds have been synthesized by a sol-gel method, using glycolic acid as a chelating agent. Na0.7[Ni0.05Mn0.95]O2 precursors w ere used to prepare layered lithium manganese oxides by ion exchange for Na by Li, using LiBr in hexanol. Powder X-ray diffraction shows the layered Na0.7[Ni0.05Mn0.95]O2 has an O3 type structure, which exhibits a large reversible capacity of approximately 190 mA h g-1 in the 2.4-4.5 V range. Na0.7[Ni0.05Mn0.95]O2 powders undergo transformation to spinel during cycling.

• Journal of Industrial Technology
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• v.43 no.1
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• pp.43-48
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• 2023

Spinel LiNi_0.5Mn_1.5O₄ (LNMO) has been considered as one of most promising cathode material, because of its low-cost and competitive energy density. However, 4.7V vs. Li/Li⁺ of high operating potential facilitates electrolyte degradation on cathode-electrolyte interface during charge-discharge process. In particular, commercial polyvinylidene fluoride (PVDF) is not sutaible for LNMO cathode binder because its weak van der waals force induces thick and non-uniform coverage on the cathode surface. In this review, we study high performance binders for LNMO cathode, which forms uniform coating layer to prevent direct contact between electrolyte and LNMO particle as well as modifying high quality cathode electrolyte interphase, improved cell performace.

• Journal of the Korean Electrochemical Society
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• v.8 no.2
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• pp.82-87
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• 2005

The cathode material, $LiNi_{0.5}Mn_{1.5}O_4$, for high voltage applications of Li-ion batteries exhibits impurity phases due to oxygen deficiency during the high temperature heat treatment. The impurity phase reduces the electrochemical properties of the electrode since the deficiency spinel structure disturbs the lithium ion intercalation and deintercalation. In this study, Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$ powders are synthesized by a sol-gel method in order to reduce the amount of the impurity phases in the $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$. Thermal analysis of the cathode material shows that the $LiNi_{0.5}Mn_{1.5}O_4$ without Cr substitution looses $2\%$ of its weight due to oxygen deficiency but the amount of weight loss is diminished when Cr is substituted. XRD analysis also supports the reduction of the impurity phases in the cathode after chromium substitution, suggesting that the improvement of the electrochemical properties such as the capacity retention and electrochemical stability are attributed to the low content of impurity phases in the Cr-substituted $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4.$

• 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.

• 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.

• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• Journal of Electrochemical Science and Technology
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• v.8 no.1
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• pp.53-60
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• 2017

Fluoroethylene carbonate (FEC) was studied as an additive for the electrolyte in lithium ion batteries with the $LiNi_{0.5}Mn_{1.5}O_4$ (LNMO) spinel cathode operating at a high potential beyond 4.7 V (vs. $Li/Li^+$). It was found that the FEC additive was electrochemically active for the $1^{st}$ charge cycle on the LNMO cathode. The presence of a large amount of FEC (more than 40 vol%) in the electrolyte caused severe side reactions with abnormally long voltage plateaus. In contrast, when the electrolyte contained less than 30 vol% FEC, the surface of the LNMO cathode was stabilized by the formation of the solid-electrolyte interphase (SEI), leading to improved cyclability. However, the resistance from the SEI limited the rate capability because of sluggish lithium transportation through the SEI and electronic insulation between the particles in the electrode.

• Journal of the Korean Electrochemical Society
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• v.18 no.2
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• pp.51-57
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• 2015

We report the effect of the impurities including water and bromide in the propylmethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PMPyr-TFSI) on the electrochemical performance of lithium ion batteries. The several kinds of PMPyr-TFSI electrolytes with different amount of impurities are applied as the electrolyte to the cell with the high potential electrode, $LiNi_{0.5}Mn_{1.5}O_4$ spinel. It is found that the impurities in the electrolytes cause the detrimental effect on the cell performance by tracing the cycleability, voltage profile and Coulombic efficiency. Especially, the polarization and Coulombic efficiency go to worse by both impurities of water and bromide, but the cycleability was not highly influenced by bromide impurity unlike the water impurity.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.89-94
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• 2013

Layered $Li_{1+x}(Mn_{0.4}Ni_{0.4}Fe_{0.2})_{1-x}O_2$ (0 < x < 0.3) solid solutions were synthesized using solgel method with adipic acid as chelating agent. Structural and electrochemical properties of the prepared powders were examined by means of X-ray diffraction, Scanning electron microscopy and galvanostatic charge/discharge cycling. All powders had a phase-pure layered structure with $R\bar{3}m$ space group. The morphological studies confirmed that the size of the particles increased at higher x content. The charge-discharge profiles of the solid solution against lithium using 1 M $LiPF_6$ in EC/DMC as electrolyte revealed that the discharge capacity increases with increasing lithium content at the 3a sites. Among the cells, $Li_{1.2}(Mn_{0.32}Ni_{0.32}Fe_{0.16})O_2$ (x = 0.2)/$Li^+$ exhibits a good electrochemical property with maximum initial capacity of 160 $mAhg^{-1}$ between 2-4.5 V at 0.1 $mAcm^{-2}$ current density and the capacity retention after 25 cycles was 92%. Whereas, the cell fabricated with x = 0.3 sample showed continuous capacity fading due to the formation of spinel like structure during the subsequent cycling. The preparation of solid solutions based on $LiNiO_2-LiFeO_2-Li_2MnO_3$ has improved the properties of its end members.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3553-3558
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• 2014

The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.