• 제목/요약/키워드: Oxygen ion diffusion

검색결과 45건 처리시간 0.03초

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

  • 정종식;정철구;김림;성용욱
    • 한국신재생에너지학회:학술대회논문집
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    • 한국신재생에너지학회 2006년도 춘계학술대회
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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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인산형 연료전지용 기체확산전극의 백금촉매 담지방법에 따른 산소환원 특성 (Oxygen Reduction of PAFC Gas Diffusion Electrode with Various Pt Impregnation Methods)

  • 유덕영;은영찬;심중표;이주성
    • 공업화학
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    • 제7권5호
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    • pp.999-1005
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    • 1996
  • Carbon 표면에 작용기를 도입하기 위해 산화처리한 후, $H^+$과 Pt 양이온을 교환시키는 이온교환법과 백금용액을 계면활성제가 들어있는 메탄올로 환원을 시켜 carbon에 백금을 담지하는 메탄올 환원법으로 촉매를 제조하여 이미 널리 쓰이고 있는 colloid 방법으로 제조한 촉매와 비교하였다. 메탄올 환원법에서 계면활성제는 carbon과 백금입자의 분산효과를 높이고, 안정한 백금 colloid 용액의 유지를 위해 첨가하였다. 각 담지방법에 의해 담지된 백금입자가 $30{\sim}50{\AA}$의 크기로 분산되어 담지된 것을 TEM과 XRD를 통해 확인하였고, 담지방법에 따른 백금의 담지율은 모두 100%에 가까웠고, 그 중 이온교환법의 담지율이 DCP 측정으로는 99.92%, 연소법으로는 99.87%였다. 각 촉매의 활성을 전기화학적으로 비교하기 위하여 산소환원전류밀도를 측정한 결과, 초기에는(60시간 이내) colloid 방법에 의해 제조된 촉매로 제작한 산소극이 0.7V(vs. RHE)에서 $460mA/cm^2$로 이온교환법, 메탄올 환원법에 의해 제조된 촉매보다 더 우수한 전극성능을 나타냈지만, 장시간(약 100시간 이후) 운전시에 전극성능 감소율은 colloid 방법으로 제조한 촉매로 제작한 전극이 가장 높게 증가하였으며, 메탄올 환원법으로 제조한 전극이 가장 안정된 특성을 보였다.

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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
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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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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    • 제35권2호
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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
    • 한국재료학회:학술대회논문집
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    • 한국재료학회 2011년도 추계학술발표대회
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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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    • 제43권4호
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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.

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

  • 김종표;박정훈;윤여일
    • 공업화학
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    • 제19권4호
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    • pp.382-387
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    • 2008
  • 착체중합법을 이용하여 $Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ 조성의 산화물을 합성하였으며, 합성된 분말은 압축 성형 후 $1080^{\circ}C$에서 소결하여 치밀한 페롭스카이트 분리막을 제조하였다. 밀봉 재료로 gold ring, Pyrex ring 및 Pyrex 분말을 사용하여 가스누출 실험을 수행하였다. $Ba_{0.5}Sr_{0.5}Co_{0.8}Fe_{0.2}O_{3-{\delta}}$ 분리막의 산소투과량 분석결과 온도가 증가함에 따라 산소투과량은 증가하였고, $900^{\circ}C$에서 $0.74mL/min{\cdot}cm^2$의 값을 나타내었다. $950^{\circ}C$에서 밀봉 재료에 따른 투과 특성 분석 결과, gold ring을 이용할 경우 높은 산소투과량을 보인 반면, Pyrex를 밀봉재로 사용할 경우 낮은 투과량을 보였다. 이는 Pyrex를 밀봉재로 이용할 경우 분리막 표면으로 유리가 침투하여 유효 산소투과면적을 감소시켰기 때문이며, 광화학 현미경 분석으로 Pyrex 유리의 확산 침투를 확인하였다.

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

  • 윤중철;이종호;김주선;이해원;김병호
    • 한국세라믹학회지
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    • 제42권4호
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    • pp.251-259
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    • 2005
  • 혼합전도체 산화물, LSCF의 전극반응점 분포에 따른 분극현상을 관찰하기 위해 다공성 양극의 기공률을 변화시켜가며 분극특성을 관찰하였다. 전극의 기공률을 달리하기 위해 크기가 다른 두 종류의 LSCF 분말들을 혼합비를 달리하여 사용하였으며 GDC 전해질 기판에 스크린 인쇄법을 통해 전극을 구성한 후 반쪽전지 실험을 수행하였다. 제조된 후막전극의 기공률은 화상 분석법을 통해 측정하였으며 전극의 전체 비표면적을 유추하기 위해 2차원 이미지에서의 기공의 둘레 길이를 측정하였다. 교류 임피던스법을 이용해 분극 특성을 관찰한 결과 혼합전도체인 LSCF 양극에서의 전극반응은 i) 양극표면에서 이온화된 산소이온이 전해질과의 삼상계면까지 이동해 오는 단계, ii) 이동해온 산소이온이 양극으로부터 전해질로 전달되는 반응단계에 의해 제어됨을 알 수 있었다. 이러한 양극에서의 분극은 기공률의 증가에 따라 전극 반응에 필요한 활성 표면이 증가됨으로써 줄어드는 것을 알 수 있었다.

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

  • 김도완;김진성;후이;이희수
    • 한국결정성장학회지
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    • 제20권6호
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    • pp.278-282
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    • 2010
  • Tm 도핑에 따른 $BaTiO_3$ ceramics의 전기적 특성과 열화 거동에 미치는 영향에 대하여 core-shell 형성과 가속열화시험에 의한 미세화학변화의 관점에서 연구하였다. $Tm_2O_3$를 첨가하지 않은 $BaTiO_3$와 1 mol%를 첨가한 $BaTiO_3$를 펠렛과 적층 형태의 시편으로 각각 제조하였다. 1 mol% $Tm_2O_3$가 첨가된 유전체 시편의 유전상수는 $Tm_2O_3$를 첨가하지 않은 시편에 비해 약 40% 높게 나타났고 X7R 조건을 만족하였다. 절연저항 또한 1 mol% $Tm_2O_3$가 첨가된 시편은 $5.43{\times}10^{10}{\Omega}$으로 $Tm_2O_3$를 첨가하지 않은 시편의 $1.11{\times}10^{10}{\Omega}$보다 높게 나타났다. 이는 $Tm^{3+}$ 이온이 Ba site와 Ti site에 선택적으로 치환되고 유전체 미세조직 내에 core-shell 구조를 형성하여 전기적 특성을 향상시킨 것으로 설명된다. 각각의 조성에 따라 제조된 적층 시편의 $150^{\circ}C$, 70 V, 24시간 가속열화시험결과에 따르면, 1 mol% $Tm_2O_3$가 첨가된 $BaTiO_3$는 첨가되지 않은 시편에 비해 전극 층으로의 산소확산이 감소됨을 확인하였고, 이는 $Tm^{3+}$ 이온의 Ti site 치환에 의해 발생한 산소공공이 Ni 전극과 반응할 수 있는 과잉 산소를 줄여주기 때문으로 판단된다.

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
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
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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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