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Eelectrochemical Performance of Perovskite Materials coated Cathode for MCFC (perovskite 물질이 코팅된 MCFC용 공기극의 전기화학적 성능 고찰)

  • Song, Shin Ae;Kang, Min Gu;Yoon, Sung Pil;Han, Jong Hee;Oh, In Hwan
    • 한국신재생에너지학회:학술대회논문집
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    • 2010.06a
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    • pp.133.2-133.2
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    • 2010
  • 현재 융융탄산염 연료전지의 공기극으로 다공성의 lithiated NiO를 사용하고 있는데 이 재료의 경우 크게 두 가지의 문제점을 안고 있다. 첫 번째는 Ni이 전해질 내로 용해하는 것이고, 두 번째는 낮은 활성으로 인한 높은 공기극의 분극이다. Ni이 전해질로 용해되는 문제는 Co나 Fe를 코팅하여 공기극 표면에 $Li_x(Ni_yCo_{1-y})1-xO_2$$Li_x(Ni_yFe_{1-y})_{1-x}O_2$를 형성시켜 NiO의 전해질 내로 용해되는 것을 억제하는 방법이나 ZnO, MgO, $La_2O_3$ 등의 산화물을 NiO 표면에 코팅하여 전해질과 접촉을 막는 방식으로 해결하는 등 많은 연구가 이루어져 왔다. 하지만 연료극의 비해 상당히 높은 공기극의 분극으로 인해 큰 전압손실이 일어나 용융탄산염 연료전지 성능이 낮아지는 문제의 경우 이를 해결하고자 하는 연구는 상대적으로 많이 진행되지 못한 상태이다. 특히 현재 용융탄산염 연료전지의 장기수명화를 위해 기존의 작동온도인 $650^{\circ}C$ 보다 다소 낮은 온도인 $600{\sim}620^{\circ}C$에서 작동하려는 움직임이 있다. 작동 온도가 내려가면 전해질이 휘발되는 속도가 낮아져 전해질 부족에 따른 운전시간이 줄어드는 문제를 해결할 수 있어 장기 수명화를 위해서는 작동온도를 낮추는 것이 매우 유리하다. 하지만 작동 온도가 내려가면서 양 전극에서 일어나는 전기화학 반응 속도가 느려지기 때문에 각 전극에서의 활성화 분극으로 인한 전압손실은 더욱 커질 수밖에 없다. 특히 연료극의 수소산화반응 속도는 공기극의 산소환원반응에 비해 매우 빠르기 때문에 작동 온도가 내려감에 따라 연료극의 분극이 커지는 것에 비해 공기극의 분극이 급격히 커지게 된다. 따라서 운전온도가 낮아지는 상황에서는 낮은 작동온도에서도 성능감소가 적게 일어나 0.8V 이상 운전(150mA/$cm^2$, 단위전지 기준)이 가능한 공기극의 개발이 매우 필요한 실정이다. 이를 해결하고자 본 연구에서는 고체 산화물 연료전지의 공기극의 재료로 많이 연구되고 있는 혼합전도성 물질의 페로브스카이트 구조의 물질을 기존 NiO 전극에 코팅하여 새로운 공기극을 개발하였다. 페로브스카이트 구조의 물질로 대표적인 LSCF 물질을 사용하였으며 LSCF를 코팅한 공기극을 이용한 단위전지에서 150mA/$cm^2$의 전류를 흘려주었을 때 0.84V의 성능을 1000hr 유지하였다. 이는 기존의 NiO 전극을 사용했을 때보다 15~20mV 높은 값이다. 낮은 작동온도에서도 좋은 성능을 보였는데, 기존의 NiO 전극의 경우 $630^{\circ}C$에서 0.79V의 성능을 보인 반면 LSCF가 코팅된 공기극의 경우 $620^{\circ}C$에서 0.811V의 매우 좋은 성능을 보였다. 이는 LSCF의 산소이온전도성 및 전기전도성이 공기극에서의 분극을 낮추어 성능을 증가시키는 것으로 보인다.

