• Economic and Environmental Geology
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• v.50 no.6
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• pp.545-554
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• 2017

Birnessite is one of the dominant Mn (oxyhydr)oxide phases commonly found in soil and deep ocean environments. It typically occurs as nano-sized and poorly crystalline aggregates in the natural environment. It is well known that birnessite participates in a wide variety of bio/geochemical reactions as a reactive mineral phase with structural defects, cation vacancies, and mixed valences of structural Mn. These various bio/geochemical reactions control not only the fate and transport of inorganic and organic substances in the environment, but also the formation of diverse Mn (oxyhydr)oxides through birnessite transformation. This review assessed and discussed about the phase transformation of birnessite under a wide range of environmental conditions and about the potential geochemical factors controlling the corresponding reactions in the literature. Birnessite transformation to other types of Mn (oxyhydr)oxides were affected by dissolved Mn(II), dissolved oxygen, solution pH, and co-existing cation (i.e., $Mg^{2+}$). However, there still have been many issues to be unraveled on the complex bio/geochemical processes involved in the phase transformation of birnessite. Future work on the detail mechanisms of birnessite transformation should be further investigated.

• Journal of the Korean Applied Science and Technology
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• v.23 no.3
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• pp.223-229
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• 2006

Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at $450^{\circ}C$, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by $O_2-TPD$ and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the $O_2-TPD$ result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around $800^{\circ}C$.

• Journal of the Mineralogical Society of Korea
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• v.27 no.4
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• pp.197-205
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• 2014

Study area (Jikjeon-ri) is located in south end of the Hadong anorthositic rocks. And along the south-western boundary, diorite intruded the Hadong anorthosite. Ilmenite ore bodies are extended in both anorthosite and diorite. And their occurrence in the diorite are not studied yet. While no particular textures are found in the ilmenite within the anorthosite, the ilmenite within the diorite shows characteristic exsolution texture, that is, ilmenite phases are separated into rutile and Fe-oxide and the ilmenite and Fe-oxide. MnO composition in ilmenite ratios are 2.14~3.74wt%, it has higher composition in diorite than that in anorthosite. The plagioclase composition display andesine ($An_{28.7-42.9}$) in the diorite and labradorite ($An_{57.1-72.8}$) in the anorthosite in composition. The exsolution of ilmenite has been developed during the cooling of partly melted ilmenite into rutile and Fe-oxides which is related to the intrusion of the diorite.

• Journal of the Korean Magnetics Society
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• v.13 no.2
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• pp.47-52
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• 2003

Ferromagnetic tunnel junctions were fabricated by dc magnetron sputtering and plasma oxidation process. The local transport properties of the ferromagnetic tunnel junctions were studied using contact-mode Atomic Force Microscopy (AFM) and the local current-voltage analysis. Tunnel junctions with the structure of sub./Ta/Cu/Ta/NiFe/Cu/Mn$\_$75/Ir$\_$25//Co$\_$70/Fe$\_$30//Al-oxide were prepared on thermally oxidized Si wafers. Al-oxide layers were formed with microwave excited plasma using radial line slot antenna (RLSA) for 5 and 7 sec. Kr gas was used as the inert gas mixed with $O_2$ gas for the plasma oxidization. No correlation between topography and current image was observed while they were measured simultaneously. The local current distribution was well identified with the distribution of local barrier height. Assuming the gaussian distribution of the local barrier height, the ferromagnetic tunnel junction with longer oxidation time was well fitted with the experimental results. As contrast, in the case of the shorter time oxidation junction, the current mainly flow through the low barrier height area for its insufficient oxygen. Such leakage current might result in the decrease of tunnel magnetoresistance (TMR) ratio.

