• Title/Summary/Keyword: oxide cathode

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Cathode Materials LaNi1−xCuxO3 for Low Temperature Solid Oxide Fuel Cells

  • Sun, Juncai;Wang, Chengli;Li, Song;Ji, Shijun
    • Journal of the Korean Ceramic Society
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    • v.45 no.12
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    • pp.755-759
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    • 2008
  • New cathode materials $LaNi_{1-x}{Cu_x}{O_3}$ (typically $LaNi_{0.8}Cu_{0.2}O_3$) were synthesized using a co-precipitation method. The structure and morphology of the powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The composite material [$Ce_{0.8}Sm_{0.2}O_{2-\ddot{a}}$(SDC) and carbonate (${Na_2}{CO_3},{Li_2}{CO_3}$)], NiO and $LaNi_{1-x}{Cu_x}{O_3}$ were used as the electrolyte, anode and cathode, respectively. The electrochemical performance of La-Ni-Cu-O perovskite oxide at low temperatures ($400{\sim}550^{\circ}C$) was studied. The results showed that $LaNi_{0.8}Cu_{0.2}O_3$ precursor powder prepared through a co-precipitation method and calcined at $860^{\circ}C$ for 2 h formed uniform grains with diameters in the range of $400{\sim}500\;nm$. The maximum power density and the short circuit current density of the single cell unit at $550^{\circ}C$ were found to be $390\;mW/cm^2$ and $968\;mA/cm^2$, respectively.

Fabrication and Cell Properties of Flattened Tube Segmented-in-Series Solid Oxide Fuel Cell-Stack Using Decalcomania Paper (전사지를 이용한 다전지식 평관형 고체산화물 연료전지 제작 및 셀 특성)

  • An, Yong-Tae;Ji, Mi-Jung;Park, Sun-Min;Shin, Sang-Ho;Hwang, Hae-Jin;Choi, Byung-Hyun
    • Korean Journal of Materials Research
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    • v.23 no.3
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    • pp.206-210
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    • 2013
  • In the segmented-in-series solid-oxide fuel cells (SIS-SOFCs), fabrication techniques which use decalcomania paper have many advantages, i.e., an increased active area of the electrode; better interfacial adhesion property between the anode, electrolyte and cathode; and improved layer thickness uniformity. In this work, a cell-stack was fabricated on porous ceramic flattened tube supports using decalcomania paper, which consists of an anode, electrolyte, and a cathode. The anode layer was $40{\mu}m$ thick, and was porous. The electrolyte layers exhibited a uniform thickness of about $20{\mu}m$ with a dense structure. Interfacial adhesion was improved due to the dense structure. The cathode layers was $30{\mu}m$ thick with porous structure, good adhesion to the electrolyte. The ohmic resistance levels at 800, 750 and $700^{\circ}C$ were measured, showing values of 1.49, 1.58 and $1.65{\Omega}{\cdot}cm^2$, respectively. The polarization resistances at 800, 750 and $700^{\circ}C$ were measured to be 1.63, 2.61 and $4.17cm^2$, respectively. These lower resistance values originated from the excellent interfacial adhesion between the anode, electrolyte and cathode. In a two-cell-stack SOFC, open-circuit voltages(OCVs) of 1.915, 1.942 and 1.957 V and maximum power densities(MPD) of 289.9, 276.1 and $220.4mW/cm^2$ were measured at 800, 750 and $700^{\circ}C$, respectively. The proposed fabrication technique using decalcomania paper was shown to be feasible for the easy fabrication of segmented-in-series flattened tube SOFCs.

In-situ spectroscopic studies of SOFC cathode materials

  • Ju, Jong-Hun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2012.05a
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    • pp.70.1-70.1
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    • 2012
  • In-situ X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy studies of SOFC cathode materials will be discussed in this presentation. The mixed conducting perovskites (ABO3) containing rare and alkaline earth metals on the A-site and a transition metal on the B-site are commonly used as cathodes for solid oxide fuel cells (SOFC). However, the details of the oxygen reduction reaction are still not clearly understood. The information about the type of adsorbed oxygen species and their concentration is important for a mechanistic understanding of the oxygen incorporation into these cathode materials. XPS has been widely used for the analysis of adsorbed species and surface structure. However, the conventional XPS experiments have the severe drawback to operate at room temperature and with the sample under ultrahigh vacuum (UHV) conditions, which is far from the relevant conditions of SOFC operation. The disadvantages of conventional XPS can be overcome to a large extent with a "high pressure" XPS setup installed at the BESSY II synchrotron. It allows sample depth profiling over 2 nm without sputtering by variation of the excitation energy, and most importantly measurements under a residual gas pressure in the mbar range. It is also well known that the catalytic activity for the oxygen reduction is very sensitive to their electrical conductivity and oxygen nonstoichiometry. Although the electrical conductivity of perovskite oxides has been intensively studied as a function of temperature or oxygen partial pressure (Po2), in-situ measurements of the conductivity of these materials in contact with the electrolyte as a SOFC configuration have little been reported. In order to measure the in-plane conductivity of an electrode film on the electrolyte, a substrate with high resistance is required for excluding the leakage current of the substrate. It is also hardly possible to measure the conductivity of cracked thin film by electrical methods. In this study, we report the electrical conductivity of perovskite $La_{0.6}Sr_{0.4}CoO_{3-{\delta}}$ (LSC) thin films on yttria-stabilized zirconia (YSZ) electrolyte quantitatively obtained by in-situ IR spectroscopy. This method enables a reliable measurement of the electronic conductivity of the electrodes as part of the SOFC configuration regardless of leakage current to the substrate and cracks in the film.

