• Title/Summary/Keyword: Oxygen ion diffusion

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Study on a Long Term Deactivation of Electro-catalysts in PEMFC for Automobile (자동차용 PEMFC 전극 촉매의 열화 원인에 대한 연구)

  • Chung, Jong-Shik;Chung, Chul-Goo;Kim, Lim;Sung, Yong-Wook
    • 한국신재생에너지학회:학술대회논문집
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    • 2006.06a
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    • pp.63-66
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    • 2006
  • A long term deactivation study was carried out with commercial MEA provided by Hyundai Motor Co. The deactivation phenomena were observed only at high voltage region where there is no diffusion-limited reaction. A rapid deactivation was observed up to 40h owing to the sintering of Pt particles. This was followed a gradual increase in the activity up to 300 h, which is probably caused by improvement in the electrode properties in the presence of current during the reaction. After 300 h, monotonic decrease in the activity was observed owing to dissolution of Pt particles especially in the cathode. The presence oxygen is the cause of oxidation and dissolution of Pt. The dissolution rate can be somewhat retarded by generation of current, which reduces Pt ion back to Pt in the cathode.

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Oxygen Reduction of PAFC Gas Diffusion Electrode with Various Pt Impregnation Methods (인산형 연료전지용 기체확산전극의 백금촉매 담지방법에 따른 산소환원 특성)

  • Yoo, Duck-Young;Eun, Yeong-Chan;Shim, Joong-Pyo;Lee, Ju-Seong
    • Applied Chemistry for Engineering
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    • v.7 no.5
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    • pp.999-1005
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    • 1996
  • Pt catalyst on carbon black was prepared by colloidal method, ion exchanging method and methanol reducing method. The colloidal method has been used generally. At ion exchanging method, $H^+$ of functional group on carbon surface made by oxidation treatment was exchanged with Pt ion. At methanol reducing method, Pt was impregnated on carbon to reduce by methanol contained with surfactants. With TEM and XRD, Pt particle size impregnated on carbon by various methods was $30{\sim}50{\AA}$. Loading yield was about 100%, loading yield of ion exchanging method was 99.92% by DCP analysis and 99.87% by combustion method. Within 60 hour, current density of oxygen reduction was $460mA/cm^2$ at 0.7V(vs. RHE) at colloidal method. It was the better performance than catalyst prepared by ion exchanging, methanol reducing method. But, it was shown some decrease of performance for long operation time(after 100hour), catalyst prepared by methanol reducing method was shown stable performance.

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Water Repellency on a Nanostructured Superhydrophobic Carbon Fibers Network

  • Ko, Tae-Jun;Her, Eun-Kyu;Shin, Bong-Su;Kim, Ho-Young;Lee, Kwang-Ryeol;Hong, Bo-Ki;Kim, Sae-Hoon;Oh, Kyu-Hwan;Moon, Myoung-Woon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.224-224
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    • 2012
  • For decades, carbon fiber has expanded their application fields from reinforced composites to energy storage and transfer technologies such as electrodes for super-capacitors and lithium ion batteries and gas diffusion layers for proton exchange membrane fuel cell. Especially in fuel cell, water repellency of gas diffusion layer has become very important property for preventing flooding which is induced by condensed water could damage the fuel cell performance. In this work, we fabricated superhydrophobic network of carbon fiber with high aspect ratio hair-like nanostructure by preferential oxygen plasma etching. Superhydrophobic carbon fiber surfaces were achieved by hydrophobic material coating with a siloxane-based hydrocarbon film, which increased the water contact angle from $147^{\circ}$ to $163^{\circ}$ and decreased the contact angle hysteresis from $71^{\circ}$ to below $5^{\circ}$, sufficient to cause droplet roll-off from the surface in millimeter scale water droplet deposition test. Also, we have explored that the condensation behavior (nucleation and growth) of water droplet on the superhydrophobic carbon fiber were significantly retarded due to the high-aspect-ratio nanostructures under super-saturated vapor conditions. It is implied that superhydrophobic carbon fiber can provide a passage for vapor or gas flow in wet environments such as a gas diffusion layer requiring the effective water removal in the operation of proton exchange membrane fuel cell. Moreover, such nanostructuring of carbon-based materials can be extended to carbon fiber, carbon black or carbon films for applications as a cathode in lithium batteries or carbon fiber composites.