• Bulletin of the Korean Chemical Society
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• v.35 no.12
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• pp.3553-3558
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• 2014

The reduced graphene oxide(rGO)/aluminum phosphate($AlPO_4$)-coated $LiMn_{1.5}Ni_{0.5}O_4$ (LMNO) cathode material has been developed by hydroxide precursor method for LMNO and by a facile solution based process for the coating with GO/$AlPO_4$ on the surface of LMNO, followed by annealing process. The amount of $AlPO_4$ has been varied from 0.5 wt % to 1.0 wt %, while the amount of rGO is maintained at 1.0 wt %. The samples have been characterized by X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. The rGO/$AlPO_4$-coated LMNO electrodes exhibit better cyclic performance compared to that of pristine LMNO electrode. Specifically, rGO(1%)/$AlPO_4$(0.5%)- and rGO(1%)/$AlPO_4$(1%)-coated electrodes deliver a discharge capacity of, respectively, $123mAhg^{-1}$ and $122mAhg^{-1}$ at C/6 rate, with a capacity retention of, respectively, 96% and 98% at 100 cycles. Furthermore, the surface-modified LMNO electrodes demonstrate higher-rate capability. The rGO(1%)/$AlPO_4$(0.5%)-coated LMNO electrode shows the highest rate performance demonstrating a capacity retention of 91% at 10 C rate. The enhanced electrochemical performance can be attributed to (1) the suppression of the direct contact of electrode surface with the electrolyte, resulting in side reactions with the electrolyte due to the high cut-off voltage, and (2) smaller surface resistance and charge transfer resistance, which is confirmed by total polarization resistance and electrochemical impedance spectroscopy.

• Nuclear Engineering and Technology
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• v.48 no.4
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• pp.997-1001
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• 2016

Conductive ceramics are being developed to replace current Pt anodes in the electrolytic reduction of spent oxide fuels in pyroprocessing. While several conductive ceramics have shown promising electrochemical properties in small-scale experiments, their long-term stabilities have not yet been investigated. In this study, the chemical stability of conductive $La_{0.33}Sr_{0.67}MnO_3$ in $LiCl-Li_2O$ molten salt at $650^{\circ}C$ was investigated to examine its feasibility as an anode material. Dissolution of Sr at the anode surface led to structural collapse, thereby indicating that the lifetime of the $La_{0.33}Sr_{0.67}MnO_3$ anode is limited. The dissolution rate of Sr is likely to be influenced by the local environment around Sr in the perovskite framework.

• Applied Biological Chemistry
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• v.37 no.5
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• pp.414-420
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• 1994

Birnessite, pyrolusite and hausmannite were synthesized and tested for the ability to oxidize Cr(III) to Cr(VI). These oxides differed in zero point of charge, surface area, and crystallinity. The kinetic study showed that Cr(III) oxidation on the Mn-oxide surface is a first-order reaction. The reaction rate was various for different oxide at different conditions. Generally the reaction by hausmannite, containing Mn(III), was faster than the others, and oxidation by pyrolusite was much slower. Solution pH and initial Cr(III) concentration had a significant effect on the reaction. Inhibited oxidation at higher pH and initial Cr(III) concentration could be due to the chance of Cr(III) precipitation or complexing on the oxide surface. Oxidations by birnessite and hausmannite were faster at lower pH, but pyrolusite exhibited increased oxidation capacity at higher pH in the range between 3.0 and 5.0. Reactions were also temperature sensitive. Although calculated activation energies for the oxidation reactions at pH 3.0 were higher than the general activation energy for diffusion, there is no experimental evidence to suggest which reaction is the rate limiting step.