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Cathode materials advance in solid oxide fuel cells (고체산화물연료전지 공기극의 재료개발동향)

  • Son, Young-Mok;Cho, Mann;Nah, Do-Baek;Kil, Sang-Cheol;Kim, Sang-Woo
    • Journal of Energy Engineering
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    • v.19 no.2
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    • pp.73-80
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    • 2010
  • A solid oxide fuel cells(SOFC) is a clean energy technology which directly converts chemical energy to electric energy. When the SOFC is used in cogeneration then the efficiency can reach higher than 80%. Also, it has flexibility in using various fuels like natural gases and bio gases, so it has an advantage over polymer electrolyte membrane fuel cells in terms of fuel selection. A typical cathode material of the SOFC in conjunction with yttria stabilized zirconia(YSZ) electrolyte is still Sr-doped $LaMnO_3$(LSM). Recently, application of mixed electronic and ionic conducting perovskites such as Sr-doped $LaCoO_3$(LSCo), $LaFeO_3$(LSF), and $LaFe_{0.8}Co_{0.2}O_3$(LSCF) has drawn much attention because these materials exhibit lower electrode impedance than LSM. However, chemical reaction occurs at the manufacturing temperature of the cathode when these materials directly contact with YSZ. In addition, thermal expansion coefficient(TEC) mismatch with YSZ is also a significant issue. It is important, therefore, to develop cathode materials with good chemical stability and matched TEC with the SOFC electrolyte, as well as with high electrochemical activity.

First-Principles Investigation of the Surface Properties of LiNiO2 as Cathode Material for Lithium-ion Batteries (제일원리계산을 이용한 리튬이차전지 양극활물질 LiNiO2의 표면 특성에 관한 연구)

  • Choi, Heesung;Lee, Maeng-Eun
    • Journal of the Korean Electrochemical Society
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    • v.16 no.3
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    • pp.169-176
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    • 2013
  • Solid state lithium oxide compounds of layered structure, which has high stability of structure, are mainly used as the cathode materials in lithium-ion batteries (LIBs). Recently, the investigation of Solid Electrolyte Interphase (SEI) between active materials and electrolyte has been focusing to improve the performance of lithium-ion batteries. For the investigation of the SEI, the study of surface properties of cathode materials and anode materials is also required in advance. $LiNiO_2$ and $LiCoO_2$ are very similar layered structure of cathode active materials and representative solid state lithium oxide compounds in LIBs. Various experimental and theoretical studies have been doing for $LiCoO_2$. The theoretical investigation of $LiNiO_2$ is not sufficient, however, even if experimental studies of $LiNiO_2$ are enough. In this study, the surface energies of nine facets of $LiNiO_2$ crystal facets were calculated by Density Functional Theory. In XRD data of $LiNiO_2$, (003), (104), (101), et al. facets are main surfaces in order. However, the results of calculation are different with XRD data. Thus, both (104) and (101) facets, which are energetically stable and measured in XRD, are mainly exposed in the surface of $LiNiO_2$ and it is expected that intercalation and de-intercalation of Li-ion will be affected by them.

Cathode Characteristics in the Synthesis of $(La,\;Sr)MnO_{3+{\delta}$ of Precursor ($(La,\;Sr)MnO_{3+{\delta}$ 합성에 있어서 출발물질에 따른 양극특성)

  • Lee, Mi-Jai;Kim, Sei-Ki;Ji, Mi-Jung;Choi, Byung-Hyun;Park, Sang-Sun
    • 한국신재생에너지학회:학술대회논문집
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    • 2006.11a
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    • pp.360-363
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    • 2006
  • We synthesized $(La,\;Sr)MnO_{3+{\delta}$ 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 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 210.3S/cm at $700^{\circ}C$ On the other side, when we used oxide solution as a starting material, we found main crystal phase of $LnMnO_3$ 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 4hrs was 152.7s/cm at $700^{\circ}C$. The sintered $(La,\;Sr)MnO_3$ powder at $1000^{\circ}C$ for 4hrs got the deoxidization peak, depending on the temperature md in case of using nitrate solution as a start ing 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 m properly. And we found it to have different electrical conduct ivity the synthesized $(La,\;Sr)MnO_3$ powder by using different start ing materials like nitrate solution and oxide solution which influence a sintering density and crystal phase.

