• 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.

• Resources Recycling
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• v.11 no.1
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• pp.3-8
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• 2002

In order to make the high purity Mn$_3$O$_4$powder for the raw material of soft ferrite, Mn is extracted from the dust and the extracted solution is refined. The dust is generated in producing a medium-low carbon ferromanganese and contains 90% Mn$_3$O$_4$. Mn$_3$O$_4$in the dust was reduced into MnO by roasting with charcoal. Injection of the 180g/L of the reduced dust into 4N HCI solution increased pH of the leaching solution higher than 5 and then a ferric hydroxide was precipitated. Because the ferric hydroxide co-precipitates with Si ion etc, Fe and Si ion was removed from the solution and the about 10% Mn solution was obtained. The solution was diluted with water to Mn-15000 ppm and $NH_4$F was injected into the diluted solution at $70^{\circ}C$ to the F-3000 ppm. As a result, Ca ion is precipitated as $CaF_2$and the residual concentration of Ca was 14 ppm. Injection of the equivalent (NH$1.5M_4$)$_2$$CO_3$solution as 2 L/min at $25^{\circ}C$ into the above solution precipitated a fine and high purity $MnCO_3$powder. The deposition was filtrated and roasted at $1000^{\circ}C$ for 2 hours. As a result, $MnCO_3$powder is converted into $Mn_3$$O_4$powder and it had $8.2\mu$m of median size. The final production is above 99% $Mn_3$$O_4$powder and it satisfied the requirement of high purity $Mn_3$$O_4$powder for a raw material of soft ferrite.

• Journal of the Korean Applied Science and Technology
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• v.20 no.1
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• pp.33-43
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• 2003

$LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

• Journal of Hydrogen and New Energy
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• v.14 no.3
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• pp.268-275
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• 2003

The water-splitting process by the metal oxides using solar heat is one of the hydrogen production method. The hydrogen production process using the metal oxides (NiFe2O4/NiAl2O4,CoFe2O4/CoAl2O4, CoMnNiFerrite, CoMnSnFerrite, CoMnZnFerrite, CoSnZnFerrite) was carried out by two steps. The first step was carried out by the CH4-reduction to increase activation of metal oxides at operation temperature. And then, it was carried out the water-splitting reaction using the water at operation temperature for the second step. Hydrogen was produced in this step. The production rates of H2 were 110, 160, 72, 29, 17, $21m{\ell}/hr{\cdot}g-_{Metal\;Oxide}$ for NiFe2O4/NiAl2O4, CoFe2O4/CoAl2O4, CoMnNiFerrite, CoMnSnFerrite, CoMnZnFerrite, CoSnZnFerrite respectively in the second step. CoFe2O4/CoAl2O4 had higher H2 production rate than the other metal oxides.

• Journal of the Korean Magnetics Society
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• v.5 no.5
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• pp.552-555
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• 1995

The magnetic properties of Mg-Mn ferrites were investigated in the composition range of $Mg_{a}Mn_{b}Fe_{c}O_{4\pm\delta}$ (a+b+c=3) with the addition of $Al_{2}O_{3}$. In $MgO-MnO-Fe_{2}O_{3}$ ternary system, the spinel single phase existed within the composition range of MgO-50 mol%, MnO-70 mol% and $Fe_{2}O_{3}-60\;mol%$. The saturation magnetic flux density increased with the increase of $Fe_{2}O_{3}$ content and showed the maximum at the stoichiometric composition of $(Mg,Mn)Fe_{2}O_{4}$. In $Mg_{x}Mn_{1-x}Fe_{2}O_{4}(x=0.2~0.8)$ system, the saturation magnetic flux density showed the maximum at $Mg_{0.2}Mn_{0.8}Fe_{2}O_{4}$. The addition of $Al_{2}O_{3}$ resulted in the decrease of saturation magnetic flux density but increased the electrical resistivity.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.12 no.1
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• pp.537-544
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• 2011

This work was conducted to investigate the oxidation characteristics of methane having the highest ignition temperature among the other hydrocarbon gases using transition metal catalysts. The catalyst used for methane oxidation was manganese oxide having a various oxidation number, such as MnO, $MnO_2$, $Mn_2O_3$, $Mn_3O_4$, $Mn_4O_5$. The manganese oxide(MnxOy) catalyst is impregnated on $TiO_2$, $Al_2O_3$ for methane oxidation. To enhanced both of activity and life time of catalysts, Ni and Co was used as a promoter. In this study, various co-catalysts were synthesized by using excess wet impregnation method. The effect of reaction temperature and space velocity was measured to calculate the activity of catalysts such as, activation energy of $T_{50}$, and $T_{90}$. The life time of bi-metallic manganese mixture, such as Mn-Co and Mn-Ni catalysts, were increased more 10 % than manganese oxide catalyst, but activity of those was decreased slightly.

• Journal of the Korean Ceramic Society
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• v.38 no.12
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• pp.1174-1179
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• 2001

Mn-Co-Ni oxide system has been used as the NTC thermistors for normal temperature applications. Mn-Co-Ni oxide-based thermistors with various compositions were sintered at 1250$^{\circ}C$ for 3 hours and then maintained at 1000$^{\circ}C$ for 3 hours. The electrical properties of the thermistors fabricated were measured. In particular the MCN622 composition (Mn$_3$O$_4$60 wt%, Co$_3$O$_4$20 wt%, NiO 20wt%) exhibited the lowest resistivity and relatively high B constant. The MCN721 composition (Mn$_3$O$_4$70wt%, Co$_3$O$_4$20wt%, NiO 10 wt%) showed the higher resistivity than any other compositions. The aging properties of each composition showed comparatively stable characteristics within ${\pm}$2%.