• Journal of Electrochemical Science and Technology
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• v.13 no.2
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• pp.269-278
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• 2022

Utilization of high-voltage electrolyte additive(s) at a small fraction is a cost-effective strategy for a good solid electrolyte interphase (SEI) formation and performance improvement of a lithium-rich layered oxide-based high-energy lithium-ion cell by avoiding the occurrence of metal-dissolution that is one of the failure modes. To mitigate metal-dissolution, we explored fluorinated dual-additives of fluoroethylene carbonate (FEC) and di(2,2,2-trifluoroethyl)carbonate (DFDEC) for building-up of a good SEI in a 4.7 V full-cell that consists of high-capacity silicon-graphite composite (15 wt% Si/C/CF/C-graphite) anode and Li_1.13Mn_0.463Ni_0.203Co_0.203O₂ (LMNC) cathode. The full-cell including optimum fractions of dual-additives shows increased capacity to 228 mAhg^-1 at 0.2C and improved performance from the one in the base electrolyte. Surface analysis results find that the SEI stabilization of LMNC cathode induced by dual-additives leads to a suppression of soluble Mn²⁺-O formation at cathode surface, mitigating metal-dissolution event and crack formation as well as structural degradation. The SEI and structure of Si/C/CF/C-graphite anode is also stabilized by the effects of dual-additives, contributing to performance improvement. The data give insight into a basic understanding of cathode-electrolyte and anode-electrolyte interfacial processes and cathode-anode interaction that are critical factors affecting full-cell performance.

• Journal of the Korean Electrochemical Society
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• v.7 no.3
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• pp.131-137
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• 2004

Sol-gel method which provides better electrochemical and physiochemical properties compared to the solid-state method was used to synthesize the material of $LiFe_yMn_{2-y}O_4$. Fe was substituted to increase the structural stability so that the effects of the substitution amount and sintering temperature were analyzed. XRD was used for the structural analysis of produced material, which in turn, showed the same cubic spinel structure as $LiMn_2O_4$ despite the substitution of $Fe^{3+}$. During the synthesis of $LiFe_yMn_{2-y}O_4$, as the sintering temperature and the doping amount of Fe(y=0.05, 0.1, 0.2)were increased, grain growth proceeded which in turn, showed a high crystalline and a large grain size, certain morphology with narrow specific surface area and large pore volume distribution was observed. In order to examine the ability for the practical use of the battery, charge-discharge tests were undertaken. When the substitution amount of $Fe^{3+}\;into\;LiMn_2O_4$ increased, the initial discharge capacity showed a tendency to decrease within the region of $3.0\~4.2V$ but when charge-discharge processes were repeated, other capacity maintenance properties turned out to be outstanding. In addition, when the sintering temperature was $800\~850^{\circ}C$, the initial capacity was small but showed very stable cycle performance. According to EVS(electrochemical voltage spectroscopy) test, $LiFe_yMn_{2-y}O_4(y=0,\;0.05,\;0.1,\;0.2)$ showed two plateau region and the typical peaks of manganese spinel structure when the substitution amount of $Fe^{3+}$ increased, the peak value at about 4.15V during the charge-discharge process showed a tendency to decrease. From the previous results, the local distortion due to the biphase within the region near 4.15V during the lithium extraction gave a phase transition to a more suitable single phase. When the transition was derived, the discharge capacity decreased. However the cycle performance showed an outstanding result.

• Journal of the Korean Electrochemical Society
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• v.19 no.1
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• pp.1-8
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• 2016

Capacity of layered lithium nickel-cobalt-manganese oxide ($LiNi_{1-x-y}Co_xMn_yO_2$) cathode material can increase by raising the charge cut-off voltage above 4.3 V vs. $Li/Li^+$, but it is limited due to anodic instability of conventional electrolyte. We have been screening and evaluating various sulfone-based compounds of dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS) as electrolyte additives for high-voltage applications. Here we report improved cycling performance of $LiNi_{0.5}Co_{0.2}Mn_{0.3}O_2$ cathode by the use of dimethyl sulfone (DMS) additive under an aggressive charge condition of 4.6 V, compared to that in conventional electrolyte, and cathode-electrolyte interfacial reaction behavior. The cathode with DMS delivered discharge capacities of $198-173mAhg^{-1}$ over 50 cycles and capacity retention of 84%. Surface analysis results indicate that DMS induces to form a surface protective film at the cathode and inhibit metal-dissolution, which is correlated to improved high-voltage cycling performance.