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Oxide Cathodes for Reliable Electron Sources

  • Weon, Byung-Mook;Je, Jung-Ho;Park, Gong-Seog;Koh, Nam-Je;Barratt, David S.;Saito, Tsunenari
    • Journal of Information Display
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    • v.6 no.4
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    • pp.35-39
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    • 2005
  • In this paper, we investigate the oxide cathodes for the development of reliable electron sources. Poisoning in oxide cathodes is one of the serious problems in achieving reliable electron emission. In particular, early poisoning induces poor life performance as will be demonstrated herein. The survivability of electron emission sources is significantly improved by high doping of high-speed activator. The robust oxide cathodes with 0.17 % Mg operating at about 1,050 K are expected to work for very long times (>100,000 hours). We suggest that this key idea will contribute to solving the basic problems in oxide cathodes such as poisoning or ion bombardment for high power or high frequency applications of electron sources.

Role of Sulfone Additive in Improving 4.6V High-Voltage Cycling Performance of Layered Oxide Battery Cathode (층상계 산화물 양극의 4.6V 고전압 특성 향상에서의 Sulfone 첨가제의 역할)

  • Kang, Joonsup;Nam, Kyung-Mo;Hwang, Eui-Hyeong;Kwon, Young-Gil;Song, Seung-Wan
    • 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.

Accelerated Formation of Surface Films on the Degradation of LiCoO2 Cathode at High Temperature (표면 피막 형성이 LiCoO2 양극의 고온 열화에 미치는 영향)

  • Sung, Jong Hun;Hasan, Fuead;Yoo, Hyun Deog
    • Journal of the Korean Electrochemical Society
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    • v.23 no.3
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    • pp.57-65
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    • 2020
  • It is crucial to investigate the thermal degradation of lithium-ion batteries (LIBs) to understand the possible malfunction at high temperature. Herein, we investigated the effects of surface film formation on the thermal degradation of lithium cobalt oxide (LiCoO2, LCO) cathode that is one of representative cathode materials. Cycling test at 60℃ exhibited poorer cycleability compared with the cycling at 25℃. Cathodes after the initial 5 cycles at 60℃ (60-LCO) exhibited higher impedance compared to the cathode after initial 5 cycles at 25℃ (25-LCO), resulting in the lower rate capability upon subsequent cycling at 25℃, although the capacity values were similar at the lowest C-rate of 0.1C. In order to understand degradation of the LCO cathode at the high temperature, we analyzed the cathodes surface using X-ray photoelectron spectroscopy (XPS). Among various peaks, intensity of lithium hydroxide (LiOH) increased substantially after the operation at 60℃, and the C-C signal that represents the conductive agent was distinctly lower on 60-LCO compared to 25-LCO. These results pointed to an excessive formation of cathode-electrolyte interphase including LiOH at 60℃, leading to the increase in the resistance and the resultant degradation in the electrochemical performances.

Studies on the fabrication and properties of $La_ 0.7Sr_0.3MnO_3$cathode contact prepared by glycine-nitrate process and solid state reaction method for the high efficient solid oxide fuel cells applications 0.3/Mn $O_{3}$ (고효율 고체산화물 연료전지 개발을 위한 자발 착화 연소 합성법과 고상반응법에 의한 $La_ 0.7Sr_0.3MnO_3$ 양극재료 제조 및 물성에 관한 연구)

  • Shin, Woong-Shun;Park, In-Sik;Kim, Sun-Jae;Park, Sung
    • Electrical & Electronic Materials
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    • v.10 no.2
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    • pp.141-149
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    • 1997
  • L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ powders were prepared by both GNP(Glycine-Nitrate Process) and solid state reaction method in various of calcination temperature(800-1000.deg. C) and time in air. Also, L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ cathode contacts on YSZ(Yttria-Stabilized Zirconia) substrate were prepared by screen printing and sintering method as a function of sintering temperature(1100-1450.deg. C) in air. Sintering behaviors have been investigated by SEM(Scanning Electron Microscope) and porosity measurement. Compositional and structural characterization were carried out by X-ray diffractometer and ICP AES(Inductively Coupled Plasma-Atomic Emission Spectrometry) analysis. Electrical characterization was carried out by the electrical conductivity with linear 4 point probe method. As the calcination period increased in solid state reaction method, L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ phase increased. Although L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ single phase was obtained only for 48hrs at 1000.deg. C, in GNP method it was easy to get single and ultra-fine L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ powders with submicron particle size at 650.deg. C for 30min. The particle size and thickness of L $a_{0.7}$S $r_{0.3}$Mn $O_{3}$ cathode contact by solid state reaction method did not change during the heat treatment, while those by GNP method showed good sintering characteristics because initial powder size fabricated from GNP method is smaller than that fabricated from solid state reaction method. Based on enthalpy change from thermodynamic data and ICP-AES analysis, it was suggested to make cathode contact in composition of (L $a_{0.7}$S $r_{0.3}$)$_{0.91}$ Mn $O_{3}$ which have little second phase (L $a_{2}$Z $r_{2}$ $O_{7}$) for high efficient solid oxide fuel cells applications. As (L $a_{0.7}$S $r_{0.3}$)$_{0.91}$Mn $O_{3}$ cathode contact on YSZ substrate was sintering at 1250.deg. C the temperature that liquid phase sintering did not occur. It was possible to obtain proper cathode contacts with electrical conductivity of 150(S/cm) and porosity content of 30-40%.m) and porosity content of 30-40%.

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