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Effect of Calcination Temperature of Size Controlled Microstructure of LiNi0.8Co0.15Al0.05O2 Cathode for Rechargeable Lithium Battery

  • Park, Tae-Jun;Lim, Jung-Bin;Son, Jong-Tae
    • Bulletin of the Korean Chemical Society
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    • v.35 no.2
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    • pp.357-364
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    • 2014
  • Size controlled, $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ cathode powders were prepared by co-precipitation method followed by heat treatment at temperatures between 750 and $850^{\circ}C$. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The synthesized $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ after calcined at $750^{\circ}C$ has a good electrochemical performance with an initial discharge capacity of $190mAhg^{-1}$ and good capacity retention of 100% after 30 cycles at 0.1C ($17mAg^{-1}$). The capacity retention of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ after calcined at $750^{\circ}C$ is better than that at 800 and $850^{\circ}C$ without capacity loss at various high C rates. This is ascribed to the minimized cation disorder, a higher conductivity, and higher lithium ion diffusion coefficient ($D_{Li}$) observed in this material. In the differential scanning calorimetry DSC profile of the charged sample, the generation of heat by exothermic reaction was decreased by calcined at high temperature, and this decrease is especially at $850^{\circ}C$. This behavior implies that the high temperature calcinations of $LiNi_{0.8}Co_{0.15}Al_{0.05}O_2$ prevent phase transitions with the release of oxygen.

Nanomaterials Research Using Quantum Beam Technology

  • Kishimoto, Naoki;Kitazawa, Hideaki;Takeda, Yoshihiko
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.10a
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    • pp.7-7
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    • 2011
  • Quantum beam technology has been expected to develop breakthroughs for nanotechnology during the third basic plan of science and technology (2006~2010). Recently, Green- or Life Innovations has taken over the national interests in the fourth basic science and technology plan (2011~2015). The NIMS (National Institute for Materials Science) has been conducting the corresponding mid-term research plans, as well as other national projects, such as nano-Green project (Global Research for Environment and Energy based on Nanomaterials science). In this lecture, the research trends in Japan and NIMS are firstly reviewed, and the typical achievements are highlighted over key nanotechnology fields. As one of the key nanotechnologies, the quantum beam research in NIMS focused on synchrotron radiation, neutron beams and ion/atom beams, having complementary attributes. The facilities used are SPring-8, nuclear reactor JRR-3, pulsed neutron source J-PARC and ion-laser-combined beams as well as excited atomic beams. Materials studied are typically fuel cell materials, superconducting/magnetic/multi-ferroic materials, quasicrystals, thermoelectric materials, precipitation-hardened steels, nanoparticle-dispersed materials. Here, we introduce a few topics of neutron scattering and ion beam nanofabrication. For neutron powder diffraction, the NIMS has developed multi-purpose pattern fitting software, post RIETAN2000. An ionic conductor, doped Pr2NiO4, which is a candidate for fuel-cell material, was analyzed by neutron powder diffraction with the software developed. The nuclear-density distribution derived revealed the two-dimensional network of the diffusion paths of oxygen ions at high temperatures. Using the high sensitivity of neutron beams for light elements, hydrogen states in a precipitation-strengthened steel were successfully evaluated. The small-angle neutron scattering (SANS) demonstrated the sensitive detection of hydrogen atoms trapped at the interfaces of nano-sized NbC. This result provides evidence for hydrogen embrittlement due to trapped hydrogen at precipitates. The ion beam technology can give novel functionality on a nano-scale and is targeting applications in plasmonics, ultra-fast optical communications, high-density recording and bio-patterning. The technologies developed are an ion-and-laser combined irradiation method for spatial control of nanoparticles, and a nano-masked ion irradiation method for patterning. Furthermore, we succeeded in implanting a wide-area nanopattern using nano-masks of anodic porous alumina. The patterning of ion implantation will be further applied for controlling protein adhesivity of biopolymers. It has thus been demonstrated that the quantum beam-based nanotechnology will lead the innovations both for nano-characterization and nano-fabrication.

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Formation of Amorphous Oxide Layer on the Crystalline Al-Ni-Y Alloy

  • Kim, Kang Cheol;Kim, Won Tae;Kim, Do Hyang
    • Applied Microscopy
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    • v.43 no.4
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    • pp.173-176
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    • 2013
  • The oxidation behavior of the crystallized $Al_{87}Ni_3Y_{10}$ alloy has been investigated with an aim to compare with that of the amorphous $Al_{87}Ni_3Y_{10}$ alloy. The oxidation at 873 K occurs as follows: (1) growth of an amorphous aluminum-yttrium oxide layer (~10 nm) after heating up to 873 K; and (2) formation of $YAlO_3$ crystalline oxide (~220 nm) after annealing for 30 hours at 873 K. Such an overall oxidation step indicates that the oxidation behavior in the crystallized $Al_{87}Ni_3Y_{10}$ alloy occurs in the same way as in the amorphous $Al_{87}Ni_3Y_{10}$ alloy. The simultaneous presence of aluminum and yttrium in the oxide layer significantly enhances the thermal stability of the amorphous structure in the oxide phase. Since the structure of aluminum-yttrium oxide is dense due to the large difference in ionic radius between aluminum and yttrium ions, the diffusion of oxygen ion through the amorphous oxide layer is limited thus stabilizing the amorphous structure of the oxide phase.

