• 전기화학회지
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• 제6권1호
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• pp.1-5
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• 2003

[ $LiNi_{1-x}Co_xO_2\;(x=0.0,\;0.3,\;05,\;0.7,\;1.0)$ ]을 구연산법을 이용하여 합성하고, Co 치환량에 따른 결정구조와 리튬 이차전지 양극특성을 조사하였다 X-선 회절분석 결과로부터 Co치환량에 무관하게 모든 조성에서 단일상의 고용체를 형성함을 알 수 있었다. 또한 Rietveld 구조정산을 통하여 고용체의 결정구조가 Co 치환량에 따라 크게 변화함을 확인하였다. 즉, Co치환량이 적은 경우는 (x=0-0.5)는 격자상수의 비가 작은(c/a<4.98) 입방구조에 가까웠으며, Co치환량이 큰 경우(x^gt;0.7)는 격자상수의 비가 큰$(c/a\geq4.98)$ 층상구조를 보였다. 이와 같은 차이는 electrochemical voltage spectroscopy를 통하여 확인할 수 있었는데, 고용체를 형성하고 있는 Co성분은 Co치환량이 적을 경우는 $3.7V\;(vs.\;Li/Li^+)$, 그리고 치환량이 클 경우는 $3.92V\;(vs.\;Li/Li^+)$에서 충전되는 현상을 보였다.

• 한국세라믹학회지
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• 제42권9호
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• pp.602-606
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• 2005

[ $LiCoO_{2}$ ] is the most common cathode electrode materials in Lithium-ion batteries. $LiCo_{0.97}Mg_{0.03}O_2$ was synthesized by the solid-state reaction method. We investigated crystal structures, electrical conductivities and electrochemical properties. The crystal structure of $LiCo_{0.97}Mg_{0.03}O_2$ was analyzed by X-ray powder diffraction and Rietveld refinement. The material showed a single phase of a layered structure with the space group R-3m. The lattice parameter(a, c) of $LiCo_{0.97}Mg_{0.03}O_2$ was larger than that of $LiCoO_2$. The electrical conductivity of sintered samples was measured by the Van der Pauw method. The electrical conductivities of $LiCoO_2$ and $LiCo_{0.97}Mg_{0.03}O_2$ were $2.11{\times}10^{-4}\;S/cm$ and $2.41{\times}10^{-1}\;S/cm$ at room temperature, respectively. On the basis of the Hall effect analysis, the increase in electrical conductivities of $LiCo_{0.97}Mg_{0.03}O_2$ is believed due to the increased carrier concentrations, while the carrier mobility was almost invariant. The electrochemical performance was investigated by coin cell test. $LiCo_{0.97}Mg_{0.03}O_2$ showed improved cycling performance as compared with $LiCoO_2$.

• Bulletin of the Korean Chemical Society
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• 제30권11호
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• pp.2603-2607
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• 2009

$LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ (x = 0, 0.1, 1/6, 1.2, 0.3) were synthesized by the solid-state reaction method. The crystal structure was analyzed by X-ray powder diffraction and Rietveld refinement. $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$ samples give single phases of hexagonal layered structures with a space group of R-3m for x = 0.1, 1/6, 0.2, and 0.3. The lattice constants of a and c-axis were decreased with the increase in Co contents in samples. The thickness of MO2 slab was decreased and inter-slab distance was increased with the increase in Co contents in $LiNi_{0.5-x}Co_{2x}Mn_{0.5-x}O_{2}$. According to XPS analysis, the valence states of Mn, Co, and Ni in the sample are mainly +4, +3, and +3, respectively. The discharge capacity of 202 mAh/g at 0.1C-rate in the potential range of 4.7 - 3.0 V was obtained in $LiNi_{0.3}Co_{0.4}Mn_{0.3}O_2$ sample, and $LiNi_{0.4}Co_{0.2}Mn_{0.4}O_2$ gives excellent cycle performance in the same potential range.

• 자원리싸이클링
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• 제14권6호
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• pp.37-43
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• 2005

페리튬이온전지로부터 회수된 코발트와 리튬 침출액으로부터 화염분부열분해법에 의하여 $LiCoO_{2}$ 나노분말을 제조하였다. 리튬 및 코발트 성분을 함유하는 전극물질은 열처리 및 기계적 처리에 의해 그 농도를 증가 시켰다. 리튬이온전지 양극물질을 질산으로 용해한 다음 침출액중 Li과 Co의 당량비가 1.0 되도록 $LiNO_{3}$로 조절하여 화염분무열분해용 전구체를 제조하었다. 화염분무열분해법에 의해 제조된 $LiCoO_{2}$ 분말의 평균입자크기는 전구체의 몰 농도가 증가하면서 증가되었으며, 화염온도 역시 입자의 크기를 증가시켰다. 변수실험 결과 $11{\~}35nm$ 크기의 결정형 $LiCoO_{2}$ 나노분말을 제조할 수 있었다 또한 나노 $LiCoO_{2}$의 전극재료로서의 가능성을 확인하기 위하여 충방전 특성 평가와 같은 전기화학적 분석을 수행하였다.

