• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.19 no.7
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• pp.650-654
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• 2006

[ $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ ] cathode material was synthesized by a mixed hydroxide method. Structural characterization was carried out using X-ray diffraction studies. Electrochemical studies were performed by assembling 2032 coin cells with lithium metal as an anode. DSC (Differential scanning calorimetry) data showed that exothermic reactions of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ charged to 4.3 V versus Li started at high temperatures$(280\sim390^{\circ}C)$. The cell of $LiNi_{0.4}Mn_{0.3}Co_{0.3}O_2$ mixed cathode delivered a discharge capacity of 150 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of 134 mAh/g was obtained at a 2 C rate. The reversible capacity after 100th cycles was 126 mAh/g when a cell was cycled at a current rate of 0.5 C in $2.8\sim4.3V$.

• 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 the Korean Institute of Electrical and Electronic Material Engineers
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• v.22 no.10
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• pp.890-896
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• 2009

Li(Ni, Co, Mn)$O_2$ has been known as one of the most promising cathode materials for lithium secondary batteries. However, it has some problems to overcome for commercialization such as inferior rate capability and unstable thermal stability. In order to address these problems, surface modification of cathode materials by coating has been investigated. In the coating techniques, selection of coating material is a key factor of obtaining enhanced properties of cathode materials. In this work, we introduced solid electrolyte (Li-La-Ti-O) as a coating material on the surface of $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_2$ cathode. Specially, we focused on a rate performance of Li-La-Ti-O coated $Li[Ni_{0.3}Co_{0.4}Mn_{0.3}]O_2$ cathode. Both bare and Li-La-Ti-O 2 wt.% coated sample showed similar discharge capacity at 0.5C rate. However, as the increase of charge-discharge rate to 3C, the coated samples displayed better discharge capacity and cyclic performance than those of bare sample.

• Journal of Electrochemical Science and Technology
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• v.15 no.1
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• pp.168-177
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• 2024

Ni-rich cathode is one of the promising candidates for high-energy lithium-ion battery applications. Due to its specific capacity, easy industrialization, and good circulation ability, Ni-rich cathode materials have been widely used for lithium-ion batteries. However, due to the limitation of the co-precipitation method, including sewage pollution, and the instability of the long production cycles, developing a new efficient and environmentally friendly synthetic approach is critical. In this study, the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder was successfully synthesized by an efficient spray-drying method using carbonate compounds as a raw material. This Ni_0.91Co_0.06Mn_0.03CO₃ precursor was calcined by mixing with LiOH·H₂O (5 wt% excess) at 480℃ for 5 hours and then sintered at two different temperatures (780℃/800℃) for 15 hours under an oxygen atmosphere to complete the cathode active material preparation, which is a key component of lithium-ion batteries. As a result, LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were obtained successfully via a simple sintering process on the Ni_0.91Co_0.06Mn_0.03CO₃ precursor powder. Furthermore, the obtained LiNi_0.91Co_0.06Mn_0.03O₂ cathode active material powders were characterized. Overall, the material sintered at 780℃ shows superior electrochemical performance by delivering a discharge capacity of 190.76 mAh/g at 1^st cycle (0.1 C) and excellent capacity retention of 66.80% even after 50 cycles.

• 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 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.16 no.3
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• pp.151-156
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• 2013

As the cathode material for li-ion battery, $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ were synthesized by supercritical hydrothermal method and calcined $850^{\circ}C$ and $900^{\circ}C$ for 10hrs in air. The effect of temperature in the heat treatment on the powder and its performance were studied of xray diffraction pattern, SEM-image, physical properties and electrochemical behaviors. As a result, calcined at $900^{\circ}C$ material particle size more increase than calcined at $850^{\circ}C$ material, especially shows excellent electrochemical performance with initial reversible specific capacity of 163.84 mAh/g (0.1C/2.0-4.3V), 186.87 mAh/g (0.1C/2.0-4.5V) and good capacity retention of 91.49% (0.2C/2.0-4.3V) and 90.36% (0.2C/2.0-4.5V) after 50th charge/discharge cycle.

• 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 Electrochemical Society
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• v.9 no.2
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• pp.64-69
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• 2006

Cathode materials of Al-doped $Li(Ni_{1/3}Co_{1/3}Mn_{1/3-x}Al_x)O_2$ (x=0.0, 0.005, 0.01 0.05) for lithium ion batteries were synthesized with ultra-sonic spray pyrolysis method and single-step heat treatment. No secondary phases were found in all synthesized powders. The intensity ratio of $I_{003}\;to\;I_{104}$, however, slightly decreased and the particle size increased with the Al contents. The cells with bare, 0.5 and 1.0 at% Al-doped powders showed the initial discharge capacities of 182, 180 and $184mAhg^{-1}$ in a voltage range of $3.0\sim4.5V$ at 1C rate, and the capacity retentions of 81, 77 and 78% at the end of 30 cycles, respectively. But in the voltage range of $3.0\sim4.6V$, the Al-doping significantly enhanced the cycle stability. For example, the discharge capacity after 50 cycles was maintained to 70% in the 0.5 at% Al-doped sample compared to only 30% in no doped sample. The improvement of the cycle stability was thought to be due to $Mn^{3+}$ ion decrease as the Al doping from the XPS analysis results.

• Proceedings of the Materials Research Society of Korea Conference
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• 2011.05a
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• pp.5-5
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• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.