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Investigation of Water Channel Formation in Sufonated Polyimides Via Mesoscale Simulation (메조스케일 전산모사를 통한 술폰화 폴리이미드의 수화채널 형성 연구)

  • Park, Chi Hoon;Lee, So Young;Lee, Chang Hyun
    • Membrane Journal
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    • v.27 no.5
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    • pp.389-398
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    • 2017
  • The most important characteristic of the polymer electrolyte membranes (PEMs) for fuel cells, the proton conducting ability is mainly influenced by the distribution and morphology of the water channels inside the PEMs. Non-perfluorinated hydrocarbon PEMs are known to have weaker water channels than perfluorinated PEM, Nafion, and thus relatively low proton conducting ability. In this study, we used a mesoscale simulation technique to observe the water channel formation and phase separation behavior of hydrocarbon PEM, sulfonated polyimides, under the humidification condition. It was observed that the water molecules were distributed evenly through the entire hydrophilic region, and clear water clusters were formed only in the sulfonated polyimide having high sulfonation degree. In addition, it was observed that sulfonated polyimides have a difficulty in forming water channel under the low hydrated condition. These results clearly support the theories of the formation of water channels in non-perfluorinated hydrocarbon PEMs, and also well explain the tendency of proton conducting abilities of sulfonated polyimides. Thus, it is confirmed that mesoscale simulation techniques can be very effective in analyzing phase separation behavior and water channel formation in PEMs for fuel cells and elucidating the ion conducting abilities.

Proton Conducting Composite Membranes Consisting of PVC-g-PSSA Graft Copolymer and Heteropolyacid (PVC-g-PSSA가지형 공중합체와 헤테로폴리산을 이용한 수소이온 전도성 복합 전해질막)

  • Kim, Jong-Hak;Koh, Jong-Kwan;Choi, Jin-Kyu;Yeon, Seung-Hyeon;Ahn, Ik-Sung;Park, Jin-Won
    • Membrane Journal
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    • v.19 no.2
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    • pp.96-103
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    • 2009
  • A series of organic-inorganic composite membranes from poly(vinyl chloride) (PVC) graft copolymer electrolyte and heteropolyacid (HPA) were prepared for proton conducting membranes. First, poly(vinyl chloride)-g-poly(styrene sulfonic acid) (PVC-g-PSSA) was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. HPA nanoparticles were then incorporated into the PVC-g-PSSA graft copolymer though the hydrogen bonding interactions, as confirmed by FT-IR spectroscopy. The proton conductivity of the composite membranes increased from 0.049 to 0.068 S/cm at room temperature with HPA contents up to 0.3 weight traction of HPA, presumably due to both the intrinsic conductivity of HPA particles and the enhanced acidity of the sulfonic acid of the graft copolymer. The water uptake decreased from 130 to 84% with the increase of HPA contents up to 0.45 of HPA weight traction, resulting from the decrease in number of water absorption sites due to hydrogen bonding interaction between the HPA particles and the polymer matrix. Thermal gravimetric analysis (TGA) demonstrated the enhancement of thermal stabilities of the composite membranes with increasing concentration of HPA.

Corrosion Behavior of $Y_2O_3$ Coating in an Electrolytic Reduction Process (전해환원공정에서 $Y_2O_2$ 코팅층의 부식거동)

  • Cho, Soo-Haeng;Hong, Sun-Seok;Kang, Dae-Seung;Jeong, Myeong-Soo;Park, Byung-Heong;Hur, Jin-Mok;Lee, Han-Soo
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.8 no.1
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    • pp.33-39
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    • 2010
  • The electrolytic reduction of a spent oxide fuel involves a liberation of the oxygen in a molten LiCl electrolyte, which results in a chemically aggressive environment that is too corrosive for typical structural materials. Accordingly, it is essential to choose the optimum material for the processing equipment that handles the high molten salt. In this study, hot corrosion studies were performed on bare as well as coated superalloy specimens after exposure to lithium molten salt at $675^{\circ}C$ for 216 h under an oxidizing atmosphere. The IN713LC superalloy specimens were sprayed with an aluminized NiCrAlY bond coat and then with an $Y_2O_3$ top coat. The bare superalloy reveals an obvious weight loss due to spalling of the scale by the rapid scale growth and thermal stress. The chemical and thermal stability of the top coat has been found to be beneficial for increasing to the corrosion resistance of the structural materials for handling high temperature lithium molten salts.