Effect of Sealant Materials on Oxygen Permeation in Perovskite Oxide Membrane (밀봉 재료에 따른 페롭스카이트 막의 산소투과 특성)

  • Kim, Jong Pyo;Park, Jung Hoon;Yoon, Yeoil
    • Applied Chemistry for Engineering
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    • v.19 no.4
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    • pp.382-387
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    • 2008
  • $Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ oxide was synthesized by polymerized complex method. Dense membrane of perovskite oxide was prepared using as-prepared powder by pressing and sintering at $1080^{\circ}C$. Leakage test was conducted on the membrane sealed by gold ring, Pyrex ring or Pyrex powder as a sealing material. The oxygen permeation flux of $Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ membrane increased with increasing temperature and was $0.74mL/min{\cdot}cm^2$ at $900^{\circ}C$. In the case of the membrane applied by sealing material, oxygen permeation flux of the membrane using gold ring at $950^{\circ}C$ was higher than that using Pyrex materials because the undesired spreading of Pyrex glass materials in the membrane led to the reduction of effective permeation area. Microphotograph analysis results for the membrane after permeation test confirmedthe diffusion of Pyrex glass seal into the membrane.

Effect of Cathode Porosity on the Cathodic Polarization Behavior of Mixed Conducting LSCF(La0.6Sr0.4Co0.2Fe0.8O3) (혼합전도체 LSCF(La0.6Sr0.4Co0.2Fe0.8O3) 양극의 기공률에 따른 양극분극 특성)

  • Yun, Joong-Cheul;Lee, Jong-Ho;Kim, Joosun;Lee, Hae-Weon;Kim, Byong-Ho
    • Journal of the Korean Ceramic Society
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    • v.42 no.4
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    • pp.251-259
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    • 2005
  • In order to characterize the influence of the reaction-site density on the cathodic polarization property of LSCF, we chose the porosity of LSCF as a main controlling variable, which is supposed to be closely related with active sites for the cathode reaction. To control the porosity of cathodes, we changed the mixing ratio of fine and coarse LSCF powders. The porosity and pore perimeter of cathodes were quantitatively analyzed by image analysis. The electrochemical half cell test for the cathodic polarization was performed via 3-probe AC-impedance spectroscopy. According to the investigation, the reduction of oxygen at LSCF cathode was mainly controlled by following two rate determining steps; i) surface diffusion and/or ionic conduction of ionized oxygen through bulk LSCF phase, ii) charge transfer of oxygen ion at cathode/electrolyte interface. Moreover, the overall cathode polarization was diminished as the cathode porosity increased due to the increase of the active reaction sites in cathode layer.

Electrical properties and degradation behavior of Tm2O3 doped barium titanate ceramics for MLCCs (Tm2O3가 첨가된 MLCC용 BaTiO3 유전체의 전기적 특성 및 열화거동)

  • Kim, Do-Wan;Kim, Jin-Seong;Hui, K.N.;Lee, Hee-Soo
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.20 no.6
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    • pp.278-282
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    • 2010
  • The doping effect of thulium on electrical properties and degradation behavior in barium titanate ceramics ($BaTiO_3$) was investigated in terms of generations of core-shell structure and micro-chemical changes through highly accelerated degradation test. The dielectric specimens of pellet type and multi-layered sheets were prepared by using $BaTiO_3$ with undoped and doped with 1 mol% $Tm_2O_3$. The $BaTiO_3$ ceramics doped with 1 mol% $Tm_2O_3$ had 40% higher dielectric constant (${\varepsilon}$ = 2700) than that of the undoped $BaTiO_3$ specimen at curie temperature and met X7R specification. According to the result of highly accelerated degradation test conducted at $150^{\circ}C$, 70 V, and 24 hr, the oxygen diffusion was declined in dielectrics doped with 1 mol% $Tm_2O_3$. The $Tm^{3+}$ ion substituted selectively Ba site and Ti site and contributed to the generation of the core-shell structure. Oxygen vacancies occurred by substitution for Ti site could reduce excess oxygen that reacted to the Ni electrode.

