• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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• pp.216-216
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• 2003

The layered nickel oxides (LiNiO$_2$) have been studied for possible use as cathode materials i3l 4V lithium batteries. Although LiCoO$_2$ has been known as the best candidate material for Li-ion batteries, which produces the best performance LiNiO$_2$ is generally accepted as an attractive cathode material, because of its various advantages such as lower cost higher discharge capacity and better reversibility. In this investigation, we calculated the electric state of LiNiO$_2$ using DV-X$\alpha$ molecular orbital method in order to obtain the information of chemical bonding among the Li, Ni and O. In LiNiO$_2$, alternate layers of Li and Ni occupy the octahedral sites of a cubic close packing of oxide ions, making up a rhombohedral structure with an R-3m space group, Li in 3a, Ni in 3b, and O in 6c sites. On the basis of this, we made the cluster model and studied ionization of each atoms and interaction between atoms according to Mullilcen population analysis.

• Composites Research
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• 제34권6호
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• pp.345-349
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• 2021

The continued environmental pollution caused by fossil fuel consumption has prompted researchers around the world to develop environmentally friendly energy technologies. Electrochemical energy storage is the significant area of research in this development process, and the research significance of supercapacitors in this field is increasing. Herein, a simple electrodeposition synthetic route was explored to develop the MoP layered cathode material. The layered structure provided a highly ion-accessible surface for smooth and faster ion adsorption/desorption. After Fe was doped into MoP, the morphology of MoP changes and the electrochemical performance was significantly improved. Specific capacitance value of the binder-free FeMoP electrode was found to be 269 F g^-1 at 2 A g^-1 current density in 6 M aqueous KOH electrolyte. After adding Fe to MoP, an additional redox contribution was observed in the redox conversion from Fe³⁺ to Fe²⁺ redox pair, and the charge transfer kinetics of MoP was effectively improved. This research can provide guidance for the development of supercapacitor electrode materials through simple electrodeposition technology.

• Journal of Electrochemical Science and Technology
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• 제2권2호
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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.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2011년도 춘계학술발표대회
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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.

• 전기화학회지
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• 제19권1호
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• pp.1-8
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• 2016

층상구조 삼성분계 $LiNi_{1-x-y}Co_xMn_yO_2$ 양극활물질을 4.3 V 이상 고전압으로 충전시키면 용량 증가를 기대할 수 있으나 기존 전해액의 산화안정성이 낮아 고전압 성능 구현에 제한이 있다. 본 연구에서는 설폰계 전해액 첨가제인 dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS)을 사용하여 $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ 양극의 고전압 특성을 향상시키고자 한다. 본 논문은 다양한 선형 sulfone계 첨가제가 포함된 전해액에서 3.0-4.6 V 전압범위에서 양극의 충방전 특성과 양극-전해액간 계면거동과 표면층 분석에 대한 내용으로 이루어져 있다. 특히 Dimethyl sulfone (DMS) 첨가제 사용시, 50 사이클 중 $198-173mAhg^{-1}$의 방전 용량과 87%의 용량유지율을 보여 기존 전해액 대비 상당히 향상된 충방전 안정성을 보였다. 표면조성 분광분석 결과, DMS 첨가제 사용시 양극에 안정한 표면보호층이 형성되고 금속 용출이 억제되어 고전압 충방전 특성이 향상되었음 알 수 있었다.

• Transactions on Electrical and Electronic Materials
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• 제18권2호
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• pp.89-92
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• 2017

The performance of three-layered organic light-emitting diodes (OLEDs) was investigated using TPD hole-transport and injection layers, Teflon-AF, and the electron-injection layer of $Li_2CO_3$ and LiF. The OLEDs were manufactured in a structure of TPD/$Alq_3$/LiF, TPD/$Alq_3$/$Li_2CO_3$, and AF/$Alq_3$/LiF using low-molecular organic materials. In three different three-layered OLEDs, it was found that the device with the TPD/$Alq_3$/LiF structure shows higher performance in maximum luminance, and maximum external quantum efficiency compared to those of the device with TPD/$Alq_3$/$Li_2CO_3$ and TPD/$Alq_3$/LiF by 35% and 17%, and 193% and 133%, respectively. It is thought that the combined LiF/Al cathode contributes to a reduced work function and improves an electrical conduction mechanism due to the electron injection rather than the hole transport, which then increases a recombination rate of charge carriers.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2010년도 춘계학술발표대회
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• pp.37.2-37.2
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• 2010