Effect of process conditions on crystal structure of Al PEO coating. II. Bipolar and electrolyte (알루미늄 PEO 코팅의 결정상에 미치는 공정 조건에 대한 연구 II. Bipolar 펄스와 전해액)

  • Kim, Bae-Yeon;Ham, Jae-Ho;Lee, Deuk Yong;Kim, Yong-Nam;Jeon, Min-Seok;Kim, Kiyoon;Choi, Ji-Won;Kim, Sung Youp;Kim, Kwang Youp
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.24 no.2
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    • pp.65-69
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    • 2014
  • Crystallographic phases of Plasma electrolytic oxidized Al alloy, A1100, A5052, A6061, A6063, A7075, were investigated. Two types of electrolyte $Na_2Si_2O_3$ and Na2P2O7 were also compared. Bipolar pulse, $2000{\mu}sec$ with $400{\mu}sec+420V$ impulse and $300{\mu}sec$ - impulse were applied for 20 min. ${\alpha}-alumina$, ${\gamma}-alumina$, ${\eta}-alumina$, $Al_{4.95}Si_{1.05}O_{9.52}$, and $(Al_{0.9}Cr_{0.1})_2O_3$ were mainly observed. Si, component of electrolyte, were moved into the PEO layer by bipolar pulse. Glassy phase was also observed at the surface of $Na_2Si_2O_3$ electrolyte treated PEO layer, and increased with the Mg content of Al alloy. It is concluded that at first glassy phase was formed by the micro plasma, and the high temperature of plasma turns glassy phase to several crystalline phases. And we could expect that many other crystalline phase could be formed by PEO process.

Fabrication of Electrolyte for Direct Carbon Fuel Cell and Evaluation of Properties of Direct Carbon Fuel Cell (직접탄소 연료전지용 전해질 제조 및 직접탄소 연료전지 특성 평가)

  • Pi, Seuk-Hoon;Cho, Min-Je;Lee, Jong-Won;Lee, Seung-Bok;Lim, Tak-Hyoung;Park, Seok-Joo;Song, Rak-Hyun;Shin, Dong-Ryul
    • Korean Chemical Engineering Research
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    • v.49 no.6
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    • pp.786-789
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    • 2011
  • In order to estimate the possibility of applying electrolytes generally used in solid oxide fuel cells(SOFCs) to direct carbon fuel cells(DCFCs), properties of YSZ(yttria stabilized zirconia) electrolyte were evaluated. In this study, vacuum slurry coating method was adapted to coat thin layer on anode support substrate. After sintering the electrolyte at $1400^{\circ}C$ for 5hrs, microstructure was analyzed by using SEM image. Also, gas permeability and ionic conductivity were measured to find out the potential possibility of electrolyte for DCFCs. The YSZ electrolyte represented dense coating layer and low gas permeability value. The ionic conductivity of YSZ electrolyte was high over $800^{\circ}C$. After measurement of the electrolyte properties, direct carbon fuel cell was fabricated and its performance was measured at $800^{\circ}C$.

Charge-Discharge Characteristics of Lithium Metal Polymer Battery Adopting PVdF-HFP/(SiO2, TiO2) Polymer Electrolytes Prepared by Phase Inversion Technique (상반전 기법으로 제조한 PVdF-HFP/(SiO2, TiO2) 고분자 전해질을 채용한 리튬금속 고분자 2차전지의 충방전 특성)

  • Kim, Jin-Chul;Kim, Kwang-Man
    • Korean Chemical Engineering Research
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    • v.46 no.1
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    • pp.131-136
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    • 2008
  • Silica- or titania-filled poly (vinylidene fluoride-co-hexafluoropropylene)-based polymer electrolytes were prepared by phase inversion technique using N-methyl-2-pyrrolidone and dimethyl acetamide as solvent and water as non-solvent. The polymer electrolytes were adopted to the lithium metal polymer battery using high-capacity cathode $Li[Ni_{0.15}Co_{0.10}Li_{0.20}Mn_{0.55}]O_2$ and lithium metal anode. After the repeated charge-discharge test for the cell, it was proved that the cell adopting the polymer electrolyte based on the phase-inversion membrane containing 40~50 wt% silica showed the highest discharge capacity (180 mAh/g) until 80th cycle and then abrupt capacity fade was just followed. The capacity fade might be due to the deposition of lithium dendrite on the polymer electrolyte, in which the capacity retention was no longer sustainable.

