• 제목/요약/키워드: 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.
    • 한국세라믹학회지
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    • 제47권1호
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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
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2011년도 제40회 동계학술대회 초록집
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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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GNP법에 의해 합성한 (La1-xSrx)Mn1+yO3−δ 분말의 출발물질에 따른 특성 (Effect of Starting Materials on the Characteristics of (La1-xSrx)Mn1+yO3−δ Powder Synthesized by GNP)

  • 이미재;김세기;지미정;최병현;박상선;이경희
    • 한국세라믹학회지
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    • 제44권1호
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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.

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

  • 김재원;이동영
    • 대한화학회지
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    • 제10권1호
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    • pp.32-42
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    • 1966
  • $CaCl_2$, CaO 및 $WO_3$로 構成되는 熔融鹽을 黑鉛 陽極과 鐵 陰極으로 電解하여 순수한 金屬텅스텐을 얻는 方法에 관하여 실험하였다. 電氣分解에 적합한 熔融浴을 選定하기 위하여 $CaCl_2$-CaO系와 $CaCl_2-CaWO_4$系에 관한 二相 狀態圖를 작성하였으며 同時에 $CaCl_2$$WO_3$와의 高溫下에서의 化學反應을 검토하여 安定한 電解浴을 얻기 위해서는 一定量의 CaO가 添加되어야 할 것임을 알 수 있었다. 炭素陽極을 사용하여 $WO_3$를 W와 CO로 분해시킬 때의 分解電壓은 -0.1 volt이었으며 熱力學的 計算에 의한 것은 -0.3 volt이었다. 熔融鹽을 電氣分解한 結果 金屬텅스텐이 100%에 가까운 電流效率로 電極에 析出되나 이는 陽極에서 二次的으로 발생하는 CO가스에 의하여 쉽게 WC등으로 변화하므로 순수한 텅스텐을 얻기 위해서는 電解浴의 溫度를 $1100^{\circ}C$이상으로 유지하여야 된다는 것을 알게 되었다. 電解浴의 組成은 可及的 低融點과 $WO_3$의 分解, $CaCl_2$의 蒸發 등을 억제하기 위해서는 $CaCl_2$ 100分에 대하여 CaO와 $WO_3$가 각 10 乃至 20分이 適切하였으며 CaO와 $WO_3$의 몰比率은 1이상이 요구되었다. 陰極 電流密度를 1~5 $amp/cm^2$의 範圍에서 變化시켜도 電流效率에 큰 影響이 없었다.

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The Study on the Trap Density in Thin Silicon Oxide Films

  • 강창수;김동진
    • 한국전기전자재료학회:학술대회논문집
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    • 한국전기전자재료학회 2000년도 춘계학술대회 논문집 전자세라믹스 센서 및 박막재료 반도체재료 일렉트렛트 및 응용기술
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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.
    • 한국결정성장학회지
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    • 제10권6호
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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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(Ba0.5Sr0.5)0.99Co0.2Fe0.8O3-δ(BSCF)의 합성 및 BSCF/GDC(Buffer)/ScSZ의 전기화학적 특성 (Synthesis of (Ba0.5Sr0.5)0.99Co0.2Fe0.8O3-δ (BSCF) and the Electrochemical Performance of the BSCF/GDC(Buffer)/ScSZ)

  • 임용호;황해진;문지웅;박선민;최병현;이미재
    • 한국세라믹학회지
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    • 제43권6호
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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.

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

  • 박성빈;강영호;황성찬;이한수;백승우;안도희
    • 방사성폐기물학회지
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    • 제13권4호
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    • pp.315-319
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    • 2015
  • 전해환원공정의 금속전환체로부터 우라늄을 회수하는 전해정련공정의 수율을 높이기 위해 고수율 전해정련장치가 개발되었다. 전해정련장치의 수율을 증대시키기 위해서는 고체음극에 전착되는 우라늄 덴드라이트를 음극 표면으로부터 효율적으로 회수할 수 있어야 한다. 철강 재료의 음극을 고체음극으로 사용하면, 우라늄 덴드라이트가 전착되어 쉽게 떨어지고 않고 고착 되어 점착계수(sticking coefficient)가 높아진다. 본 연구에서는 효율적으로 고체음극의 점착계수를 낮출 수 있는 진동 탈리법을 개발하였고 이를 적용하였다. 고체음극에 진동을 가함으로써 고체 표면에서 우라늄 전착물이 흑연음극의 자발특성과 유사하게 효율적으로 탈리됨을 확인하였다. 이러한 진동모드에 의한 고체음극에서의 전착물의 탈리 특성을, 고수율 전해정련장치 개념으로 개발한 흑연음극의 자발탈리 특성과 비교 검토하였다. 그리고 우라늄 덴드라이트의 진동 탈리에 대한 인가전류밀도와 진동 스트로크에 의한 영향 등을 고찰하였다.

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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    • 제8권2호
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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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    • 제12권1호
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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.