• Journal of Electrochemical Science and Technology
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• v.2 no.2
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• pp.97-102
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• 2011

Different amounts of excess lithium in the range of x = 0~0.3 were added to $Li_{1+x}[Mn_{0.720}Ni_{0.175}Co_{0.105}]O_2$ cathode materials synthesized using the co-precipitation method to investigate its microstructure and electrochemical properties. Pure layered structure without impurities was confirmed in the XRD pattern analysis and increasing peak intensity of $Li_2MnO_3$ was observed along with the addition of over 0.2 mol Li. The initial discharge capacity of the stoichiometric composition was determined to be 246 mAh/g, while the discharge capacity of the addition of 0.1 mol Li was obtained to be 241 mAh/g, which was not significantly different from that of the stoichiometric composition. However, the discharge capacities decreased dramatically after the addition of 0.2 and 0.3 mol Li to 162 mAh/g and 146 mAh/g, respectively. In the rate capability test, the active $Li_{1+x}[Mn_{0.720}Ni_{0.175}Co_{0.105}]O_2$ cathode material of the stoichiometric composition showed a dramatic decrease in its discharge capacity with increasing C-rate, as evidenced by the result that the discharge capacity at 5C was 13% compared with 0.1C. On the other hand, the discharge capacity of compositions containing excess lithium was improved at higher current rates. The cycling test showed that the composition containing an excess of 0.1 mol Li had the most outstanding capacity retention.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.5
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• pp.443-449
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• 2007

The structural and thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ electrode during cycling process was studied. The sample was prepared by simple combustion method. Although there were irreversible changes on the initial cycle, O3 stacking for $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ structure was retained during the first and subsequent cycling process. Impedance of the test cell was decreased after the first charge-discharge process, which would be of benefit to intercalation and deintercalation of lithium ion on subsequent cycling. As expected, cycling test for 75 times increased impedance of the cell a little, instead, thermal stability of $Li[Co_{0.1}Ni_{0.15}Li_{0.2}Mn_{0.55}]O_2$ was improved. Moreover, based on DSC analysis, the initial exothermic peak was shifted to high temperature range and the amount of heat was also decreased after cycling test, which displayed that thermal stability was not deteriorated during cycling.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3233-3237
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• 2010

A $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_2$ cathode was modified by coating with Li-La-Ti-O, and the effect of the coating thickness on their electrochemical properties was studied. The thickness of the coating on the surface of $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_2$ was increased by increasing the wt % of the coating material. The rate capability of the Li-La-Ti-O-coated electrode was superior to that of the pristine sample. 1- and 2-wt %-coated samples showed considerable improvement in capacity retention at high C rates. However, the rate capability of a 5-wt %-coated sample decreased. All the coated samples showed a high discharge capacity and slightly improved cyclic performance under a high cut-off voltage (4.8 V) condition. Results of a storage test confirmed that the Li-La-Ti-O coating layer was effective in suppressing the dissolution of the transition metals as it offered protection from the attack of the acidic electrolyte. In particular, the 2- and 5-wt %-coated samples showed a better protection effect than the 1-wt %-coated sample.

• Journal of Powder Materials
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• v.23 no.2
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• pp.136-142
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• 2016

As precursors of cathode materials for lithium ion batteries, $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$ powders are prepared in a continuously stirred tank reactor via a co-precipitation reaction between aqueous metal sulfates and NaOH in the presence of $NH_4OH$ in air or nitrogen ambient. Calcination of the precursors with $Li_2CO_3$ for 8 h at $1,000^{\circ}C$ in air produces dense spherical cathode materials. The precursors and final powders are characterized by X-ray diffraction (XRD), scanning electron microscopy, particle size analysis, tap density measurement, and thermal gravimetric analysis. The precursor powders obtained in air or nitrogen ambient show XRD patterns identified as $Ni_{1/3}Co_{1/3}Mn_{1/3}(OH)_2$. Regardless of the atmosphere, the final powders exhibit the XRD patterns of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (NCM). The precursor powders obtained in air have larger particle size and lower tap density than those obtained in nitrogen ambient. NCM powders show similar tendencies in terms of particle size and tap density. Electrochemical characterization is performed after fabricating a coin cell using NCM as the cathode and Li metal as the anode. The NCM powders from the precursors obtained in air and those from the precursors obtained in nitrogen have similar initial charge/discharge capacities and cycle life. In conclusion, the powders co-precipitated in air can be utilized as precursor materials, replacing those synthesized in the presence of nitrogen injection, which is the usual industrial practice.