Fabrication of Niobium Oxide Nanorods by the Anodization Method (양극산화법에 의한 니오븀 산화물 나노로드 제조)

  • Jung, Eun-Hye;Chang, Jeong-Ho;Jeong, Bong-Yong
    • Journal of the Korean Electrochemical Society
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    • v.14 no.4
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    • pp.196-200
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    • 2011
  • The formation of niobium oxide microcones on niobium substrates was investigated in NaF to the HF electrolytes. This condition builds on the uniqueness of the microstructures niobium oxide. The dimensions and integrity of the bulk microstructures were found to be strongly dependent on potential, temperature, electrolyte composition, and anodization time. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodization. From XRD patterns of the anodized specimens, the microcones consisted of crystalline $Nb_2O_5$. We demonstrated niobium oxide microcone structures with nanorods. The anodized niobium oxide microcone texture revealed nanorod bundles. The surface of $Nb_2O_5$ microcones is very regular and has a nano-scale. The surface morphologies of the nanorods were examined using FE-SEM. EDS analyses show that the anodically prepared niobium oxide consists of $Nb_2O_5$. The aim of this study is to find the condition of forming the favorable nanorods by anodization method.

Photoelectrochemical Water Splitting Using GaN (GaN를 이용한 광전기화학적 물분해)

  • Oh, Ilwhan
    • Journal of the Korean Electrochemical Society
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    • v.17 no.1
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    • pp.1-6
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    • 2014
  • This review article summarizes photoelectrochemical water splitting using gallium nitride (GaN). GaN materials have been studied as novel photoelectrode material due to its chemical stability and easy band gap engineering. Unlike other semiconductor materials that are easily corroded in strongly acidic or alkaline electrolyte, n-type GaN is chemically stable enough to be used as photoanode in oxygen evolution reaction. Furthermore, studies on p-type GaN have been recently reported. This review briefly discusses problems that need to be solved before GaN materials find widespread use in solar fuel application.

A Study on Heat Transfer Characteristics of Humidifier/HRU for MCFC (MCFC용 가습기 및 HRU의 열전달 특성 연구)

  • Park, Sungho;Kal, Hanjoo;Jeong, Youngsik;Lee, Sanghoon;Lee, Jaejun;Oh, Yongmin;Kim, Seonhwa
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.05a
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    • pp.97.2-97.2
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    • 2011
  • 본 연구는 연료전지 중 용융탄산염을 전해질로 하는 MCFC의 MBOP에 포함된 부품으로 매우 중요한 역할을 하는 가습기와 이때 발생되는 폐열을 회수하기 위한 장치인 HRU에 관한 것이다. 가습기는 연료와 물이 가습기 상부로 유입되어 가습기 하부로 유입되는 배가스와 열교환을 하면서 물이 스팀화 되어 연료가 가습된 상태로 가습기 출구로 일정온도를 유지하며 배출된다. 또한 HRU는 가습기에서 배출된 고온의 배가스를 물을 이용하여 열교환을 통해서 열을 회수하여 난방 및 온수로 사용할 수 있는 열교환 장치를 말한다. 먼저 이들의 특성을 파악하기 위해 가습기 및 HRU를 설계, 제작하여 각각의 특성을 확인하였다. 가습기와 HRU의 성능 향상을 위해 먼저 열교환부에 적용될 튜브의 수치해석적 분석을 통해서 최적의 열전달 성능을 얻을 수 있는 가습기 및 HRU를 설계, 제작하였으며 이들의 성능을 파악하기 위해 120,000kcal/h 용량을 테스트 할 수 있는 장치를 구축하여, 이들의 열전달 특성, 압력강하, 회수 열량, 가습기 온도 등의 특성을 파악하였다. 이 장치를 통해서 확인된 가습기와 HRU의 특성은 수치해석을 통해서 얻은 값과 거의 유사함을 확인할 수 있었으며, 가습 성능도 효과적으로 달성할 수 있었다. 가습기와 HRU의 특성 중 압력강하 부분은 지속적인 연구가 필요한 부분이며, 가습기와 HRU의 일체화를 통하여 소형화 및 설치공간 축소 효과를 얻을 것으로 본다.

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