• 한국세라믹학회지
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• 제40권6호
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• pp.507-512
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• 2003

The LiN $i_{l-y}$ $Co_{y}$ $O_2$ samples were synthesized at 80$0^{\circ}C$ and 85$0^{\circ}C$, by the solid-state reaction method, from the various starting materials LiOH, L $i_2$C $O_3$, NiO, NiC $O_3$, $Co_3$ $O_4$, CoC $O_3$, and their electrochemical properties are investigated. The LiN $i_{l-y}$ $Co_{y}$ $O_2$ pre-pared from L $i_2$C $O_3$, NiO, and $Co_3$ $O_4$ exhibited the $\alpha$-NaFe $O_2$ structure of the rhombohedral system (space group; R3m). As the Co content increased, the lattice parameters a and c decreased. The reason is that the radius of Co ion is smaller than that of Ni ion. The increase in da shows that two-dimensional structure develops better as the Co content increases. The LiN $i_{0.7}$ $Co_{03}$. $O_2$［HOO(800,0.3)] synthesized at 80$0^{\circ}C$from LiOH, NiO, and $Co_3$ $O_4$ exhibited the largest first discharge capacity 162 mAh/g. The size of particles increases roughly as the valve of y increases. The samples with the larger particles have the larger first discharge capacities. The cycling performances of the samples with the first discharge capacity larger than 150 mAh/g were investigated. The LiN $i_{0.9}$ $Co_{0.1}$ $O_2$［COO(850,0.1)］ synthesized at 85$0^{\circ}C$ from L $i_2$C $O_3$, NiO, and $Co_3$ $O_4$ showed an excellent cycling performance. The sample with the larger first discharge capacity will be under the more severe lattice destruction, due to the expansion and contraction of the lattice during intercalation and deintercalation, than the sample with the smaller first discharge capacity. As the first discharge capacity increases, the capacity fading rate thus increases.increases.s.s.s.

• Transactions on Electrical and Electronic Materials
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• 제7권2호
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• pp.76-80
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• 2006

Well-defined orthorhombic $LiMnO_2\;and\;LiCo_{0.1}Mn_{0.9}O_2$ were synthesized by a solid-state reaction and quenching process. X-ray diffraction (XRD) results revealed that the as-synthesized powders showed an orthorhombic phase of a space group with Pmnm. The $Li/LiMnO_2\;and\;Li/LiCo_{0.1}Mn_{0.9}O_2$ cells were constituted and cycled galvanostatically in the voltage range of 2.0-4.3 V vs. $Li/Li^+$ at a current density of $0.5\;mA\;cm^{-2}$ at room temperature and $50^{\circ}C$, respectively. The results demonstrated that the highest specific capacity of $Li/LiMnO_2$ cells at room temperature and $50^{\circ}C$ was 95 and $155\;mAh\;g^{-1}$, respectively. As for $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells, the highest specific capacity at room temperature and $50^{\circ}C$ was 160 and $250\;mAh\;g^{-l}$, respectively. It could be seen that the performance of $Li/LiCo_{0.1}Mn_{0.9}O_2$ cells was better than that of $Li/LiMnO_2$ cells.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2003년도 추계학술발표강연 및 논문개요집
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• pp.124-124
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• 2003

To improve the electrochemical properties of thin-film LiCoO$_2$ cathodes, metal oxides were coated on the LiCoO$_2$ thin films using f sputtering. Galvanostatic charge-discharge experiments showed the enhanced cycling behaviors in the metal-oxide coated LiCoO$_2$ thin films than the uncoated ones. These results are because the metal-oxide coating layer suppresses the degradation of Li-diffusion kinetics during cycling, which is related to the protection of cathode surface from the electrolytes [l-3]. The variation in the metal-oxide coating thickness ranging from 10 to 300 nm did not affect the electrochemical properties. Changes of lattice constants in the coated and bare LiCoO$_2$ thin films at different charged states will also be discussed.

• 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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• 제16권2호
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• pp.59-64
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• 2013

$Na_2CO_3$와 [M($SO_4$)(M = Ni, Co, Mn)]을 사용함으로써, Carbonate 공침 합성법에 의해 $[Ni_{0.6}Co_{0.2}Mn_{0.2}]CO_3$ 전구체를 합성하였다. 합성된 전구체는 공기분위기에서 $Li_2CO_3$와 혼합하여 각각, 750, 850 그리고 $950^{\circ}C$에서 소성되었고, 이로 인한 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$ 양극활 물질의 소성온도가 미치는 영향을 조사하였다. $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$의 구조와 특성은 X-선 회절 분석(XRD), 시차주사현미경(SEM) 그리고 전기화학적 측정으로 분석되었는데, X-선 회절 결과 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 소성온도가 증가함에 따라서 $I_{(003)}/I_{(104)}$는 증가하고 R-factor 는 감소하였으며, 시차주사현미경 결과에서는 1차 입자의 크기가 증가하는 경향을 보였다. 특히, $950^{\circ}C$에서 24시간 동안 소성된 $Li[Ni_{0.6}Co_{0.2}Mn_{0.2}]O_2$는 가역 용량이 $165.3mAhg^{-1}$[cut-off voltage 2.5~4.3 V, 0.1 C($17mAhg^{-1}$)] 그리고 50번째 충 방전 사이클 [cut-off voltage 2.5~4.3 V, 1 C($170mAhg^{-1}$)]까지 95.4%의 우수한 용량 보존율을 가지면서 가장 우수한 전기화학적 특성을 보여주었다.

• 한국전기전자재료학회논문지
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• 제19권7호
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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 $2.8\sim4.3V$.