• 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.3 no.4
• /
• pp.178-184
• /
• 2012

A porous nickel (P-Ni) substrate was prepared by selective leaching of zinc from pressed pellets containing powders of Ni & Zn in 4 M NaOH solution. Anodic deposition of manganese oxide onto the porous Ni substrate ($MnO_x$/P-Ni) formed nano-flakes of manganese oxide layers as revealed in SEM studies. Pseudocapacitance of this oxide electrode was evaluated by cyclic voltammetry (CV) and chronopotentiometry (CHP) in 2 M NaOH solution. The specific capacitance of the Mn oxide electrode was as high as 1515 F $g^{-1}$, which was ten times higher than Mn oxide deposited on a flat Ni-ribbon. 80% of capacity was retained after 200 charge/discharge cycles. The system showed no loss of activity in dry form over period of days. The impedance studies indicated highly conducting $MnO_x$/P-Ni substance and the obtained specific capacitance from impedance data showed good agreement with the charge/discharge measurements.

• Journal of Surface Science and Engineering
• /
• v.50 no.5
• /
• pp.386-391
• /
• 2017

Two kinds of steels whose compositions were Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) were centrifugally cast, and oxidized at $900^{\circ}C$ for 50-350 h in order to find the effect of sulfur on the high-temperature oxidation of Fe-34.4Cr-14.5Ni-2.5Mo-0.4W-0.4Mn-0.5Si-(0.009 or 0.35)S (wt.%) alloys. These alloys formed oxide scales that consisted primarily of $Cr_2O_3$ as the major oxide and $Cr_2MnO_4$ as the minor one through preferential oxidation of Cr and Mn. They additionally formed $SiO_2$ particles around the scale/alloy interface as well as inside the matrices. The high affinity of Mn with S led to the formation of scattered MnS inclusions particularly in the 0.35S-containing cast alloy. Sulfur was harmful to the oxidation resistance, because it deteriorated the scale/alloy adherence so as to accerelate the adherence and compactness of the formed scales.

• Journal of Magnetics
• /
• v.18 no.1
• /
• pp.21-25
• /
• 2013

Nickel substituted manganese ferrites, $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.6$), were fabricated by sol-gel method. The effects of sintering and substitution on their crystallographic and magnetic properties were studied. X-ray diffractometry of $Mn_{0.6}Ni_{0.4}Fe_2O_4$ ferrite sintered above 523 K indicated a spinel structure; particles increased in size with hotter sintering. The M$\ddot{o}$ssbauer spectrum of this ferrite sintered at 523 K could be fitted as a single quadrupole doublet, indicative of a superparamagnetic phase. Sintering at 573 K led to spectrum fitted as the superposition of two Zeeman sextets and a single quadrupole doublet, indicating both ferrimagnetic and paramagnetic phase. Sintering at 673 K and at 773 K led to spectra fitted as two Zeeman sextets due to a ferrimagnetic phase. The saturation magnetization and the coercivity of $Mn_{0.6}Ni_{0.4}Fe_2O_4$ ferrite sintered at 773 K were 53.05 emu/g and 142.08 Oe. In $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.6$) ferrites, sintering of any composition at 773 K led to a single spinel structure. Increased Ni substitution decreased the ferrites' lattice constants and increased their particle sizes. The M$\ddot{o}$ssbauer spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and the octahedral sites of the $Fe^{3+}$ ions. The variations of saturation magnetization and coercivity with changing Ni content could be explained using the changes of particle size.

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

• 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.

• Journal of Electrochemical Science and Technology
• /
• v.9 no.2
• /
• pp.93-98
• /
• 2018

$MnO_2$, a metal oxide used as an electrode material in electrochemical capacitors (EDLCs), has been applied in binary oxide and conducting polymer hybrid electrodes to increase their stability and capacitance. We developed a method for electrodepositing Mn-Ni oxide/PANI, Mn-Ni oxide/PEDOT, and Mn-Ni-Ru oxide/PEDOT films on carbon paper in a single step using a mixed bath. Mn-Ni oxide/PEDOT and Mn-Ni-Ru oxide/PEDOT electrodes used in an electro-osmotic pump (EOP) have shown better efficiency compared to Mn-Ni oxide and Mn-Ni oxide/PANI electrodes through testing in water as a pumping solution. EOP using a Mn-Ni-Ru oxide/PEDOT electrode was also tested in a 0.5 mM $Li_2SO_4$ solution as a pumping solution to confirm the effect of the $Li^+$ insertion/de-insertion reaction of Ruthenium oxide on the EOP. Experimental results show that the flow rate increases with the increase in current in a 0.5 mM $Li_2SO_4$ solution compared to that obtained when water was used as a pumping solution.

• Korean Chemical Engineering Research
• /
• v.55 no.2
• /
• pp.242-246
• /
• 2017

The application of composite cathode materials including $LiFePO_4$ (lithium iron phosphate) of olivine crystal structure, which has high thermal stability, were investigated as alternatives for hybrid battery-capacitors with a $LiMn_2O_4$ (spinel crystal structure) cathode, which exhibits decreased performance at high temperatures due to Mn-dissolution. However, these composite cathode materials have been shown to have a reduction in capacity by conducting life cycle experiments in which a $LiFePO_4$/activated carbon cell was charged and discharged between 1.0 V and 2.3 V at two temperatures, $25^{\circ}C$ and $60^{\circ}C$, which caused a degradation of the anode due to the lowered voltage in the anode. To avoid the degradation of the anode, composite cathodes of $LiFePO_4/LiMn_2O_4$ (50:50 wt%), $LiFePO_4$/activated carbon (50:50 wt%) and $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ (50:50 wt%) were prepared and the life cycle experiments were conducted on these cells. The composite cathode including $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ of layered crystal structure showed stable voltage behavior. The discharge capacity retention ratio of $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ was about twice as high as that of a $LiFePO_4/LiMn_2O_4$ cell at thermal stability experiment for a duration of 1,000 hours charged at 2.3 V and a temperature of $80^{\circ}C$.

• Journal of the Korean Ceramic Society
• /
• v.20 no.4
• /
• pp.315-323
• /
• 1983

Effect of NiO and $MnO_2$ addtivies on the dielectric piezoelectrics and polarization-reversal properties of $(Pb_{0.936} La_{0.064})$$(Zr_{0.60}Ti_{0.40})O_3$ ceramics have been investigated. The specimens were prepared by the mixed oxide techni-que and atmosphere sintering method. The room temperature X-ray diffraction studies show that perfect perovskite solution with tetragonal structure was obtained from PLZT and its additives. The dielectric constant and dissipation factor decreased with the addition of both NiO and $MnO_2$ The Curie of Curie temperature was not observed but they displayed broadened maxima. The planar coupling factor was improved by addition of NiO and also increased with increasing sintering time carried out at 105$0^{\circ}C$ Addition of $MnO_2$ yielded a markedly high mechanical quality factor. The space-charge field decreased with the addition of NiO but increased with the addition of $MnO_2$ The planar coupling factor and space-charge field showed same dependence on the additivies. The tetragonality Curie temperature and planar coupling factor of $(Pb_{0.936} La_{0.064})$$(Zr_{0.60}Ti_{0.40})O_3$ were higher than those of $(Pb_{0.936} La_{0.064})$$(Zr_{0.568}NU_{0.032}Ti_{0.40})_{0.984}O_3$ but the grain size lattic parameter dielectric constant dissipation factor mechanical quality factor and space-charge field of the former were lower than those of the latter.

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