• Journal of Magnetics
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• v.21 no.1
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• pp.40-45
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• 2016

Nickel substituted nano-sized ferrite powders, $Co_{1-x}Ni_xFe_2O_4$, $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$), were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently compared. The lattice constants decreased as quantity of nickel substitution increased, while the particle size decreased in $Co_{1-x}Ni_xFe_2O_4$ ferrite but increased for the $Mn_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites. For the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-x}Ni_xFe_2O_4$ ($0.0{\leq}x{\leq}0.2$) ferrite powders, the $M{\ddot{o}}ssbauer$ spectra could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of $Mn_{0.8}Zn_{0.1}Ni_{0.1}Fe_2O_4$ consisted of two Zeeman sextets and one single quadrupole doublet due to the ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explain the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. The saturation magnetization decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. The coercivity decreased in the $Co_{1-x}Ni_xFe_2O_4$ and $Mn_{1-2x}Zn_xNi_xFe_2O_4$ ferrites but increased in the $Mn_{1-x}Ni_xFe_2O_4$ ferrite with nickel substitution. These variations could thus be explained by using the site distribution equations, particle sizes and spin magnetic moments of the substituted ions.

• Journal of the Korean Magnetics Society
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• v.16 no.1
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• pp.23-27
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• 2006

By substituting Mn or Cr for Co in inverse spinel $CoFe_2O_4,\;Mn_xCo_{1-x}Fe_2O_4\;and\;Cr_xCo_{1-x}Fe_2O_4$ and thin films were prepared by sol-gel method and their structural and magnetic properties were investigated. X-ray diffraction indicates that the cubic lattice constant increase for the Mn substitution while it hardly changes for the Cr substitution. Substitution of $Mn^{2+}$ for octahedral $Co^{2+}$ sites can explain the increase of lattice constant in $Mn_xCo_{1-x}Fe_2O_4$. On the other hand, Substitution of $Cr^{3+}$ for octahedral $Co^{2+}$ and subsequent reduction of $Fe^{3+}$ ion into $Fe^{2+}$ are expected to happen. Mossbauer spectroscopy measurements on $Cr_xCo_{1-x}Fe_2P_4$ indicate the existence of tetrahedral $Fe^{2+}$ ions that are created through reduction of tetrahedral $Fe^{3+}$ ions in order to compensate charge imbalance happened by $Cr^{3+}$ substitution for octahedral $Co^{2+}$ sites. On the other hand, no $Fe^{2+}$ ions were detected by Mossbauer spectroscopy for $Mn_xCo_{1-x}Fe_2O_4$. A migration of $Fe^{3+}$ ions from octahedral to tetrahedral sites In $Mn_xCo_{1-x}Fe_2O_4$ was detected by Mossbauer spectroscopy for x>0.47. Vibrating sample magnetometry measurements on the samples at room temperature revealed that the saturation magnetization increases by Mn and Cr substitution for certain range of x, qualitatively explainable in terms of the comparison of spin magnetic moment among the related transition-metal ions.

• Journal of Magnetics
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• v.21 no.3
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• pp.308-314
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• 2016

Cobalt-, zinc-, and nickel-zinc-substituted nano-size manganese ferrite powders, $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, $Mn_{0.8}Zn_{0.2}Fe_2O_4$ and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$, were fabricated using a sol-gel method, and their crystallographic and magnetic properties were subsequently studied. The $MnFe_2O_4$ ferrite powder annealed at temperatures above 523 K exhibited a spinel structure, and the particle size increased as the annealing temperature increased. All ferrites annealed at 773 K showed a single spinel structure, and the lattice constants and particle size decreased with the substitution of Co, Zn, and Ni-Zn. The $M{\ddot{o}}ssbauer$ spectrum of the $MnFe_2O_4$ ferrite powder annealed at 523 K only showed a doublet due to its superparamagnetic phase, and the $M{\ddot{o}}ssbauer$ spectra of the $MnFe_2O_4$, $Mn_{0.8}Co_{0.2}Fe_2O_4$, and $Mn_{0.8}Zn_{0.2}Fe_2O_4$ ferrite powders annealed at 773 K could be fitted as the superposition of two Zeeman sextets due to the tetrahedral and octahedral sites of the $Fe^{3+}$ ions. However, the $M{\ddot{o}}ssbauer$ spectrum of the $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$ ferrite powder annealed at 773 K consisted of two Zeeman sextets and one quadrupole doublet due to its ferrimagnetic and paramagnetic behavior. The area ratio of the $M{\ddot{o}}ssbauer$ spectra could be used to determine the cation distribution equation, and we also explained the variation in the $M{\ddot{o}}ssbauer$ parameters by using this cation distribution equation, the superexchange interaction and the particle size. Relative to pure $MnFe_2O_4$, the saturation magnetizations and coercivities were larger in $Mn_{0.8}Co_{0.2}Fe_2O_4$ and smaller in $Mn_{0.8}Zn_{0.2}Fe_2O_4$, and $Mn_{0.8}Ni_{0.1}Zn_{0.1}Fe_2O_4$. These variations could be explained using the site distribution equations, particle sizes and magnetic moments of the substituted ions.