• Title/Summary/Keyword: oxide cathode

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Materials Chemical Point of View for Durability Issues in Solid Oxide Fuel Cells

  • Yokokawa, Harumi;Horita, Teruhisa;Yamaji, Katsuhiko;Kishimoto, Haruo;Brito, M.E.
    • Journal of the Korean Ceramic Society
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    • v.47 no.1
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    • pp.26-38
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    • 2010
  • Degradation in Solid Oxide Fuel Cell performance can be ascribed to the following fundamental processes from the materials chemical point of view; that is, diffusion in solids and reaction with gaseous impurities. For SOFC materials, diffusion in solids is usually slow in operation temperatures $800\sim1000^{\circ}C$. Even at $800^{\circ}C$, however, a few processes are rapid enough to lead to some degradations; namely, Sr diffusion in doped ceria, cation diffusion in cathode materials, diffusion related with metal corrosion, and sintering of nickel anodes. For gaseous impurities, chromium containing vapors are important to know how the chemical stability of cathode materials is related with degradation of performance. For LSM as the most stable cathode among the perovskite-type cathodes, electrochemical reduction reaction of $CrO_3$(g) at the electrochemically active sites is crucial, whereas the rest of the cathodes have the $SrCrO_4$ formation at the point where cathodes meet with the gases, leading to rather complicated processes to the degradations, depending on the amount and distribution of reacted Cr component. These features can be easily generalized to other impurities in air or to the reaction of nickel anodes with gaseous impurities in anode atmosphere.

Electrochemical properties of all solid state Li/LiPON/Sn-substituted LiMn2O4 thin film batteries

  • Kong, Woo-Yeon;Yim, Hae-Na;Yoon, Seok-Jin;Nahm, Sahn;Choi, Ji-Won
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.409-409
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    • 2011
  • All solid-state thin film lithium batteries have many applications in miniaturized devices because of lightweight, long-life, low self-discharge and high energy density. The research of cathode materials for thin film lithium batteries that provide high energy density at fast discharge rates is important to meet the demands for high-power applications. Among cathode materials, lithium manganese oxide materials as spinel-based compounds have been reported to possess specific advantages of high electrochemical potential, high abundant, low cost, and low toxicity. However, the lithium manganese oxide has problem of capacity fade which caused by dissolution of Mn ions during intercalation reaction and phase instability. For this problem, many studies on effect of various transition metals have been reported. In the preliminary study, the Sn-substituted LiMn2O4 thin films prepared by pulsed laser deposition have shown the improvement in discharge capacity and cycleability. In this study, the thin films of LiMn2O4 and LiSn0.0125Mn1.975O4 prepared by RF magnetron sputtering were studied with effect of deposition parameters on the phase, surface morphology and electrochemical property. And, all solid-state thin film batteries comprised of a lithium anode, lithium phosphorus oxy-nitride (LiPON) solid electrolyte and LiMn2O4-based cathode were fabricated, and the electrochemical property was investigated.

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Effect of Starting Materials on the Characteristics of (La1-xSrx)Mn1+yO3−δ Powder Synthesized by GNP (GNP법에 의해 합성한 (La1-xSrx)Mn1+yO3−δ 분말의 출발물질에 따른 특성)

  • Lee, Mi-Jai;Kim, Sei-Ki;Jee, Mi-Jung;Choi, Byung-Hyun;Park, Sang-Sun;Lee, Kyung-Hee
    • Journal of the Korean Ceramic Society
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    • v.44 no.1 s.296
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    • pp.52-57
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    • 2007
  • We synthesized $(La_{1-x}Sr_x)MnO_3$ as a cathode for SOFC by glycine nitrate process (GNP) and knew the different properties of $(La_{1-x}Sr_x)MnO_3$ by using nitrate solution and oxide solution as a starting material. In case of using nitrate solution as a starting material, main crystal phase peak of $LaMnO_3$ increased as Sr content added up and a peak of $Sr_2MnO_4\;and\;La_2O_3$ was showed as a secondary phase. We added Mn excess to control a crystal phase. In this case, the electrical conductivity had a high value 210.3 S/cm at $700^{\circ}C$. On the other side, when we used oxide solution as a starting material, we found main crystal phase of $LaMnO_3$ to increase as Sr content added up and a peak of $La_2O_3$ as a secondary phase. Similary, we added Mn excess to control a crystal phase in this case. We knew $(La,Sr)MnO_3$ powder to sinter well and the electrical conductivity of the sintered body at $1200^{\circ}C$ for 4 h was 152.7 S/cm at $700^{\circ}C$. The sintered $(La,Sr)MnO_3$ powder at $1000^{\circ}C$ for 4 h got the deoxidization peak, depending on the temperature and in case of using nitrate solution as a starting material, the deoxidization peak was showed at $450^{\circ}C$ which is lower than used a oxide solution as a starting material. As a result, when $(La,Sr)MnO_3$ powder was synthesized to add Mn excess and to use nitrate solution as a starting material, we found it to have the higher deoxidization property and considered it as a cathode for SOFC properly. And we found it to have different electrical conductivity the synthesized $(La,Sr)MnO_3$ powder by using different starting materials like nitrate solution and oxide solution which influence a sintering density and crystal phase.