New Approaches for Overcoming Current Issues of Plasma Sputtering Process During Organic-electronics Device Fabrication: Plasma Damage Free and Room Temperature Process for High Quality Metal Oxide Thin Film

  • Hong, Mun-Pyo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.02a
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    • pp.100-101
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    • 2012
  • The plasma damage free and room temperature processedthin film deposition technology is essential for realization of various next generation organic microelectronic devices such as flexible AMOLED display, flexible OLED lighting, and organic photovoltaic cells because characteristics of fragile organic materials in the plasma process and low glass transition temperatures (Tg) of polymer substrate. In case of directly deposition of metal oxide thin films (including transparent conductive oxide (TCO) and amorphous oxide semiconductor (AOS)) on the organic layers, plasma damages against to the organic materials is fatal. This damage is believed to be originated mainly from high energy energetic particles during the sputtering process such as negative oxygen ions, reflected neutrals by reflection of plasma background gas at the target surface, sputtered atoms, bulk plasma ions, and secondary electrons. To solve this problem, we developed the NBAS (Neutral Beam Assisted Sputtering) process as a plasma damage free and room temperature processed sputtering technology. As a result, electro-optical properties of NBAS processed ITO thin film showed resistivity of $4.0{\times}10^{-4}{\Omega}{\cdot}m$ and high transmittance (>90% at 550 nm) with nano- crystalline structure at room temperature process. Furthermore, in the experiment result of directly deposition of TCO top anode on the inverted structure OLED cell, it is verified that NBAS TCO deposition process does not damages to the underlying organic layers. In case of deposition of transparent conductive oxide (TCO) thin film on the plastic polymer substrate, the room temperature processed sputtering coating of high quality TCO thin film is required. During the sputtering process with higher density plasma, the energetic particles contribute self supplying of activation & crystallization energy without any additional heating and post-annealing and forminga high quality TCO thin film. However, negative oxygen ions which generated from sputteringtarget surface by electron attachment are accelerated to high energy by induced cathode self-bias. Thus the high energy negative oxygen ions can lead to critical physical bombardment damages to forming oxide thin film and this effect does not recover in room temperature process without post thermal annealing. To salve the inherent limitation of plasma sputtering, we have been developed the Magnetic Field Shielded Sputtering (MFSS) process as the high quality oxide thin film deposition process at room temperature. The MFSS process is effectively eliminate or suppress the negative oxygen ions bombardment damage by the plasma limiter which composed permanent magnet array. As a result, electro-optical properties of MFSS processed ITO thin film (resistivity $3.9{\times}10^{-4}{\Omega}{\cdot}cm$, transmittance 95% at 550 nm) have approachedthose of a high temperature DC magnetron sputtering (DMS) ITO thin film were. Also, AOS (a-IGZO) TFTs fabricated by MFSS process without higher temperature post annealing showed very comparable electrical performance with those by DMS process with $400^{\circ}C$ post annealing. They are important to note that the bombardment of a negative oxygen ion which is accelerated by dc self-bias during rf sputtering could degrade the electrical performance of ITO electrodes and a-IGZO TFTs. Finally, we found that reduction of damage from the high energy negative oxygen ions bombardment drives improvement of crystalline structure in the ITO thin film and suppression of the sub-gab states in a-IGZO semiconductor thin film. For realization of organic flexible electronic devices based on plastic substrates, gas barrier coatings are required to prevent the permeation of water and oxygen because organic materials are highly susceptible to water and oxygen. In particular, high efficiency flexible AMOLEDs needs an extremely low water vapor transition rate (WVTR) of $1{\times}10^{-6}gm^{-2}day^{-1}$. The key factor in high quality inorganic gas barrier formation for achieving the very low WVTR required (under ${\sim}10^{-6}gm^{-2}day^{-1}$) is the suppression of nano-sized defect sites and gas diffusion pathways among the grain boundaries. For formation of high quality single inorganic gas barrier layer, we developed high density nano-structured Al2O3 single gas barrier layer usinga NBAS process. The NBAS process can continuously change crystalline structures from an amorphous phase to a nano- crystalline phase with various grain sizes in a single inorganic thin film. As a result, the water vapor transmission rates (WVTR) of the NBAS processed $Al_2O_3$ gas barrier film have improved order of magnitude compared with that of conventional $Al_2O_3$ layers made by the RF magnetron sputteringprocess under the same sputtering conditions; the WVTR of the NBAS processed $Al_2O_3$ gas barrier film was about $5{\times}10^{-6}g/m^2/day$ by just single layer.

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