• Proceedings of the Korea Crystallographic Association Conference
• /
• 2002.11a
• /
• pp.16-16
• /
• 2002

The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).

• Journal of the Korean Electrochemical Society
• /
• v.13 no.4
• /
• pp.264-269
• /
• 2010

$LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ active material was prepared by simple-combustion method and investigated as the cathode material for li-ion battery. The structural characterization was analyzed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM), respectively. The XRD patterns of $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ sample was indicated a phase of layered hexagonal structure. The size of particles has not uniform diameters ranging from 100 to 300 nm. The electrochemical performance of the $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ was measured by Cyclic Voltammetry and galvanostatics. The $LiNi_{0.5}Mn_{0.3}Co_{0.2}O_2$ shows the discharge capacity of ~162 mAh/g in the range of 2.8 to 4.3 V at the first cycle.

• Journal of Electrochemical Science and Technology
• /
• v.3 no.1
• /
• pp.29-34
• /
• 2012

The structural changes of $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material for lithium ion battery during the first charge was investigated in comparison with $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$ using a synchrotron based in situ X-ray diffraction technique. The structural changes of these two cathode materials show similar trend during first charge: an expansion along the c-axis of the unit cell with contractions along the a- and b-axis during the early stage of charge and a major contraction along the c-axis with slight expansions along the a- and b-axis near the end of charge at high voltage limit. In $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode, however, the initial unit cell volume of H2 phase is bigger than that of H1 phase since the c-axis undergo large expansion while a- and b- axis shrink slightly. The change in the unit cell volume for $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ during charge is smaller than that of $Li_{1-x}Ni_{0.8}Co_{0.15}Al_{0.05}O_2$. This smaller change in unit cell volume may give the $Li_{1-x}Ni_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode material a better structural reversibility for a long cycling life.

• Journal of the Korean Electrochemical Society
• /
• v.16 no.4
• /
• pp.191-197
• /
• 2013

The one of the cathode material, $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$, was synthesized by the precursor, $Ni_{0.5}Co_{0.2}Mn_{0.3}(OH)_2$, from the co-precipitation method and the morphologies of the primary particle of precursors were flake and needle-shape by controlling the precipitation parameters. Identical powder properties, such as particle size, tap density, chemical composition, were obtained by same process of lithiation and heat-treatment. The relation between electrochemical performances of $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$ and the primary particle morphology of precursors was analyzed by SEM, XRD and EELS. In the $Li(Ni_{0.5}Co_{0.2}Mn_{0.3})O_2$ cathode from the needle-shape precursor, the primary particle size was smaller than that from flake-shape precursor and high Li concentration at grain edge comparing grain center. The cycle and rate performances of the cathode from needle-shape precursor shows superior to those from flake-shape precursor, which might be attributed to low charge-transfer resistance by impedance measurement.

• Journal of Electrochemical Science and Technology
• /
• v.5 no.3
• /
• pp.87-93
• /
• 2014

The fluorine-substituted $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode materials were synthesized by using the transition metal precursor, $LiOH{\cdot}H_2O$ and LiF. This was to facilitate the movement of lithium ions by forming more compact SEI layer and to reduce the dissolution of transition metals. The $0.3Li_2MnO_3{\cdot}0.7Li[Mn_{0.60}Ni_{0.25}Co_{0.15}]O_{2-x}F_x$ cathode material was sphere-shaped and each secondary particle had $10{\sim}15{\mu}m$ in size. The fluorine-substituted cathodes initially delivered low discharge capacity, but it gradually increased until 50th charge-discharge cycles. These results indicated that fluorine substitution gave positive effects on the structural stabilization and resistance reduction in materials.

• Bulletin of the Korean Chemical Society
• /
• v.30 no.11
• /
• pp.2603-2607
• /
• 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.

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

• Journal of the Korean Electrochemical Society
• /
• v.16 no.2
• /
• pp.59-64
• /
• 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 Electrochemical Science and Technology
• /
• v.5 no.1
• /
• pp.32-36
• /
• 2014

The $0.3Li_2MnO_3{\cdot}0.7LiMn_{0.55}Ni_{0.30}Co_{0.15}O_2$ cathode material was prepared via a co-precipitation method. The vapor grown carbon fiber (VGCF) was used as a conductive material and its effects on electrochemical properties of the $0.3Li_2MnO_3{\cdot}0.7LiMn_{0.55}Ni_{0.30}Co_{0.15}O_2$ cathode material were investigated. From the XRD pattern, the typical complex layered structure was confirmed and a solid solution between $Li_2MnO_3$ and $LiMO_2$ (M = Ni, Co and Mn) was formed without any secondary phases. The VGCF was properly distributed between cathode materials and conductive sources by a FE-SEM. In voltage profiles, the electrode with VGCF showed higher discharge capacity than the pristine electrode. At a 5C rate, 146 mAh/g was obtained compared with 232 mAh/g at initial discharge in the electrode with VGCF. Furthermore, the impedance of the electrode with VGCF did not changed much around $9-10{\Omega}$ while the pristine electrode increased from 21.5${\Omega}$ to $46.3{\Omega}$ after the $30^{th}$ charge/discharge cycling.

• Journal of the Korean Ceramic Society
• /
• v.38 no.5
• /
• pp.424-430
• /
• 2001

Cut-off 전압 변화에 따른 충방전 특성을 알아보기 위하여 Mn을 다른 전이 금속이 Co와 Ni로 소량 치환시킨 Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$(M=Ni, Co, $\delta$=0, 0.05, 0.1, 0.2)를 고상 반응법으로 80$0^{\circ}C$에서 48시간 동안 유지하여 합성하였다. 충방전의 cut-off 전압은 2.5~4.4V, 3.0~4.5V, 3.5~4.5V, 3.5V~4.7V의 네 가지 전압범위고 하였다. 충방전 실험결과, Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$의 용량은 각각 Co와 Ni의 $\delta$=0.1에서 최대를 보였다. Co 치환 조성 재료와 순물질 모두에서 최대의 용량을 보인 cut-off 전압대는 3.5~4.5V 이었는데 이때의 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$와 LiM $n_2$ $O_4$의 초기 충전용량과 초기 방전용량은 각각 118, 119mAh/g과 114, 104mAh/g 이었다. 또한 모든 cut-off 전압대에서 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$는 순수한 LiM $n_2$ $O_4$보다 더 높은 용량과 우수한 싸이클 성능을 보였으며 그 결과는 밀착형 전지구성에서도 일치하였다.하였다.