Recently $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ has been consistently examined and investigated by scientists because of its high lithium storage capacity, which exceeds beyond the conventional theoretical capacity based on conventional chemical concepts. Consequently, $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ is considered as one of the most promising cathode candidates for next generation in Li rechargeable batteries. Yet the mechanism and the origin of the overcapacity have not been clarified. Previously, many authors have demonstrated simultaneous oxygen evolution during the first delithiation. However, it may only explain the high capacity of the first charge process, and not of the subsequent cycles. In this work, we report a clarified interpretation of the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$, which is the key element in understanding its anomalously high capacity. We identify how the structural evolution of $Li_{1.2}Ni_{0.2}Mn_{0.6}O_2$ occurs upon the electrochemical cycling through careful study of electrochemical profiles, ex-situ X-ray diffraction (XRD), HR-TEM, Raman spectroscopy, and first principles calculation. Moreover, we successfully separated the structural change at subsequent cycles (mainly cation rearrangement) from the first charge process (mainly oxygen evolution with Li extraction) by intentionally synthesizing sample with large particle size. Consequently, the intermediate states of structural evolution could be well resolved. All observations made through various tools lead to the result that spinel-like cation arrangement and lithium environment are created and embedded in layered framework during repeated electrochemical cycling.

• 전기화학회지
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• 제14권3호
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• pp.176-183
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• 2011

본 연구에서는 Sr이 치환된 이중층 페로브스카이트($SmBa_{0.5}Sr_{0.5}Co_2O_{5+{\delta}}$, SBSCO)와 전해질 물질로 사용되는 $Ce_{0.9}Gd_{0.1}O_{2-{\delta}}$ (CGO91)을 기반으로 한 중 저온형 고체산화물 연료전지 (ITSOFC) 복합공기극의 분말 크기와 열 사이클에 대한 전기화학특성을 연구하였다. 복합공기극의 모체가 되는 SBSCO에 CGO91물질을 이용하여 면적비저항을 확인 한 결과 약 $0.54\sim9.04{\mu}m$의 분말 크기를 보이는 SBSCO와 $0.4\sim42{\mu}m$의 분말 크기를 보인 CGO91이 각각 50 wt%로 구성된 SBSCO : 50 복합공기극이 600 및 $700^{\circ}C$에서 약 0.102 및 $0.013{\Omega}cm^2$의 우수한 면적비 저항을 가지는 것을 확인 하였으며 상대적으로 분말 크기가 큰 CGO91 분말을 이용한 두 개의 공기극의 경우 $700^{\circ}C$에서 약 $0.260{\Omega}cm^2$와 $0.055{\Omega}cm^2$의 특성을 보여주었다. 10회에 걸친 열 사이클실험을 통하여 SBSCO : 50의 면적비저항은 $0.0193{\Omega}cm^2$에서 $0.094{\Omega}cm^2$로 증가하였으며 7회 이후의 면적비저항은 일정하게 유지됨을 확인하였다.

• 한국분말재료학회지
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• 제24권2호
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• pp.87-95
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• 2017

Lithium silicate, a lithium-ion conducting ceramic, is coated on a layer-structured lithium nickel manganese oxide ($LiNi_{0.7}Mn_{0.3}O_2$). Residual lithium compounds ($Li_2CO_3$ and LiOH) on the surface of the cathode material and $SiO_2$ derived from tetraethylorthosilicate are used as lithium and silicon sources, respectively. Powder X-ray diffraction and scanning electron microscopy with energy-dispersive spectroscopy analyses show that lithium silicate is coated uniformly on the cathode particles. Charge and discharge tests of the samples show that the coating can enhance the rate capability and cycle life performance. The improvements are attributed to the reduced interfacial resistance originating from suppression of solid-electrolyte interface (SEI) formation and dissolution of Ni and Mn due to the coating. An X-ray photoelectron spectroscopy study of the cycled electrodes shows that nickel oxide and manganese oxide particles are formed on the surface of the electrode and that greater decomposition of the electrolyte occurs for the bare sample, which confirms the assumption that SEI formation and Ni and Mn dissolution can be reduced using the coating process.

• 전기화학회지
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• 제8권1호
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• pp.42-46
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• 2005

It has been known that the synthesis of the cathode materials for the lithium rechargeable batteries by the sol-gel process has many advantages over the conventional solid-state method. It has been, however, a continuing issue that new additional steps should be introduced to commercialize this process. In this work, spray drying was introduced to the existing sol-gel process as a continuous mass production method of the pre-heat treatment precursor materials. The precursors of $LiCoO_2$ and $LiNi_{0.8}Co_{0.2}O_2$ were continuously produced through spray drying from the solution containing stoichiometric amount of lithium, cobalt, and nickel sources as well as a chelating agent. The process variables, such as pH of the starting solution, spray drying conditions, and calcination conditions were optimized. The XRD pattern for the synthesized material indicated a good crystallinity with a layered structure.