• Transactions of the Korean hydrogen and new energy society
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• v.24 no.2
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• pp.160-171
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• 2013

$LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ powder for cathode materials in lithium rechargeable batteries was treated by atmospheric plasma containing hydrogen to investigate the relationship between charge/discharge performance and physical/chemical changes of materials. Hydrogen plasma at atmosphere pressure was irradiated on the surface of active materials, and the change for their crystal structure, surface morphology, and chemical composition were observed by XRD, SEM-EDS and titration method, respectively. The crystal structure and surface morphology of $H_2$ plasma-treated powders were not changed but their chemical compositions were slightly varied. For charge/discharge test, $H_2$ plasma affected initial capacity and rate capability of active materials but continuous cycling was not subject to plasma treatment. Therefore, it was observed that $H_2$ plasma treatment affected the surface of materials and caused the change of chemical composition.

• Journal of the Korean Electrochemical Society
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• v.16 no.2
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• pp.59-64
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• 2013

Using $Na_2CO_3$ and $MeSO_4$ (Me = Ni, Co and Mn) as starting materials, the precursor of $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ has been synthesized by carbonate co-precipitation. The precursor was mixed with $Li_2CO_3$, and calcined at 750, 850, and$950^{\circ}C$ in air. Effect of calcinations temperature on characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ cathode materials was investigated. The structure and characteristics of $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ were determined by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and electrochemical measurements. The X-ray diffraction (XRD) results show that the intensity ratio of $I_{(003)}/I_{(104)}$ increased and the R-factor ratio decreased with the increase of calcinations temperature. And Scanning electron microscopy (SEM) result show that the primary particle size increased. Especially, the $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ calcined at $950^{\circ}C$ for 24 H shows excellent electrochemical performances with reversible specific capacity of $165.3mAhg^{-1}$ [cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] and good capacity retention of 95.4% after 50th charge/discharge cycles[cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)].

• Journal of the Korean Electrochemical Society
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• v.19 no.1
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• pp.1-8
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• 2016

Capacity of layered lithium nickel-cobalt-manganese oxide ($LiNi_{1-x-y}Co_xMn_yO_2$) cathode material can increase by raising the charge cut-off voltage above 4.3 V vs. $Li/Li^+$, but it is limited due to anodic instability of conventional electrolyte. We have been screening and evaluating various sulfone-based compounds of dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS) as electrolyte additives for high-voltage applications. Here we report improved cycling performance of $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode by the use of dimethyl sulfone (DMS) additive under an aggressive charge condition of 4.6 V, compared to that in conventional electrolyte, and cathode-electrolyte interfacial reaction behavior. The cathode with DMS delivered discharge capacities of $198-173mAhg^{-1}$ over 50 cycles and capacity retention of 84%. Surface analysis results indicate that DMS induces to form a surface protective film at the cathode and inhibit metal-dissolution, which is correlated to improved high-voltage cycling performance.

• Proceedings of the Korean Ceranic Society Conference
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• 2002.10a
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• pp.164.2-164
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• 2002

• Journal of the Korean Electrochemical Society
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• v.17 no.4
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• pp.222-228
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• 2014

Ni-rich system $Li[Ni_{1-x-y}Co_xMn_y]O_2$ of lithium secondary battery cathode material keep a high discharge capacity. However, by the Ni content increases, there is a problem that the electrochemical properties and stability of the structure are reduced. In order to solve these problems, research for positive ion doping is performed. The one of the cathode material, barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01), was synthesized by the precursor, $Ni_{0.6}Co_{0.1}Mn_{0.3}(OH)_2$, from the co-precipitation method. The barium doped materials have studied the structural and electrochemical properties. The analysis of structural properties, results of X-ray diffraction analysis, and those results confirmed the change of the lattice from the binding energy in the structure by barium doping. Increased stability of the layered structure was observed by $I_{(006)}+I_{(102)}/I_{(101)}$(R-factor) ratio decrease. we expected that the electrochemical characteristics are improved. 23 mAh/g discharge capacity of barium-doped $Li[Ni_{0.6-x}Ba_xCo_{0.1}Mn_{0.3}]O_2$ (x=0.01) electrode is higher than discharge capacity of $Li[Ni_{0.6}Co_{0.1}Mn_{0.3}]O_2$ due to decrease overvoltage. And, through the structural stability was confirmed that improved the cycle characteristics. We caused a reduction in charge transfer resistance between the electrolyte and the electrode was confirmed that the C-rate characteristics are improved.

• 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.