Electrowinning of Tungsten From Fused Bath Composed of Calcium Chloride, Calcium Oxide and Tungstic Oxide (텅그스텐의 熔融鹽電解)

  • Kim, Jae-Won;Lee, Dong-Nyung
    • Journal of the Korean Chemical Society
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    • v.10 no.1
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    • pp.32-42
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    • 1966
  • The electrolysis of tungstic oxide dissolved in the bath of calcium chloride and calcium oxide was studied to produce metallic tungsten using carbon as anode and iron as cathode in the temperature range of 900^{\circ}$ to $1200^{\circ}C$. The binary phase diagrams $CaCl_2$-CaO and $CaCl_2-CaWO_4$ systems were constructed to determine the suitability of bath composition and the range of temperatures for the electrolysis. As $WO_3$ reacted with $CaCl_2$ to form oxychloride in the fused salt, the addition of the proper amount of CaO was necessary to avoid the loss of $WO_3$. The optimum compositions of fused bath were $CaCl_2$ 100 parts, CaO and $WO_3$ each 10 to 20 parts, with the CaO, $WO_3$ ratio greater than unity, to keep freezing point low and to prevent the vaporization of $CaCl_2$. The observed decomposition voltage at which $WO_3$ decomposes to W and CO was-0.1 volt, whereas the calculated was -0.3 volt. Metallic tungsten deposited at the cathode reacted easily with CO formed secondarily at the anode surface, to form WC below $1050^{\circ}C$, so that the cell temperature should be above $1050^{\circ}C$. The effects of cathode current densities on current efficiency were minor in the range of 1 to 5 $amp/cm^2$.

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The Study on the Trap Density in Thin Silicon Oxide Films

  • Kang, C.S.;Kim, D.J.
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2000.04b
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    • pp.43-46
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    • 2000
  • In this paper, the stress and transient currents associated with the on and off time of applied voltage were used to measure the density and distribution of high voltage stress induced traps in thin silicon oxide films. The transient currents were due to the discharging of traps generated by high stress voltage in the silicon oxides. The trap distributions were relatively uniform near both cathode and anode interface. The trap densities were dependent on the stress polarity. The stress generated trap distributions were relatively uniform the order of $10^{11}\sim10^{21}$[states/eV/$cm^2$] after a stress. The trap densities at the oxide silicon interface after high stress voltages were in the $10^{10}\sim10^{13}$[states/eV/$cm^2$]. It appear that the stress and transient current that flowed when the stress voltage were applied to the oxide was caused by carriers tunneling through the silicon oxide by the high voltage stress generated traps.

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Transient trap density in thin silicon oxides

  • Kang, C.S.;Kim, D.J.;Byun, M.G.;Kim, Y.H.
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.10 no.6
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    • pp.412-417
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    • 2000
  • High electric field stressed trap distributions were investigated in the thin silicon oxide of polycrystalline silicon gate metal oxide semiconductor capacitors. The transient currents associated with the off time of stressed voltage were used to measure the density and distribution of high voltage stress induced traps. The transient currents were due to the discharging of traps generated by high stress voltage in the silicon oxides. The trap distributions were relatively uniform near both cathode and anode interface in polycrystalline silicon gate metal oxide semiconductor devices. The stress generated trap distributions were relatively uniform the order of $10^{11}$~$10^{12}$ [states/eV/$\textrm{cm}^2$] after a stress. The trap densities at the oxide silicon interface after high stress voltages were in the $10^{10}$~$10^{13}$ [states/eV/$\textrm{cm}^2$]. It was appeared that the transient current that flowed when the stress voltages were applied to the oxide was caused by carriers tunneling through the silicon oxide by the high voltage stress generated traps.

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Synthesis of (Ba0.5Sr0.5)0.99Co0.2Fe0.8O3-δ (BSCF) and the Electrochemical Performance of the BSCF/GDC(Buffer)/ScSZ ((Ba0.5Sr0.5)0.99Co0.2Fe0.8O3-δ(BSCF)의 합성 및 BSCF/GDC(Buffer)/ScSZ의 전기화학적 특성)

  • Lim, Yong-Ho;Hwang, Hae-Jin;Moon, Ji-Woong;Park, Sun-Min;Choi, Byung-Hyun;Lee, Mi-Jai
    • Journal of the Korean Ceramic Society
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    • v.43 no.6 s.289
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    • pp.369-375
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    • 2006
  • [ $(Ba_{0.5}Sr_{0.5})_{0.99}Co_{x}Fe_{1-x}O_{3-{\delta}}$ ] [x=0.8, 0.2](BSCF) powders were synthesized by a Glycine-Nitrate Process (GNP) and the electrochemical performance of the BSCF cathode on a scandia stabilized zirconia, $[(Sc_{2}O_3)_{0.11}(ZrO_2)_{0.89}]-1Al_{2}O_3$ was investigated. In order to prevent unfavorable solid-state reactions between the cathode and zirconia electrolyte, a GDC ($Gd_{0.1}Ce_{0.9}O_{2-{delta}}$) buffer layer was applied on ScSZ. The BSCF (x = 0.8) cathode formed on GDC(Buffer)/ScSZ(Disk) showed poor electrochemical property, because the BSCF cathode layer peeled off after the heat-treatment. On the other hand, there were no delamination or peel off between the BSCF and GDC buffer layer, and the BSCF (x = 0.2) cathode exhibited fairly good electrochemical performances. It was considered that the observed phenomenon was associated with the thermal expansion mismatch between the cathode and buffer layer. The ohmic resistance of the double layer cathode was slightly lower than that of the single layer BSCF cathode due to the incorporation of platinum particle into the BSCF second layer.

Study on the Vibrational Scraping of Uranium Product from a Solid Cathode of Electrorefiner (진동 탈리에 의한 전해정련 고체음극에서의 우라늄 생성물 회수 연구)

  • Park, Sungbin;Kang, Young-Ho;Hwang, Sung Chan;Lee, Hansoo;Paek, Seungwoo;Ahn, Do-Hee
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.13 no.4
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    • pp.315-319
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    • 2015
  • A high-throughput electrorefiner has been developed for commercialization use by enhancing the uranium recovery from the reduced metal which is produced from the oxide reduction process. It is necessary to scrap and effectively collect uranium dendrites from the surface of the solid cathode for high yield. When a steel electrode is used as the cathode in the electrorefining process, uranium is deposited and regularly stuck to the steel cathode during electrorefining. The sticking coefficient of a steel cathode is very high. In order to decrease the sticking coefficient of the steel cathode effectively, vibration mode was applied to the electrode in this study. Uranium dendrites were scraped and fell apart from the steel cathode by a vibration force. The vibrational scraping of the steel cathode was compared to the self-scraping of the graphite cathode. Effects of the applied current density and the vibration stroke on the scraping of the uranium dendrites were also investigated.

Surface Modification of a Li[Ni0.8Co0.15Al0.05]O2 Cathode using Li2SiO3 Solid Electrolyte

  • Park, Jin Seo;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.8 no.2
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    • pp.101-106
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    • 2017
  • $Li_2SiO_3$ was used as a coating material to improve the electrochemical performance of $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$. $Li_2SiO_3$ is not only a stable oxide but also an ionic conductor and can, therefore, facilitate the movement of lithium ions at the cathode/electrolyte interface. The surface of the $Li_2SiO_3$-coated $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ was covered with island-type $Li_2SiO_3$ particles, and the coating process did not affect the structural integrity of the $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ powder. The $Li_2SiO_3$ coating improved the discharge capacity and rate capability; moreover, the $Li_2SiO_3$-coated electrodes showed reduced impedance values. The surface of the lithium-ion battery cathode is typically attacked by the HF-containing electrolyte, which forms an undesired surface layer that hinders the movement of lithium ions and electrons. However, the $Li_2SiO_3$ coating layer can prevent the undesired side reactions between the cathode surface and the electrolyte, thus enhancing the rate capability and discharge capacity. The thermal stability of $Li[Ni_{0.8}Co_{0.15}Al_{0.05}]O_2$ was also improved by the $Li_2SiO_3$ coating.

Electrochemical Properties of Cathode according to the Type of Sulfide Electrolyte and the Application of Surface Coating

  • Yoon, Da Hye;Park, Yong Joon
    • Journal of Electrochemical Science and Technology
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    • v.12 no.1
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    • pp.126-136
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    • 2021
  • The electrochemical performance of all-solid-state cells (ASSCs) based on sulfide electrolytes is critically affected by the undesirable interfacial reactions between oxide cathodes and sulfide electrolytes because of the high reactivity of sulfide electrolytes. Based on the concept that the interfacial reactions are highly dependent on the type of sulfide electrolyte, the electrochemical properties of the ASSCs prepared using three types of sulfide electrolytes were observed and compared. The Li2MoO4-LiI coating layer was also introduced to suppress the interfacial reactions. The cells using argyrodite electrolyte exhibited a higher capacity and Coulombic efficiency than the cells using 75Li2S-22P2S5-3Li2SO4 and Li7P3S11 electrolytes, indicating that the argyrodite electrolyte is less reactive with cathodes than other electrolytes. Moreover, the introduction of Li2MoO4-LiI coating on the cathode surface significantly enhanced the electrochemical performance of ASSCs because of the protection of coating layer. Pulverization of argyrodite electrolyte is also effective in increasing the capacity of cells because the smaller size of electrolyte particles improved the contact stability between the cathode and the sulfide electrolyte. The cyclic performance of cells was also enhanced by pulverized electrolyte, which is also associated with improved contact stability at the cathode/electrolyte. These results show that the introduction of Li2MoO4-LiI coating and the use of pulverized sulfide electrolyte can exhibit a synergic effect of suppressed interfacial reaction by the coating layer and improved contact stability owing to the small particle size of electrolyte.